Vapochromic Coordination Polymer Immobilization Techniques ...summit.sfu.ca/system/files/iritems1/19228/etd20197.pdf · a transformer’s insulating materials. Current methods of

Vapochromic Coordination Polymer Immobilization Techniques for Ammonia Sensors with Applications

to Power Transformers

by

David Stevens

BASc Simon Fraser University 2015

Thesis Submitted in Partial Fulfillment of the

Requirements for the Degree of

Master of Applied Sciences

in the

School of Engineering Science

Faculty of Applied Science

copy David Stevens 2019

SIMON FRASER UNIVERSITY

Spring 2019

Copyright in this work rests with the author Please ensure that any reproduction or re-use is done in accordance with the relevant national copyright legislation

ii

Approval

Name David Stevens Degree Master of Applied Science (Engineering Science) Title Vapochromic Coordination Polymer Immobilization

Techniques for Ammonia Sensors with Applications to Power Transformers

Examining Committee Chair Michael Sjoerdsma Senior Lecturer

Bonnie Gray Senior Supervisor Professor

Daniel Leznoff Supervisor Professor

Glenn Chapman Internal Examiner Professor

Date DefendedApproved April 16 2019

iii

Abstract

Ammonia detection is important for many applications in the biomedicine

agriculture and automotive industries Sensing of ammonia is also crucial in determining

the health of power transformers as the presence of ammonia indicates a breakdown in

a transformerrsquos insulating materials Current methods of gas analysis for detecting

ammonia in such applications are costly complicated and time consuming This thesis

is concerned with the use of vapochromic coordination polymers (VCPs) which are in

this case fluorescence-based gas sensitive polymers whose emission spectrum

changes upon the binding of target gases eg ammonia VCP materials have shown

great promise in ammonia detection due to their superior fluorescence response and

selectivity to ammonia but require immobilization to enable their use as a sensor

surface The work presented in this thesis examines several different immobilization

techniques for VCPs to create a new class of ammonia sensors

The first immobilization technique explored involves creating a sheet of post

arrays in polydimethylsiloxane (PDMS) to trap and adhere the VCPs to the sensing

surface We show that as the shape of the top of the post arrays is changed (eg from

simple post to mushroom-shaped caps) the sensitivity of the sensing surface changes

Ammonia detection in the amount of 5 ppm is possible with the most pronounced

mushroom shaped posts The second immobilization method involves dissolved

polylactic acid (PLA) mixed with VCPs that are deposited on a PLA substrate resulting

in nanoporous membranes (NPMs) that immobilize the VCP This technique results in

ammonia detection of 5 ppm based on available gas concentrations and reveals that a

mix ratio of PLA to VCP of 12 wt to 88 wt results in a sensor surface with the

highest degree of reversibility This second immobilization technique also makes a

sensor surface that is able to directly detect ammonia dissolved in fluids Because of the

ability of multi-phase gas detection with this immobilization technique we determine that

it is the more promising of the two immobilization methods We explore the application of

both immobilization methods in the creation of a sealed micro-fluidic ammonia sensor

Our prototypes use a 3D printed cyclic olefin copolymer (COC) micro-fluidic cell where

COC is employed due to its exceptional optical properties and chemical inertness These

sensor cells detect ammonia both in gas and dissolved in fluids (transformer oil) but are

limited in a detection of 1000 ppm using available gas concentrations for testing

iv

Keywords power transformers ammonia sensors vapochromic coordination

polymers chemical sensors

v

Acknowledgements

I would like to thank my supervisors Prof B L Gray and Prof D B Leznoff for

their support and freedom to they gave me to work I credit my success to their advice

and assistance throughout the work on this project

Thanks go out to David Yin Prof Glenn Chapman Michael Sjoerdsma all my

lab mates in the engineering and chemistry departments and friends

Without the support of my wife parents and family I would not be able to be

where I am today

vi

Table of Contents

Approval ii Abstractiii Acknowledgements v Table of Contents vi List of Tables viii List of Figures ix List of AbbreviationsGlossary xi

Chapter 1 Introduction 1 11 Overall Contributions of the Thesis 3

Chapter 2 Vapochromic Coordination Polymers 4 21 VCP Synthesis 4 22 Previous work immobilizing VCPs 6 23 Summary 7

Chapter 3 Post Arrays 8 31 Design considerations 8 32 Fabrication 8 33 Fabrication results 10 34 Experimental Methods for Ammonia Detection 13 35 Optical results 14 36 Discussion and summary 23

Chapter 4 Polylactic acid ndash Nanoporous membrane (PLA-NPM) 24 41 Fabrication of nanoporous membranes (NPMs) 24 42 Fabrication results 25 43 Experimental methods 27 44 Optical results 27 45 Discussion and summary 31

Chapter 5 3D printed ammonia sensor 32 51 Fabrication 32 52 Fabrication results 34 53 Experimental methods 36 54 Optical results 37 55 Discussion and summary 39

Chapter 6 Conclusions and Future work 41 61 Future work 44

611 Post Arrays 44 612 PLA-NPMs and 3D printed fluidic cells 44

References 46

vii

Appendix 49 Fluorescence spectrum data 49

viii

List of Tables

Table 1 Response comparison between un-immobilized and immobilized VCP NH3 drawn from headspace of 28 NH4OH bottle [18] Oacute 2017 IEEE Sensors 16

Table 2 Response comparison between simple post array and mushroom capped post arrays to NH3 drawn from headspace of 28 NH4OH bottle 19

Table 3 Response comparison between simple post array and mushroom capped post arrays to 1000 ppm NH3

21 Table 4 Response comparison between simple post array and mushroom capped post

arrays to 5 ppm NH3 22 Table 5 Pore count size and area of NPM 25 Table 6 Response comparison between PLA-NPM wt to NH3 drawn from headspace

of 28 NH4OH bottle 29 Table 7 Response comparison between PLA-NPM wt to 5 ppm NH3 30 Table 8 Response comparison between COC fluidic cells to NH3 drawn from headspace

of 28 NH4OH bottle 38 Table 9 Comparison of immobilization techniques N2 used as balance gas instead of

air 41

ix

List of Figures

Figure 1 SEM image of VCPs α-Zn[Au(CN)2]2 (left) and β- Zn[Au(CN)2]2 (right) polymorphs 5

Figure 2 SEM image of Zn[Pt(CN)4] VCP crystallites with mixed polymorphs 6 Figure 3 Thin film crystal of Zn[AuBr2(CN)2]2 on glass substrate 7 Figure 4 (a) A silicon wafer is coated with 5nm50 nm CrAu that is followed by spin

coating and baking of PMGI and AZ 9260 photoresist (b) The photoresist is exposed to the post array mask (c) Photoresist is developed and dried leaving undercut areas (d) Slygard 184 is mixed and poured into mold and cured (e) The cured siicone is demolded and inverted producing the post array This figure has been adapted from material presented in [15] 9

Figure 5 Simple post array without mushroom capped posts 11 Figure 6 Immobilized ball milled VCPs in simple post array without mushroom capped

posts 11 Figure 7 Mushroom capped post array ndash PMGI UV exposure dose of 200 mJcm2 12 Figure 8 Mushroom capped post array with immobilized VCPs - PMGI UV exposure

dose of 250 mJcm2 12 Figure 9 Experimental setup for optical fluorescence detection [D Yin thesis in

preparation] 13 Figure 10 Fluorescence response of un-immobilized VCP to NH3 drawn from headspace

of 28 NH4OH bottle [18] Oacute 2017 IEEE Sensors 15 Figure 11 Fluorescence response of VCP on PDMS simple post array to NH3 drawn

from headspace of 28 NH4OH bottle [18] Oacute 2017 IEEE Sensors 15 Figure 12 Fluorescence response of VCP on flat PDMS surface to NH3 drawn from

headspace of 28 NH4OH bottle 17 Figure 13 Fluorescence response of VCP on mushroom capped (200 mJcm2 UV dose)

PDMS post array to NH3drawn from headspace of 28 NH4OH bottle 18 Figure 14 Fluorescence response of VCP on mushroom capped (250 mJcm2 254 nm

UV dose) PDMS post array to NH3 drawn from headspace of 28 NH4OH bottle 18

Figure 15 Fluorescence response of VCP on mushroom capped (300 mJcm2 254 nm UV dose) PDMS post array to NH3drawn from headspace of 28 NH4OH bottle 19

Figure 16 Fluorescence response of VCP on mushroom capped (200 mJcm2 254 nm UV dose) PDMS post array to 1000 ppm NH3 20


Figure 18 Fluorescence response of VCP immobilized on simple post array to 5 ppm NH3 21


x

Figure 20 SEM image A) Porosity resulting from 12 wt PLA B) Porosity resulting from 48 wt PLA (with defect in middle) The white areas are the VCP crystallites immobilized by PLA-NPM (grey) 26

Figure 21 SEM image of VCP crystals (white) immobilized by PLA-NPM (grey) 26 Figure 22 Fluorescence response of immobilized VCP using 12 wt PLA-NPM to NH3

drawn from headspace of 28 NH4OH bottle 28 Figure 23 Fluorescence response of immobilized VCP using 48 wt PLA-NPM to

NH3drawn from headspace of 28 NH4OH bottle 28 Figure 24 Fluorescence response of immobilized VCP using 24 wt PLA-NPM to 5

ppm NH3 30 Figure 25 Fluorescence response of immobilized VCP using 50 wt PLA-NPM to 5

ppm NH3 31 Figure 26 Top (left) and bottom (right) views of 3D printed sensor cell 33 Figure 27 SEM image of PLA-VCP mixture in COC fluidic channels Left α-

Zn[Au(CN)2]2 Right β- Zn[Au(CN)2]2 which no longer exhibits the intended formation of NPM to immobilize the VCPs 34

Figure 28 SEM image of α-Zn[Au(CN)2]2 PLA-VCP Left PLA covering over VCPs Right PLA enveloping VCP crystals 35

Figure 29 SEM images of α-Zn[Au(CN)2]2 VCP immobilized by COC nanofibers (thin filaments linking hexagonal VCP crystals) 36

Figure 30 Fluorescence response of immobilized VCP (PLA-NPM) in COC fluidic cell to NH3 drawn from headspace of 28 NH4OH bottle Response is due to diffusion of NH3 through the fluidic cell 37

Figure 31 Fluorescence response of immobilized VCP (COC-NF) in COC fluidic cell to NH3 drawn from headspace of 28 NH4OH bottle Response is due to diffusion of NH3 through the fluidic cell 38

Figure 32 Response of samples exposed to silicone oil which ammonia was bubbled through for 1 hour Left 12 wt PLA-NPM Right COC-NF 39

Figure 33 COC fluidic cell with immobilized VCP fluorescing under 405 nm laser light 40 Figure 34 Emission spectra of PLA between 200 and 600 nm illuminated with UV-Vis-

NIR light source using 275-375 nm band pass color filter Captured from spectrometer (Flame Ocean Optics) 49

Figure 35 Fluorescence spectra of PLA between 400 and 600 nm Captured from spectrometer (Flame Ocean Optics) 49

Figure 36 Emission spectra of COC between 200 and 600 nm illuminated with UV-Vis-NIR light source using 275-375 nm band pass color filter Captured from spectrometer (Flame Ocean Optics) 50

Figure 37 Fluorescence spectra of COC between 400 and 600 nm Captured from spectrometer (Flame Ocean Optics) 50

Figure 38 Emission spectra of PDMS between 200 and 600 nm illuminated with UV-Vis-NIR light source using 275-375 nm band pass color filter Captured from spectrometer (Flame Ocean Optics) 51

Figure 39 Fluorescence spectra of PDMS between 400 and 600 nm Captured from spectrometer (Flame Ocean Optics) 51

xi

List of AbbreviationsGlossary

COC Cyclic olefin copolymer

COC-NF Cyclic olefin copolymer ndash nanofiber

C6H12 Cyclohexane

DCM Dichloromethane

DGA Differential Gas Analysis

GC Gas Chromatography

NH3 Ammonia

NPM Nanoporous Membrane

PDMS Polydimethylsiloxane

PLA Poly(lactic) Acid

PLA-NPM Poly(lactic) Acid ndash Nanoporous Membrane

PMGI Polymethylglutarimide

PPM Parts per million

THF Tetrahydrofuran

VCP Vapochromic Coordination Polymer

VOC Volatile Organic Compound

1

Chapter 1 Introduction

Power transformers are one of the single most expensive and critical

components of todayrsquos power systems Their failures cause significant losses and risks

in terms of power outages explosions fires and loss of life and property The early

detection of potential failures can mitigate these losses and risks The most common

method currently used to detect potential failures is through the use of gas

chromatography (GC) and diffused gas analysis (DGA) Transformer oil which acts as an

insulator is extracted by an operator from the power transformer for analysis in a

laboratory which may be a long distance from where the oil sample was taken from

DGA uses different methods (ie Doernenburg Ratio [1] and Duval Triangles [2]) to

determine what gasses are present in the power transformer oil GC on the other hand

separates volatile organic compounds (VOCs) based on their relative affinities for

different phases The type of gas and relative quantity in relation to others can indicate

the severity and type of fault that has occurred within the power transformer A key

breakdown gas of interest is ammonia Ammonia is a breakdown by-product that is

released from the insulation when certain faults such as arcing partial discharge and

overheating cause the insulation around the coils to breakdown

As an alternative to using GC or DGA for the detection of ammonia many new

types of gas sensors have been developed to address the need of detecting ammonia

for many different applications Such sensors can be generally divided into different

categories such as metal oxide [2 3] catalytic [4 5] conductive polymer [6 7 8] and

optical sensing [9 10] Metal oxide sensors for example are both inexpensive and

capable of detecting ammonia at levels of 1 ppm and below However both their lack of

selectivity and high operating temperatures make them unsuitable for ammonia

detection in a power transformer environment While there has been good progress on

the development of many of the other types of ammonia sensors they have generally

been targeted for applications whose operating condition and requirements are likewise

incompatible with the detection of ammonia inside power transformers Similar to DGA

and GC these sensors are primarily limited to gas analysis and cannot directly detect

dissolved gasses

2

In order to overcome these limitations sensors based on vapochromic

coordination polymers (VCPs) are under investigation because of their chemical and

thermal stability especially in the presence of water and specific selectivity to the target

gas(es) However while these sensors show promise in terms of ammonia detection

methods to immobilize VPCs on sensor surfaces has proven to be very challenging due

to their intrinsic chemical and thermal stability especially when the sensors intended

applications are also to detect ammonia that is dissolved in oil

The overall goal of this thesis is to develop robust simple and inexpensive

immobilization techniques in order to demonstrate a new class of optical based ammonia

sensors employing VCPs The immobilization techniques should result in sensors that

may be used in the field for detection of low concentrations of the level of 1 ppm for

applications including but potentially not limited to the monitoring of power transformer

health The VCP Zn[Au(CN)2]2 is a fluorescence-based gas sensitive polymer whose

emission spectrum changes upon the binding of ammonia Its physical and chemical

nature makes it very robust but also very difficult to immobilize due to the inability of the

VCPs to dissolve in solvents to allow them to make thin films or easily combined with

other materials Other researchers working on the project have attempted to brominate it

to make it into a thin film to give the VCP the required high surface area to volume ratios

required to be most effective This thesis instead proposes physical entrapment methods

that are simple repeatable and low cost to achieve the same requirement

The first immobilization method involves creating post arrays in

polydimethylsiloxane (PDMS) based on the concept of biomimetic dry adhesives [15]

The geometries and morphology of the post arrays provide a good environment for the

physical entrapment of the VCP crystals while ensuring that gas can freely move within

the post arrays and fully access the VCPs The second immobilization method involves

creating nanoporous membranes (NPMs) from polylactic acid (PLA) The gasfluid

breathable membranes that entrap the VCPs provide long-term physical immobilization

that allows for a sensing surface that can be used to detect ammonia in gasses as well

as ammonia dissolved in fluids Both immobilization methods are tested and contrasted

against un-immobilized VCP in bulk form through the use of the optical detection

methods developed by Yin et al [19] Lastly a 3D printed cyclic olefin copolymer (COC)

micro fluidic cell is made to test the immobilization methods for ammonia gas and as

dissolved in liquid

3

The organization of the thesis is as follows Chapter 2 introduces the background

of the class of VCPs discussed in this thesis Chapter 3 introduces the first

immobilization technique including design fabrication test setup and results Chapter 4

discusses the process of the second immobilization technique test setup and results

Chapter 5 introduces the 3D printed micro fluidic cell and explores the importance of the

VCP synthesis and morphology and its effects on immobilization Chapter 6 presents

comparative results of the work presented in this thesis conclusions and future work

11 Overall Contributions of the Thesis

This thesis makes the following contributions to the area of VCP immobilization

techniques

bull Development of mushroom capped post arrays for improved physical

immobilization of VCPs resulting in sensors that are capable of 5 ppm of

ammonia detection

bull Development of PLA based nanoporous membranes (NPMs) that provide long-

term physical immobilization good reversibility and multiphase ammonia

detection (eg ammonia as gas or ammonia dissolved in fluids) This technique

results in sensors that detect ammonia at 5 ppm concentrations

bull Development of first-generation new NPMs from COC resulting in the creation of

COC nanofibers (NFs) that immobilize particles

It is noted that initial work with post arrays was published and presented at the

IEEE Sensors 2017 conference [18] The other results remain as yet unpublished

4

Chapter 2 Vapochromic Coordination Polymers

Vapochromic coordination polymers (VCPs) are a class of compounds used as

the optical equivalent of electronic noses in the detection of volatile organic compounds

(VOCs) Vapochromic compounds are compounds with an emission spectrum or color

that shifts in the presence of a target VOC The VCPs under study in this thesis undergo

a fluorescence emission spectrum shift in the presence of ammonia (NH3) The VCPs

that we explore here are also reversible (ie when gas is released emission spectrum

returns to original state) which is a key requirement for sensors and the VCPs

reversibility is positively temperature dependent

VCPs are attractive for use in VOC sensing eg ammonia sensors because of

their potential for miniaturization selectivity to ammonia and chemical and thermal

stability Additionally VCPs are attractive due to the potential to directly detect ammonia

that is dissolved in fluids allowing greater versatility in the potential sensing

environments However a major drawback due to their robust chemical and thermal

stability makes them hard to immobilize due to the fact that they cannot readily be

dissolved in solvents and manipulated

21 VCP Synthesis

The main VCP that is used in the work presented in this thesis is Zn[Au(CN)2]2 of

which there are four polymorphs (α β γ δ) that can be formed from various methods of

synthesis However after complete or saturated exposure to ammonia and the

subsequent release of ammonia from the VCP crystals all polymorphs revert to the α

polymorph The polymorphs featured in this thesis are a and b because of the relative

ease of synthesis of these two polymorphs and the subsequent reversion to the α

polymorph These two polymorphs also represent the two main physical crystal structure

morphologies hexagonal and sheet shaped or a and b respectively The two

polymorphs α-Zn[Au(CN)2]2 and b-Zn[Au(CN)2]2 are synthesized using the processes

outlined by Katz et al [12] or Hoskins et al [13] Sample formulations for the synthesis of

both α and β polymorphs are shown in equations 1 and 2 The synthesized VCP

particles have sizes ranging from a few to tens of microns as observed in Figure 1

5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)

Additionally other VCPs of the composition of Zn[Pt(CN)4] and Cd[Au(CN)2]2 are

also experimented with as it is expected that their behavior in terms of immobilization

should be identical Figure 1 shows pictures of the crystallites of α-Zn[Au(CN)2]2 and β-

Zn[Au(CN)2]2 respectively which shows hexagonal and plate morphology shapes for

each respective polymorph Figure 2 shows the crystallites of Zn[Pt(CN)4] with mixed

polymorphs

Figure 1 SEM image of VCPs α-Zn[Au(CN)2]2 (left) and β- Zn[Au(CN)2]2 (right) polymorphs

6

Figure 2 SEM image of Zn[Pt(CN)4] VCP crystallites with mixed polymorphs

22 Previous work immobilizing VCPs

Other researchers work on immobilizing the Zn[Au(CN)2]2 VCP employed

brominating it to form the chemical composition of Zn[AuBr2(CN)2]2 and make it soluble

in ethanol This makes the polymer spin-coat-able on a substrate to improve its

functionality and stability However this process requires an extremely long time to

optically trigger the reductive elimination of the bromine through the use of a frequency

doubled NdYag laser to ensure that the base VCP is regenerated and is able to

fluoresce While continuous wave laser excitation sources of the wavelengths of 345 nm

and 390 nm for the α and β polymorphs respectively are preferential for optimal

excitation a 405 nm laser source is instead chosen because of its high power and

inexpensiveness over the lower wavelength sources

Attempts are made to thermally trigger the reduction of the bromine similar to the

method that was done by Ovens et al [14] However it is discovered through

experimentation that this results in the decomposition of the coordination polymer

7

instead of the intended reduction of bromine It is thought that this result is due to the

fact that the brominated Zn[AuBr2(CN)2]2 polymer is not a pyrazine-based system that

exhibited the hydrothermal reduction (eg bromine atoms are ejected from crystal lattice

when heated) [14] Figure 3 shows the thin film crystallization of brominated VCP on a

glass substrate

This previous work on immobilization does create a fluorescing sensor surface as

a thin film with a high surface area to volume ratio The major issue with this previous

immobilization work is that is difficult to reproduce with reliable characteristics and

requires expensive equipment that may not be readily available

Figure 3 Thin film crystal of Zn[AuBr2(CN)2]2 on glass substrate

23 Summary

We have discussed the basics behind VCPs and their appeal as use in the

development of ammonia sensors due to their intrinsic fluorescence nature chemical

and thermal stability and specific selectivity to ammonia gas However we have also

discussed that the only current method of immobilization while effective in gas

detection is also difficult and expensive to perform

The next chapters focus on outlining design considerations and fabrication

processes to immobilize the VCPs into sensor surfaces to address the limitations

presented in this chapter and the current immobilization technique

8

Chapter 3 Post Arrays

31 Design considerations

VCPs have optimal performance when a high surface area to volume ratio is

realized and is exposed to gases It is also of great consideration to pick immobilization

materials that will not absorb reflect or fluoresce at the wavelengths that we are trying

to detect at (eg 400 ndash 550 nm) and therefore any physical immobilization methods

require that these criteria be met as best as possible As stated in the previous chapter

existing immobilization methods are lacking For instance the only method that has

been attempted is through the chemical alteration by bromination and the subsequent

removal to create a thin film However that method is costly and time consuming and is

not practical for large scale production of sensors

The biomimetic dry adhesives fabricated in polydimethylsiloxane (PDMS)

demonstrated by Sameoto et al [15] are examined as an alternative to fulfil the criteria of

immobilization while potentially solving problems of gas access to the VCPs The post

arrays have both the physical geometries and morphologies that should support physical

entrapment of the VCP particles while allowing gas access PDMS also does not

optically interfere with the VCPs as determined by initial experimentation with flat PDMS

samples The initial design of post sizes and spacing is chosen because it is shown that

it would create a post array that is proven to be an effective biomimetic dry adhesive [15]

and it is thought that it would be able to accept the VCP crystals within the post array

VCP crystal synthesis results in grain sizes are in the range of a few to 10rsquos of microns

which can be further reduced through the means of hand grinding the crystals with a

mortar and pestle The size range of the VCPs are therefore of the sizes where the

physical entrapment by the posts may be expected to engage to immobilize the VCP

32 Fabrication

The initial design consists of an array of posts where it employs photolithography

and soft lithography [15] for fabricating 10 μm posts spaced 20 μm apart center to

center Figure 4 outlines the micro-fabrication process that is followed to produce the

post arrays presented in this thesis A silicon wafer is coated with 5 nm50 nm

9

ChromiumGold (CrAu) to form an adhesion layer for polymethylglutarimide (PMGI)

(supplied by MicroChem Corp Westborough MA) The PMGI layer is a deep UV

sensitive photoresist that allows for undercutting and is designed for lift-off procedures

PMGI SF 19 photoresist is mixed 11 by weight with PMGI T thinner (also from

MicroChem Corp) The PMGI is spun at 500 rpm for 10 seconds followed by 1000 rpm

for 30 seconds It is then soft baked at 100 degC for one minute and then hard baked at

180 degC for three minutes

Figure 4 (a) A silicon wafer is coated with 5nm50 nm CrAu that is followed by spin coating and baking of PMGI and AZ 9260 photoresist (b) The photoresist is exposed to the post array mask (c) Photoresist is

developed and dried leaving undercut areas (d) Slygard 184 is mixed and poured into mold and cured (e) The cured siicone is demolded and inverted producing the post array

Two different designs are considered simple and mushroom capped post arrays

For the fabrication of mushroom capped post arrays an inexpensive 254 nm UV light

source is used (Stratalinker 2400 from Stratagene) The wafer is then exposed to

varying doses between 200 and 300 mJcm2 to increase the development rate of the

PMGI layer which in turn increases the amount of undercutting and therefore increases

the mushroom cap diameter No exposure is done for the simple post arrays After the

wafer is cooled andor exposed to the 254 nm light source AZ 9260 is spin coated at

500 rpm for 10 seconds and then 1000 rpm for 30 seconds The wafer is then left to

relax for 5 minutes and then rehydrated in de-ionized (DI) water for 30 minutes and then

dried with N2 gas The wafer is then exposed to 3 minutes of i-line ultraviolet (365 nm

UV) light at a nominal power of 20 mWcm2 For the simple post arrays where there was

no 254 nm UV exposure of the PMGI the development of the wafer is finished by

immersing it in AZ 400K 14 for 6 minutes Next it is immersed it in MF-319 developer

10

for 15 minutes and dried with N2 gas Development times for the mushroom capped

post arrays are varied to compensate for the changes to the rates of development for the

PMGI

Slygard 184 is mixed in a 110 (precursorsilicon) ratio and degassed for 1 hour

It is spun on the wafer at 350 rpm for 30 seconds The coated wafer is then degassed for

1 hour After degassing the wafer is cured on a hotplate at 50 degC for 12 hours and then

hard baked to promote strengthening of the PDMS for another 30 minutes at 120 degC

After the curing process the PDMS layer is demolded by hand from the wafer The

PDMS layer is then imaged by a scanning electron microscope (SEM) to reveal the

resulting post array

The Zn[Au(CN)2]2 VCPs are thoroughly mixed with ethanol to form a uniform

suspension In order to ensure consistency all suspensions are formed using exactly the

same masses of VCP crystals to volumes of ethanol The suspension solutions are

drawn into a syringe and quickly drop cast onto the PDMS post arrays The ethanol is

evaporated at room temperature leaving the VCP immobilized within the post arrays

33 Fabrication results

Figure 5 shows an example of a fabricated simple post array imaged with a

scanning electron microscope (SEM) (Explorer FEIAspex) We see that the posts are

uniform and average around 124 μm in diameter and approximately 194 μm center to

center in spacing which is within 19 and 3 of the design specifications for the posts

and spacing The post heights are approximately 20 μm tall Due to the fact that the

Zn[Au(CN)2]2 VCP is drop cast onto the PDMS post array without any surface treatment

of the post array the VCP does not fully immobilize within the post array (between the

posts) as intended (Figure 6) However we see that the VCP is attached both on the

surface and in spaces between the posts of the array Surface treatments of the

fabricated post surfaces such as oxygen plasma to induce hydrophilicity before VCP

application may help it to penetrate between the posts Also if the distance between the

posts were greater for future experiments the VCP may integrate better The degree of

immobilization that is achieved between the different types of post arrays is not

measured post fabrication other than to note how readily VCPs are ejected via physical

11

manipulation The level of immobilization between the different post arrays is inferred by

the optical response results

Figure 5 Simple post array without mushroom capped posts

Figure 6 Immobilized ball milled VCPs in simple post array without mushroom capped posts

As a comparison Figure 7 shows an example of a fabricated mushroom capped

post array that received a 200 mJcm2 dose of 254 nm UV light We see again that the

posts are uniform (some post defects observed) with an average diameter of 145 microm

12

Figure 7 Mushroom capped post array ndash PMGI UV exposure dose of 200 mJcm2

In Figure 8 we observe that the average post size increases to 156 microm when

the UV dose is increased to 250 mJcm2 Figure 8 shows VCPs in their original

synthesized form whereas their form after ball milling as observed in Figure 6 While it

appears that there is more uniform coverage with the ball milled VCP crystals in the post

array it is accompanied with what is observed as an overall reduction of VCP in the

same post array area

Figure 8 Mushroom capped post array with immobilized VCPs - PMGI UV exposure dose of 250 mJcm2

13

34 Experimental Methods for Ammonia Detection

The VCPs are immobilized on the post arrays and a piece with the dimensions of

1 cm by 05 cm is cut from the post array and put inside a 35 mL cork-sealed quartz

cuvette as shown in Figure 9 A 30 mW 405 nm deep-violet continuous wave diode

laser is used to excite the sample and causes a base emission which peaks at

approximately 480 nm A small spectrometer (PhotonControl SPM-002) records the

digital spectrum which is further computer processed using Matlab The optical results of

ammonia exposure of the samples use two different methods of data analysis in Matlab

The first method involves wavelength and intensity shifts which are clearly discernable at

concentrations of 1000 ppm and greater However for concentrations 1000 ppm and

below a different method of data analysis is needed This method called Spectral Region

Subtraction (SRS) and was developed by Yin et al [19] By tracking the integrated

emission intensities of two spectral regions (unexposed and exposed) their subtracted

difference returns the detection signal

A syringe is used to remove the diffused ammonia gas from the headspace of a

28 Ammonium Hydroxide (NH4OH) solution bottle which is thought to result in a gas

concentration of approximately 50000 ppm depending on bottle contents and

temperature at the time of extraction Next 10 mL of this highly concentrated ammonia

gas is then pumped into the cuvette at a rate of approximately 1 mLs

Figure 9 Experimental setup for optical fluorescence detection [D Yin thesis in preparation]

14

The experiment is then repeated using un-immobilized VCP attached to a 1 cm

by 05 cm piece of double-sided tape to serve as a baseline comparison It is then also

repeated with VCP on a fully cured flat PDMS surface to show the loss of adhesion that

occurs over time under gas flow The experiment is repeated with VCP in simple and

mushroom capped post arrays for comparisons

Additional experiments are performed using calibrated gas tanks of ammonia

mixed with N2 as the balancing gas for the concentration of 1000 ppm Calibrated gas

tanks of ammonia mixed with lab air as the balancing gas are used to test at

concentrations of 50 ppm and 5 ppm Using the calibrated ammonia tanks the gas is

pumped into the sample cuvette at a rate of 194 mLs

35 Optical results

Optical testing to the exposure of headspace ammonia (NH3) shows that the

optical and fluorescence characteristics of the VCP is largely unaffected by the

immobilization technique and when we compare these results using the post-based

immobilization technique to the response of a sample of un-immobilized VCP in cuvette

little difference is observed Figure 10 shows the fluorescence response for the un-

immobilized VCP while Figure 11 shows the fluorescence response of VCP that is

immobilized on a simple PDMS post array The responses between the samples is very

similar but with the immobilized VCP taking approximately 90 seconds longer to reach

maximum intensity when exposed to ammonia It is thought that the slower response

time is due to increased diffusion time of the ammonia to the VCP within the post array

15

Figure 10 Fluorescence response of un-immobilized VCP to NH3 drawn from headspace of 28 NH4OH bottle [18] Oacute 2017 IEEE Sensors

Figure 11 Fluorescence response of VCP on PDMS simple post array to NH3 drawn from headspace of 28 NH4OH bottle [18] Oacute 2017 IEEE Sensors

Looking at Figure 10 and Figure 11 the initial (unexposed) material peaks at

465 nm in the un-immobilized condition and shows a broad emission By comparison in

the case with VCP immobilized on a post array the initial spectrum is more sharply

16

peaked at about 480 nm a shift of about 15 nm The optical response is defined as the

emission peak wavelength shift from its unexposed state as well as its change in

relative intensity The response time is defined as the time required for the peak intensity

to reach 90 of the maximum value Table 1 shows the comparison of the behavior

between the un-immobilized VCP and that immobilized in our post array From Figure 10

and Figure 11 and Table 1 it is seen that the post exposure spectral peak shift is

reduced by about 25 nm in the immobilized sample The relative intensity peak gain is

still large though reduced from 495 (un-immobilized) to 389 (immobilized) but that is

likely because the pre-exposure spectrum is more highly peaked but less spectrally

broad than that of the un-immobilized spectrum

Table 1 Response comparison between un-immobilized and immobilized VCP NH3 drawn from headspace of 28 NH4OH bottle [18] Oacute 2017 IEEE Sensors

Sample Peak wavelength shift (nm)

Relative intensity boost ()

Response time (sec) (90 of max)

Un-immobilized 478 4949 115

Immobilized 253 3896 70

The actual peak intensity of the exposed material is higher for the immobilized

case In using the VCP to quantitatively measure the ammonia our work has found that

the peak spectral shift is less useful than measuring the intensity of the spectrum at the

peak wavelength Additionally the spectral width and shape is more important in the

analysis of the optical response than the peak spectral shift at lower ammonia

concentrations where there will be little difference between the pre-exposure and full-

exposure peak wavelengths

The fluorescence response is shown as a function of time but that is just to

illustrate that the response is quick the actual interest is the fluorescence response in

steady-state equilibrium and not any time or concentration variations

17

Figure 12 Fluorescence response of VCP on flat PDMS surface to NH3 drawn from headspace of 28

NH4OH bottle

Figure 12 shows the results when a flat PDMS sample is used instead of a post

array We clearly observe that the fluorescence response decreases after 60 seconds

which may indicate that the gas movement dislodges the VCP from the surface over

time

Now when we compare the response between the immobilized VCP on a simple

post array and to that of the immobilized VCP on mushroom capped post arrays we

observe empirically that with increasing mushroom cap size which is due to increasing

the 254 nm UV dosage levels to the PMGI layer during fabrication the relative intensity

response increases and response time decreases as observed in Figure 13 Figure 14

and Figure 15

18

Figure 13 Fluorescence response of VCP on mushroom capped (200 mJcm2 UV dose) PDMS post array to NH3drawn from headspace of 28 NH4OH bottle

Figure 14 Fluorescence response of VCP on mushroom capped (250 mJcm2 254 nm UV dose) PDMS post array to NH3 drawn from headspace of 28 NH4OH bottle

19

Figure 15 Fluorescence response of VCP on mushroom capped (300 mJcm2 254 nm UV dose) PDMS post array to NH3drawn from headspace of 28 NH4OH bottle

Table 2 shows the comparison of the responses of the different mushroom

capped post array morphologies that are realized due to differing 254 nm UV dosages to

the PMGI layer during the fabrication process

Table 2 Response comparison between simple post array and mushroom capped post arrays to NH3 drawn from headspace of 28 NH4OH bottle

Sample Peak

wavelength shift (nm)


Response time (sec)

(90 of max)

Immobilized Simple post 253 3896 70

Immobilized Mushroom cap from 200 mJcm2 UV dose

373 4313 80


451 6896 68


438 9516 35

After initial testing of the responses of the different morphologies of post arrays

we then set about to investigate the response of the different morphologies exposed to

20

lowered concentrations of ammonia As viewed in Figure 16 and Figure 17 the intensity

profile and response has changed from the behavior observed previously for higher

concentrations in Figure 13 and Figure 14 The spectral peaks have broadened and the

response speed to ammonia has slowed but still exhibit increases in relative intensities

at full exposure as observed in Table 3

Figure 16 Fluorescence response of VCP on mushroom capped (200 mJcm2 254 nm UV dose) PDMS post array to 1000 ppm NH3


Also noted in Table 3 is the distinctly different wavelength shifts that are observed but is

only listed for comparison purposes as the spectral shape and intensity profiles are more

important than the wavelength shifts

21


Sample Peak



Response time (sec)

(90 of max)

Immobilized Simple post -074 10327 180


-371 1258 150

Immobilized Mushroom cap

250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78

Looking at the responses for 5 ppm concentrations the spectral width and shape is

more important in the analysis of the optical response than the peak spectral shift where

there is little difference between the pre-exposure and full-exposure peak wavelengths

as observed in Figure 18 and Figure 19

Figure 18 Fluorescence response of VCP immobilized on simple post array to 5 ppm NH3

22


The detection results as observed in Table 4 demonstrate similar behavior at 5 ppm to

what is seen at 1000 ppm concentrations with negative spectral shifts As expected the

relative intensity boosts are reduced




Immobilized Simple post -1169 10570


-279 10369


112 9476


056 9780

23

36 Discussion and summary

In summary the main result for this chapter shows that the post array

immobilization technique is robust to flow and enables detection of ammonia at 5 ppm

(which is the lowest concentration currently available for testing)

However we also find that progressing to 254 nm UV dosage levels (beyond 350

mJcm2) results in subsequent fabrication failure of the post arrays The fabrication

failures we observe are likely due to undercutting levels that remove too much

underlying resist to support further processing One possible way to ensure that the

resist layers remain during development after increased irradiation is to increase the

hard bake time and temperature provided to the PMGI layer Another method may be to

change the post spacing and geometries to allow for larger mushroom cap sizes to be

realized from undercutting Another issue encountered is the short time that the VCPs

remain in suspension before precipitating out of the solution Because of this it is difficult

to reproduce the drop casting procedure ensuring that the same quantities of VCP is

deposited Ball milling is proposed as a potential solution to this problem and also to

allow greater penetration of the drop casting solution within the post array However due

to the decrease in mass of VCP crystals the drop cast suspension spreads out into a

larger area and reduces the amount of VCP that remains in the sensing area given by

the spectrometerrsquos focal point resulting in less sensitive sensing surfaces

A final issue identified by this immobilization technique is that given the flexible

nature of the post array the VCPs are ejected from the post array upon physical

manipulation To properly identify the degree of immobilization that is achieved between

the different post array samples a more systematic approach needs to be taken by

measuring the weight difference of the post array after drop cast and physical

manipulation The resulting weight difference would provide the percentage of VCP

immobilization that is achieved for each post array sample

Given that this immobilization technique does not result in complete or long-term

immobilization this method does not appear to be a good way forward in the

immobilization of VCPs

24

Chapter 4 Polylactic acid ndash Nanoporous membrane (PLA-NPM)

In this chapter we develop a second physical immobilization method for VCPs

through the creation of polylactic acid based nanoporous membranes (PLA-NPM) to

physically trap the VCPs within the nanoporous membrane (NPM) layers

Polylactic acid (PLA) was chosen as an immobilization material in an attempt to

bring the fabrication process more in line with that of additive manufacturing or 3D

printing PLA is inexpensive and sustainable can maintain physical integrity in power

transformer environments and exhibits little fluorescence in the wavelengths of detection

as observed in Figure 34 and Figure 35 in the Appendix

Similar to the post array method a drop casting solution is used to deposit the

VCPs The procedure is identical with only a change of the solution composition

41 Fabrication of nanoporous membranes (NPMs)

The drop casting solution is prepared by dissolving polylactic acid (PLA) in a

solventnon-solvent co-solution of dichloromethane (DCM) and tetrahydrofuran (THF)

with a volume ratio of 41 The ratio of the solvent (DCM) to non-solvent (THF)

determines the overall porosity of the NPM due to the difference in evaporation rates

between DCM and THF The VCPs are mixed into the solution to form a uniform

suspension Weight ratios of PLA to VCPs of between 12 and 50 are explored The

formula below shows and example preparation to produce a 12 wt PLA-NPM

198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872

Once the solutions are thoroughly mixed and the VCPs are in uniform

suspension the solutions are drawn into a syringe and quickly drop cast onto a 3D

printed PLA substrate before the VCPs had time to settle out of suspension The

substrate is then suspended approximately 12 cm above a hot plate at a temperature of

100 ordmC to rapidly and uniformly evaporate the solvent co-solution creating NPMs that

immobilize the VCPs

25


The drop cast VCP and PLA-NPM is observed with an SEM (FEI Aspex

explorer) and ImageJ software (nihgov) is used to measure the average pore size and

porosity of each sample of PLA-NPM The porosity of the NPM is calculated using

equation

119875119900119903119900119904119894119905119910() = (sum119875119900119903119890 a5b 119860119903119890119886frasl ) lowast 100 (3)

Figure 20 shows the resultant morphology of the VCP PLA-NPMs using both A)

12 wt and B) 48 wt PLA to VCP Since porosity is predominantly determined by the

solvent to non-solvent ratio of the DCM and THF which in our case was set to 41 the

average porosity of all samples was measured to be approximately 50 as shown in

Table 5 From Figure 20 we can observe that the micronano-pores are uniformly

distributed over the entire membrane surface and from Figure 21 we can clearly see that

that VCP content has little impact on the pore formation or distribution

Table 5 Pore count size and area of NPM

Sample of pores Average size of pores (microm)

Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26

Figure 20 SEM image A) Porosity resulting from 12 wt PLA B) Porosity resulting from 48 wt PLA (with defect in middle) The white areas are the VCP crystallites immobilized by PLA-NPM (grey)

Figure 21 SEM image of VCP crystals (white) immobilized by PLA-NPM (grey)

27

43 Experimental methods

Similar to the experimental method for the post arrays Samples of VCP

immobilized by PLA-NPMs on a PLA substrate are inserted inside a 35 mL cork-sealed

quartz cuvette A 30 mW 405 nm deep-violet continuous wave diode laser is used to

excite the material and causes a base emission which peaks at approximately 490 nm

A small spectrometer (PhotonControl SPM-002) records the digital spectrum which is

further computer processed using Matlab Similarly to the first immobilization method

the optical results are analyzed via the data analysis methods developed by Yin et al

[19] A syringe is used to remove the diffused ammonia gas from the headspace of a

28 Ammonium Hydroxide (NH4OH) solution bottle Next 10 mL of this highly

concentrated ammonia gas is then pumped into the cuvette at a rate of approximately 1

mLsec

The experiment is repeated using calibrated gas tanks of ammonia mixed with N2

as the balancing gas for the concentration of 1000 ppm Whereas calibrated gas tanks of

ammonia mixed with lab air as the balancing gas is used to test at concentrations of 50

ppm and 5 ppm Using the calibrated ammonia tanks the gas is pumped into the sample

cuvette at a rate of 194 mLs

44 Optical results


optical and fluorescence characteristics of the VCP is largely unaffected by the PLA-

NPM immobilization technique Figure 22 shows the fluorescence response for a sample

of VCP using 12 wt PLA-NPM while Figure 23 shows the fluorescence response of

VCP using a 48 wt PLA-NPM The NPM immobilization method immobilizes sufficient

amounts of VCPs to cause the sensor cell response to start to saturate as observed in

Figure 23 as compared to the post-based immobilization method To alleviate this issue

the spectrometer exposure rate is reduced but intensity responses cannot be compared

directly due to differences in scaling

28

Figure 22 Fluorescence response of immobilized VCP using 12 wt PLA-NPM to NH3 drawn from headspace of 28 NH4OH bottle

Figure 23 Fluorescence response of immobilized VCP using 48 wt PLA-NPM to NH3drawn from headspace of 28 NH4OH bottle

29

Table 6 Response comparison between PLA-NPM wt to NH3 drawn from headspace of 28 NH4OH bottle


Relative intensity boost

()

Response time (sec)

(90 of max)

12 wt PLA-NPM (not on substrate) 556 6372 180

12 wt PLA-NPM (on PLA substrate) 245 2477 267





As shown in Table 6 there is a general increase of response as the percentage of PLA

is increased for samples on a PLA substrate while the largest increase is from a sample

that is not on substrate which is a free floating piece of PLA-NPM with immobilized

VCP The trend of increasing response may be due to the increased amount of PLA

material to retain more the VCP within the NPMs in the sensor area However once the

percentage of PLA exceeds 24 the sensor becomes very difficult to reverse to its

original state as the ammonia molecules may become trapped within the membranes

We again look at the level of ammonia detection for this immobilization technique and

found that it is also able to detect to 5 ppm as shown in Table 7 Again the spectral

width and shape is more important in the analysis of the optical response than the peak

spectral shift at 5 ppm ammonia concentrations where there is little difference between

the pre-exposure and full-exposure peak wavelengths as observed in Figure 24 and

Figure 25

30

Table 7 Response comparison between PLA-NPM wt to 5 ppm NH3



Response time (sec)

(90 of max)


12 wt PLA-NPM - P1 (on PLA substrate) -389 10536 NA

24 wt PLA-NPM (on PLA substrate) 148 956 NA


Figure 24 Fluorescence response of immobilized VCP using 24 wt PLA-NPM to 5 ppm NH3

31



As with the post arrays the PLA-NPM immobilization technique is dependent on

the amount of VCPs that are immobilized within the narrow focal point of the

spectrometer sensing area It is also discovered through experimentation that the

experimental setup has a degree of manipulation to it to allow for varying degrees of

response for any sample This is a major drawback discovered with this experimental

setup Since the quality of the response highly dependent upon the amount of sample

that is able to be present in focal pathway of the spectrometer and the degree of focus

that can be achieved Every effort is made to fix the optical setup so that every sample is

measured with the same conditions and without altering the optical setup between

samples However it is discovered that the optical setup may be optimized for each

sample

In terms of use as a sensor it is found that 12 wt to 88 wt is the weight ratio

of PLA to VCP to provide ammonia detection of 5 ppm long-term immobilization and

greatest degree of reversibility allowing sensors employing this immobilization technique

to be repeatedly reused

32

Chapter 5 3D printed ammonia sensor

In this chapter we look at the first fully fluidic prototype ammonia sensor

application that is created for the detection of ammonia using PLA-NPMs and cyclic

olefin copolymer based nanofibers (hereby known as COC-NFs) to immobilize the

VCPs We discuss the fabrication of the prototypes via 3D printing of the sensor cell and

their characterization along with the optical test method and results

51 Fabrication

In addition to the technique presented in Chapter 4 PLA is also commonly

employed in 3D printing [26] However COC is chosen instead as the 3D printing

material for the fluidic sensor cells presented in this chapter for several reasons Firstly

while transparent PLA stock is available it is found that after printing the transparency of

PLA turns fairly opaque to light transmission in the desired wavelengths and requires the

creation of a fluidic cell that is comprised of both PLA and a glass transmission window

for optical detection However printed COC maintains near perfect optical transmission

in the required wavelength region and does not absorb or fluoresce in that region as

observed in Figure 36 and Figure 37 in the Appendix Secondly COC can maintain its

integrity without deformation in higher temperatures than PLA and can be printed as one

sealed device

Prototype designs of the fluidic cell are created in Solidworks and Autocad and

then imported to the 3D COC printer software Fluid Factory (Dolomite Fluid Factory)

which creates the layers to be printed Figure 26 illustrates the CAD drawing

representations of the top views of the top layer on the left and the bottom layer with a

microfluidic layer The size of the prototype fluidic sensor is chosen to match the size and

allowable geometries that are present with the optical setup and therefore dictated the

overall size of the cell The fluidic layer depth is set to the minimum depth possible by

the 3D printerrsquos capabilities Therefore the prototypes use a microfluidic layer that is 300 microm

in depth with the entire cell measuring 18x7x60 mm (WxHxL) The majority of the height

is attributed to the inlet and outlet ports This is because a sufficient port length is

required for the attachment of tubing that is able to resist backflow and attach with

minimal amounts of adhesive and while maintaining its physical attachment strength

33

Figure 26 Top (left) and bottom (right) views of 3D printed sensor cell

The drop casting solutions for the PLA-NPMs are prepared exactly according to

the procedures outlined in Chapter 4 The drop casting solution is prepared by dissolving

polylactic acid (PLA) in a solventnon-solvent co-solution of dichloromethane (DCM) and

tetrahydrofuran (THF) with a volume ratio of 41 The VCPs are mixed into the solution

to form a uniform suspension

As a method of more closely integrating the VCP solution with the base COC

substrate new solutions are investigated While there has been research into forming

porous COC membranes [22 23] these methods of creating membranes are not

compatible with this method of immobilization We instead follow a similar technique as

used for the creation of PLA-NPMs through a combination of solvents and non-solvents

to dissolve the COC into solution Through experimentation a suitable solventnon-

solvent combination is found in the form of cyclohexane and benzaldehyde in a ratio of

61 by volume While many other less non-polar non-solvents are experimented with to

act as the non-solvent only benzaldehyde is able to be mixed with the cyclohexane and

COC without causing the immediate re-solidification of the COC out of the solution The

VCPs are mixed into the solution to form a uniform suspension


suspension the solutions are drawn into a syringe and quickly drop cast into the fluidic

channel of a 3D printed COC substrate before the VCPs had time to settle out of

suspension The substrate is then suspended approximately 12 cm above a hot plate at

a temperature of 100 ordmC to rapidly and uniformly evaporate the solvent co-solution

creating NPMs that immobilize the VCPs

Two methods are employed to create the 3D printed COC fluidic cells The first

method involves printing the bottom fluidic layer and top inletoutlet layers separately

and the PLA-VCP or the COC-VCP solution is drop cast into the fluidic layer After the

evaporation of the solvent co-solution the two layers are bonded together employing the

technique discussed by Keller et al [20] where a mixture of cyclohexane and acetone is

used to make the bonding sides of each layer tacky enough to bond them together The

34

second method is to print the bottom fluidic layer and then pause the printing The PLA-

VCP or COC-VCP solution is drop cast into the fluidic layer and then after the

evaporation of the solvent and non-solvents the top layer is immediately printed overtop

creating a completely sealed fluidic chamber


While initially it is assumed that the PLA-VCP drop cast solution would form the

intended PLA-NPMs as observed in Figure 20 and Figure 21 it turned out that instead

the PLA acted more as a glue to adhere the VCPs to the surface of the COC fluidic cell

instead and did not form the PLA-NPM as observed in Figure 27 The most noticeable

visual difference is that the VCPs are no longer trapped beneath gas porous NPMs but

stuck on and in between PLA This change suggests a reduction of gas access to the

VCP crystal surfaces

At the time of this writing it is unclear the reason behind the failure to form the

intended PLA-NPM but could be due to any number of unintended chemical interactions

between the aqueous suspension and the COC surface or the failure of having a PLA

substrate to help form the proper bonds to facilitate the formation of the NPM during the

solventnon-solvent evaporation

Figure 27 SEM image of PLA-VCP mixture in COC fluidic channels Left α-Zn[Au(CN)2]2 Right β- Zn[Au(CN)2]2 which no longer exhibits the intended formation of NPM to immobilize the VCPs

35

It is further discovered that when attempting to drop cast using solutions that

contain the α- Zn[Au(CN)2]2 polymorph with hexagonal crystals two unintended

situations may occur When drop cast the resulting distribution of the VCPs is denser

and more uniform However what negated any positive effects is that the PLA often

overly interferes or envelops the crystals and thereby reduces the available binding sites

for ammonia This results in poor or non-reactive sensors as observed from Figure 28

Figure 28 SEM image of α-Zn[Au(CN)2]2 PLA-VCP Left PLA covering over VCPs Right PLA enveloping VCP crystals

When the solution of α- Zn[Au(CN)2]2 polymorph and COC is drop cast we

surprisingly find that it the VCP is not immobilized by an NPM but instead by nanofibers

(NF) as observed in Figure 29 The NFs ranged in size up to 500 nm in width and of

varying lengths bonding crystals together large pieces of COC and the COC substrate

36

Figure 29 SEM images of α-Zn[Au(CN)2]2 VCP immobilized by COC nanofibers (thin filaments linking hexagonal VCP crystals)


Similar to the experimental method for the post arrays and PLA-NPMs the

samples of Zn[Au(CN)2]2 VCP are immobilized by COC-NFs and the PLA-NPMs in the

fluidic channel The 3D printed COC cell is used as the replacement to the cuvette A 30

mW 405 nm deep-violet continuous wave diode laser is used to excite the material and

causes a base emission which peaks at approximately 480 nm A small spectrometer

(PhotonControl SPM-002) records the digital spectrum which is further computer

processed using Matlab Similarly to the other immobilization methods the optical

results are analyzed via the data analysis methods developed by Yin et al [19] A

syringe is used to remove the diffused ammonia gas from the headspace of a 28

Ammonium Hydroxide (NH4OH) solution bottle Next 10 mL of this highly concentrated

ammonia gas is then pumped into the cuvette at a rate of approximately 1 mLsec



ammonia mixed with lab air as the balancing gas is used to test at concentration of 5

ppm Using the calibrated ammonia tanks the gas is pumped into the sample cuvette at

a rate of 194 mLs

37

A second experimental setup is made for testing of ammonia dissolved in silicone

oil The setup used is the same as the previous experimental setup however with the

change that the oil is drawn out of an oil reserve using a micro fluidic pump at a rate of

10 mLmin into the fluidic cell Once the cell is filled the oil is held there for the duration

of the experiment

54 Optical results


optical and fluorescence characteristics of the VCP is largely unaffected immobilization

in our sensor design prototypes However one obvious change in response is the large

increase of response time as observed in Figure 30 and Figure 31 Previous

immobilizations had VCP response times in the seconds to minutes whereas the VCP

responses in the fluidic cells take upwards of an hour or longer to achieve the same

levels of exposure

Figure 30 Fluorescence response of immobilized VCP (PLA-NPM) in COC fluidic cell to NH3 drawn from headspace of 28 NH4OH bottle Response is due to diffusion of NH3 through the fluidic cell

38

Figure 31 Fluorescence response of immobilized VCP (COC-NF) in COC fluidic cell to NH3 drawn from headspace of 28 NH4OH bottle Response is due to diffusion of NH3 through the fluidic cell

Table 8 Response comparison between COC fluidic cells to NH3 drawn from headspace of 28 NH4OH bottle



Response time (90 of max)

COC PLA-NPM β polymorph 217 5983 40 minutes

COC-NF α polymorph 199 2278 258 minutes

Finally we look at the results that we achieve from exposing the fluidic cell to

ammonia saturated silicone oil The results presented are from the technique that was

developed by Yin et al [19] and can be observed in Figure 32 This second technique is

required for the detection of low concentrations of ammonia and what is used for the

detection for not only the oil-based experiments but also throughout this thesis for the

detection of the 5 ppm gas concentrations The change of detection method is required

as at these low gas concentrations as the spectral shifts and relative intensities are too

small to be determined visually From Figure 32 we observe that once the oil is drawn

into the sensing chamber the response rises quickly and comes to a steady state within

a few minutes

39

Figure 32 Response of samples exposed to silicone oil which ammonia was bubbled through for 1 hour Left 12 wt PLA-NPM Right COC-NF


The resulting microfluidic sensor cell and processes outlined in this chapter show the

successful immobilization of the VCP as well as detection of ammonia in both gas

phase and dissolved into a fluid Examination of VCP morphology reveals its role in the

effectiveness of different immobilization techniques

Using the immobilization technique employing PLA-NPMs results in most sample

cells being less responsive to similar levels of ammonia exposure as to PLA-NPMs on

PLA substrates There is also a noticeable drop in sensitivity for the COC-NFs from the

PLA-NPMs in our prototype sensor cells From our discoveries on how the PLA-VCP

suspension behaved when drop cast into the COC fluidic cell we see that this result

should not be unexpected and points to the important characteristics of the physical

morphology that comes into play for immobilization in COC fluidic cells

When we look at the SEM images of the resulting immobilization of both the a

and b polymorphs using the PLA-VCP solution we see marked differences as observed

in Figure 27 This may help to explain why when we use the b polymorph we have a

reduction in sensitivity as the crystals are now clumped together and no longer held

within NPMs Figure 28 shows how when using the a polymorph the PLA seems to

prefer to envelope the VCP crystals causing the resulting sensor to be non-sensing

40

Therefore using PLA-VCP drop cast solution with the a polymorph in a COC based cell

is determined to be not an effective or useful immobilization technique

When we look at the immobilization of the VCP when using a COC based

suspension using the a polymorph we find resulting immobilization to involve the

nanofibers as observed in Figure 29 We did not have a chance to observe the resulting

immobilization from the b polymorph as we did not have access to the b polymorph at

the time to compare

It is observed that the size or width of the fluidic channel resulted in the printer

creating the fluidic layer as more of a mixer than a straight flowing channel when printing

the entire chip in a single print job as observed in Figure 33 While this is avoided when

printing the top and bottom layers separately the binding of the layers proved

challenging to maintain a fluid tight seal and without clogging the fluidic layer

Figure 33 COC fluidic cell with immobilized VCP fluorescing under 405 nm laser light

It is shown that these fluidic cells are able to detect ammonia that has been

dissolved in silicone oil similar to that what is found inside power transformers Being

able to detect ammonia in the liquid phase extends the capabilities of this type of

ammonia sensor and shows that the presented immobilization technique can unlike

many other sensors based on previously existing techniques measure ammonia in liquid

phase (eg oil)

41

Chapter 6 Conclusions and Future work

Table 9 Comparison of immobilization techniques N2 used as balance gas instead of air

Technique Customization Concentration

50000 ppm

1000 ppm 50 ppm 5 ppm

Post array Simple Clear positive

response

Weak positive

responseinconclusive

No data Weak positive

responseinconclusive response Mushroom

200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response


response PLA-NPM 12 wt

(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response

12 wt ndash P1 (88 VCP)

Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response



COC-NF COC PLA-NPM β polymorph

Clear positive

response

Clear positive

response

No data Negative response

COC-NF α polymorph

Clear positive

response

Clear positive

response


42

Table 9 shows a summary of the different immobilization techniques that are

presented in this thesis showing the levels of response in the detection of ammonia at

given concentrations in air The exception is for the results for 1000 ppm in which the

balancing gas used during testing was N2 instead of air

We see from Table 9 that both the higher 254 nm UV dose post arrays and the

higher VCP percentage PLA-NPM immobilization techniques result in a sensing surface

that is able detect relatively low concentration levels of 5 ppm However the simple post

arrays low VCP percentage PLA-NPM and COC cell result in a sensing surface that

has experimentally been shown to only detect ammonia concentration levels of 1000

ppm The determination of the results for the lower concentration levels below 1000

ppm are complied through the comparison of data obtained through both methods of

data analysis While some samples may show weak positive responses to lower

concentrations from one data analysis method there either is insufficient data points or

conflicts between the two methods to prove the results to be conclusive

While it was sought to experiment equally with both the a and b polymorphs of

the VCP the b polymorph was the only polymorph that was used throughout all

immobilization techniques It is only the COC cells in which both the a and b polymorphs

are used It is also for these cells where it is discovered that the polymorph morphology

became an important consideration With the creation of these fluidic cells we have also

been able to show that the sensor cells are able to detect ammonia that is dissolved in

silicone oil which is promising for use of the sensor in detecting ammonia in both gas

and liquid samples

It is of great consideration to pick immobilization materials that do not absorb

reflect or fluoresce at the wavelengths of issue However it is determined that all

immobilization materials did in fact slightly interfere with the resulting spectral response

For example the un-immobilized base material has an emission peak at 480 nm

However once immobilized the base emission peak shift up to approximately 490 nm for

the post arrays and the PLA-NPMs While it is not the focus of this thesis to look at the

optical detection scheme and data analysis algorithms through experimentation it is

found that the data analysis algorithm can be tuned or manipulated to change the type of

response that is found With every immobilization method the unexposed and exposed

43

spectral peaks shifted wavelengths from what is observed in the un-immobilized

samples

In conclusion in this thesis we show development of several immobilization

techniques for VCPs aimed at improving the sensitivity reducing the cost of fabrication

and allowing the sensors surface to be able to detect ammonia in fluid flow We have

shown that through the micromachining of PDMS we are able to create post arrays with

mushroom capped tops that are able to effectively immobilize VCPs within the post array

as well as detect ammonia at low concentrations of 5 ppm which is close to the required

lower detection limit of 1 ppm The major drawback to the post-based immobilization

method is that through physical manipulation of the post array sensing surface VCPs

are lost thereby reducing the sensing surfacersquos sensitivity over time This also highlights

that the post-based immobilization technique can only be used for sensing ammonia as

a gas as any liquid may slowly remove the VCPs from the surface We have shown that

we are able to immobilize VCPs within PLA-NPMs resulting in a sensor surface that

provides for the long-term immobilization of the VCPs Using this technique surfaces are

also able to detect ammonia that has been dissolved in fluids and that can detect

ammonia at low concentrations of 5ppm which is close to the required detection limit of

1 ppm In addition we have shown through the combination of solutions consisting of

PLA-VCP and COC-VCP we are able to immobilize VCPs into the 3D printed fluidic

COC cell that can be used in the detection of ammonia as both a gas and dissolved in

fluid

While all immobilization techniques show degrees of promise we conclude that

the most promising of all the techniques is the PLA-NPM immobilization technique The

PLA-NPM immobilization technique demonstrates long-term immobilization the ability to

directly detect ammonia dissolved in oil and the ability to detect low levels of ammonia

in the concentration amount of 5 ppm This immobilization technique should be the focus

of all future work for the immobilization of VCPs for use in gas sensors

44

61 Future work

The work presented in this thesis show the development of several novel

methods for the immobilization of VCPs However some key issues need to be

addressed by future work

611 Post Arrays

bull Investigate different methods of surface activation to promote increased

VCP bonding to the surface

bull Investigate new solvents to form better VCP suspensions

bull Improve process methodologies to realize a greater control and

reproducibility of the amount of VCPs deposited and into a controlled and

confined sensor area

bull Test the effectiveness of immobilization technique with the a polymorph

of VCP

bull Develop metric (ie weight difference) to determine degree of

immobilization of VCPs for different post arrays based on the amount of

VCPs that are ejected from post arrays after drop casting

612 PLA-NPMs and 3D printed fluidic cells




bull Improve optical setup so that no manipulation is required between

samples and standardizing 3D printing process so that sensor area is

defined in correlation to optical detection area on chip

bull Modify fluidic layer to improve flow conditions around or over sensing

VCP-NPMsNFs

45

bull Continue investigation of VCP physical morphology and its role in

immobilization and formation of NPMs and NFs

bull Test the effectiveness of immobilization on PLA substrate using PLA-

NPMs with the a polymorph of VCP

bull Further test the effectiveness of immobilization for COC cells using the b

polymorph of VCP

46

References

[1] E Dornenburg W Strittma Monitoring oil-cooled transformers by gas-analysis Brown Boveri Rev 1974 Vol 61 No 5 pp 238-247

[2] M Duval A Review of faults detectable by gas-in-oil analysis in transformers IEEE Elect Insul Mag 2002 Vol 18 No 3 pp 8-17

[3] K Zakrzewska ldquoMixed oxides as gas sensorsrdquo Thin Solid Films 2001 Vol 391 Issue 2 pp 229-338

[4] R Binions A J T Naik ldquoMetal oxide semiconductor gas sensors in environmental monitoringrdquo Semiconductor Gas Sensors Woodhead Publishing Series in Electronic and Optical Materials 2013 pp 433-466 httpsdoiorg10153397808570986654433

[5] C Wang X Li F Xia H Zhang J Xiao ldquoEffect of V2O5-content on electrode catalytic layer morphology and mixed potential ammonia sensor performancerdquo Sensors and Actuators B Chemical 2016 Vol 223 pp 653-668 httpsdoiorg101016jsnb201509145

[6] A Marikutsa A Sukhanova M Rumyantseva A Gaskov ldquoAcidic and catalytic co-functionalization for tuning the sensitivity of sulfated tin oxide modified by ruthenium oxide to ammonia gasrdquo Sensors and Actuators B Chemical 2018 Vol 255 Part 3 pp 3523-3532 httpsdoiorg101016jsnb201709186

[7] L Huixia L Yong L Lanlan T Yanni Z Qing L Kun ldquoDevelopment of ammonia sensors by using conductive polymerhydroxyapatite composite materialsrdquo Materials Science and Engineering C 2016 Vol 59 pp 438-444 httpsdoiorg101016jmsec201510036

[8] S Sharma S Hussain S Singh SS Islam ldquoMWCNT-conducting polymer composite based ammonia gas sensors A new approach for complete recovery processrdquo Sensors and Actuators B Chemical 2015 Vol 194 pp 213-219 httpsdoiorg101016jsnb201312050

[9] L Kumar I Rawal A Kaur S Annapoorni ldquoFlexible room temperature ammonia sensor based on polyanilinerdquo Sensor and Actuators B Chemical 2017 Vol 240 pp 408-416 httpsdoiorg101016jsnb201608173

[10] Y Cheng Q Feng M Yin C Weng Y Zhou ldquoA fluorescence and colorimetric ammonia sensor based on a Cu(II)-27-bis(1-imidazole)fluorene metal-organic gelrdquo Tetrahedron Letters 2016 Vol 57 Issue 34 pp 3814-3818 httpsdoiorg101016jtetlet201607013

[11] F Tavoli N Alizadeh ldquoOptical ammonia gas sensor based on nanostructure dye-doped polypyrrolerdquo Sensors and Actuators B Chemical 2013 Vol 176 pp 761-767 httpsdoiorg101016jsnb201209013

47

[12] M J Katz T Ramnial H Yu D B Leznoff ldquoPolymorphism of Zn[Au(CN)2]2 and Its Luminescent Sensory Response to NH3 Vaporrdquo JACS articles 2008

[13] B F Hoskins R Robson N V Y Scarlett ldquoSix Interpenetrating Quartz-Like Nets in the Structure of ZnAu2(CN)4rdquo Angewandte Chemie International Edition in English 1995 Vol 34(11) pp 1203-1204

[14] J S Ovens D B Leznoff ldquoThermally triggered elimination of bromine from Au(III) as a path to Au(I)-based coordination polymersrdquo Dalton Transactions 2011 40 4140

[15] D Sameoto and C Menon ldquoA low-cost high-yield fabrication method for producing optimized biomimetic dry adhesivesrdquo Journal of Micromechanics and Microengineering 19 (2009) 115002 (7pp) stacksioporgJMM19115002

[16] J Kahn C Menon ldquoDry adhesives with sensing featuresrdquo Smart materials and Structures IOP Publishing 2013 Vol22(8) p085010

[17] M Hu W Kang Z Li S Jie Y Zhao L Li et al ldquoZinc(II)phophyrin-poly(lactic acid) nanoporous fiber membrane for ammonia gas detectionrdquo J Porous Mater (2016) 23911-917 DOI 101007s10934-016-0148-5

[18] D Stevens B Gray D Yin G Chapman D B Leznoff ldquoPost arrays for the immobilization of vapochromic coordination polymers for chemical sensorsrdquo In Proc 2017 IEEE SENSORS 2017 pp 1-3 httpsdoiorg101109ICSENS20178234080

[19] D Yin G Chapman D Stevens B Gray D B Leznoff ldquoDetection of low concentration ammonia using differential laser induced fluorescence on vapochromic coordination polymersrdquo In Proc SPIE West on Photonic Instrumentation Engineeringrsquo01 2018 105390K

[20] N Keller T M Nargang M Runck F Kotz A Striegel K Sachsenheimer D Klemm K Laumlnge M Worgull C Richter D Helmer B E Rapp ldquoTacky cyclic olefin copolymer a biocompatible bonding technique for the fabrication of microfluidic channels in COCrdquo Lab Chip 2016 16 1561 DOI 101039c5lc01498k

[21] Z Qi H Yu Y Chen M Zhu ldquoHighly porous fibers prepared by electrospinning a ternary system of nonsolventsolventpoly(L-lactic acid)rdquo Materials Letters 2009 Vol 63 Issue 3-4 415-418 httpsdoiorg101016jmatlet200810059

[22] Y Li C T Lim M Kotaki ldquoStudy on structural and mechanical properties of porous PLA nanofibers electrospun by channel based electrospinning systemrdquo Polymer 2015 Vol 56 572-580 httpsdoiorg101016jpolymer201410073

[23] B Timmer W Olthius A Berg ldquoAmmonia sensors and their applicationsmdasha reviewrdquo Sensors and Actuators B Chemical 2005 Vol 107 Issue 2 pp 666-677 httpsdoiorg101016jsnb200411054

48

[24] M Gel S Kandasamy K Cartledge D Haylock ldquoFabrication of free standing microporous COC membranes optimized for in vitro barrier tissue modelsrdquo Sensors and Actuators A Physical 2014 Vol 215 pp 51-55 httpsdoiorg101016jsna201310018

[25] M Dogu N Ercan ldquoHigh performance cyclic olefin copolymer (COC) membranes prepared with melt processing method and using of surface modified graphitic nano-sheets for H2CH4 and H2CO2 separationrdquo Chemical Engineering Research and Design 2016 Vol 109 pp 455-463

[26] VE Kuznetsov AN Solonin OD Urzhumtsev R Schilling AG Tavitov rdquoStrength of PLA Components Fabricated with Fused Deposition Technology Using a Desktop 3D Printer as a Function of Geometrical Parameters of the Process ldquo Polymers 2018 10 313

49

Appendix

Fluorescence spectrum data

Figure 34 Emission spectra of PLA between 200 and 600 nm illuminated with UV-Vis-NIR light source using 275-375 nm band pass color filter Captured from spectrometer (Flame Ocean Optics)

Figure 35 Fluorescence spectra of PLA between 400 and 600 nm Captured from spectrometer (Flame Ocean Optics)

50

Figure 36 Emission spectra of COC between 200 and 600 nm illuminated with UV-Vis-NIR light source using 275-375 nm band pass color filter Captured from spectrometer (Flame Ocean Optics)

Figure 37 Fluorescence spectra of COC between 400 and 600 nm Captured from spectrometer (Flame Ocean Optics)

51

Figure 38 Emission spectra of PDMS between 200 and 600 nm illuminated with UV-Vis-NIR light source using 275-375 nm band pass color filter Captured from spectrometer (Flame Ocean Optics)

Figure 39 Fluorescence spectra of PDMS between 400 and 600 nm Captured from spectrometer (Flame Ocean Optics)

ii

Approval

Name David Stevens Degree Master of Applied Science (Engineering Science) Title Vapochromic Coordination Polymer Immobilization

Techniques for Ammonia Sensors with Applications to Power Transformers

Examining Committee Chair Michael Sjoerdsma Senior Lecturer

Bonnie Gray Senior Supervisor Professor

Daniel Leznoff Supervisor Professor

Glenn Chapman Internal Examiner Professor

Date DefendedApproved April 16 2019

iii

Abstract
































iv



v

Acknowledgements







where I am today

vi

Table of Contents









References 46

vii


viii

List of Tables








air 41

ix

List of Figures


















x




















xi




C6H12 Cyclohexane

DCM Dichloromethane



NH3 Ammonia







THF Tetrahydrofuran



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



iii

Abstract
































iv



v

Acknowledgements







where I am today

vi

Table of Contents









References 46

vii


viii

List of Tables








air 41

ix

List of Figures


















x




















xi




C6H12 Cyclohexane

DCM Dichloromethane



NH3 Ammonia







THF Tetrahydrofuran



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



iv



v

Acknowledgements







where I am today

vi

Table of Contents









References 46

vii


viii

List of Tables








air 41

ix

List of Figures


















x




















xi




C6H12 Cyclohexane

DCM Dichloromethane



NH3 Ammonia







THF Tetrahydrofuran



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



v

Acknowledgements







where I am today

vi

Table of Contents









References 46

vii


viii

List of Tables








air 41

ix

List of Figures


















x




















xi




C6H12 Cyclohexane

DCM Dichloromethane



NH3 Ammonia







THF Tetrahydrofuran



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



vi

Table of Contents









References 46

vii


viii

List of Tables








air 41

ix

List of Figures


















x




















xi




C6H12 Cyclohexane

DCM Dichloromethane



NH3 Ammonia







THF Tetrahydrofuran



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



vii


viii

List of Tables








air 41

ix

List of Figures


















x




















xi




C6H12 Cyclohexane

DCM Dichloromethane



NH3 Ammonia







THF Tetrahydrofuran



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



viii

List of Tables








air 41

ix

List of Figures


















x




















xi




C6H12 Cyclohexane

DCM Dichloromethane



NH3 Ammonia







THF Tetrahydrofuran



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



ix

List of Figures


















x




















xi




C6H12 Cyclohexane

DCM Dichloromethane



NH3 Ammonia







THF Tetrahydrofuran



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



x




















xi




C6H12 Cyclohexane

DCM Dichloromethane



NH3 Ammonia







THF Tetrahydrofuran



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



xi




C6H12 Cyclohexane

DCM Dichloromethane



NH3 Ammonia







THF Tetrahydrofuran



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



1






























dissolved gasses

2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



2

































dissolved in liquid

3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



3










techniques



ammonia detection









4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



4

















21 VCP Synthesis













5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



5

2119870119860119906(119862119873)) + 119885119899(119862119897119874))6119867)1198743456789⎯⎯⎯ 120572 minus 119885119899[119860119906(119862119873))]) (1)

119885119899(119873119874A)) + 2[(119899 minus 119861119906)119873][119860119906(119862119873))] 1 2D 119867)1198743456789⎯⎯⎯ 120573 minus 119885119899[119860119906(119862119873))]) (2)






polymorphs


6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



6
















7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



7





glass substrate






23 Summary









8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



8

























32 Fabrication





9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



9























10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



10



PMGI




























11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



11








12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



12









13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



13





















14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



14











35 Optical results











15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



15






16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



16



























17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



17


NH4OH bottle




time






and Figure 15

18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



18



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



19






Sample Peak



Response time (sec)

(90 of max)



373 4313 80


451 6896 68


438 9516 35



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



20











21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



21


Sample Peak



Response time (sec)

(90 of max)



-371 1258 150


250 mJcm2 UV dose -203 18945 102


-1166 19444 78


-926 19422 78






22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



22










-279 10369


112 9476


056 9780

23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



23






























24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



24




















198119898119892119885119899[119860119906(119862119873))]) + 27119898119892119875119871119860 + 8119898119871119863119862119872 + 21198981198711198791198671198653456789⎯⎯⎯ 22511989811989211987511987111986011988111986211987511990011990312119908119905 119875119871119860 minus 119873119875119872






immobilize the VCPs

25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



25





equation











Area of pores

12 wt PLA-NPM (1) 10333 0474 540

12 wt PLA-NPM (2) 11446 3999 573

48 wt PLA-NPM (3) 7649 0531 501

48 wt PLA-NPM (4) 4533 10851 499

26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



26



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



27












mLsec






44 Optical results










28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



28



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



29




()

Response time (sec)

(90 of max)



















Figure 25

30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



30




Response time (sec)

(90 of max)






31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



31













sample





32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



32







51 Fabrication











sealed device













33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



33






























34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



34



















35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



35












36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



36


















a rate of 194 mLs

37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



37





of the experiment

54 Optical results







levels of exposure


38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



38

















a few minutes

39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



39




















40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



40







the time to compare












phase (eg oil)

41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



41




50000 ppm



response

Weak positive




200 mJcm2 Clear

positive response

Clear positive

response

Weak positive


Weak positive


Mushroom 250 mJcm2

Clear positive

response

Clear positive

response

Weak positive


Weak positive

response

Mushroom 300 mJcm2

Clear positive

response

Clear positive

response



(88 VCP) Clear

positive response

Clear positive

response

Clear positive

response

Weak positive

response


Clear positive

response

Clear positive

response

Clear positive

response

Weak positive

response 24 wt

(76 VCP) Clear

positive response

Clear positive

response



48 wt (52 VCP)

Clear positive

response

Clear positive

response

No data No data

50 wt (50 VCP)

Clear positive

response

Clear positive

response




Clear positive

response

Clear positive

response


COC-NF α polymorph

Clear positive

response

Clear positive

response


42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



42






















and liquid samples










43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



43


samples



















fluid







44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



44

61 Future work




611 Post Arrays








of VCP












VCP-NPMsNFs

45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



45






polymorph of VCP

46

References












47













48




49

Appendix




50



51



46

References












47













48




49

Appendix




50



51



47













48




49

Appendix




50



51



48




49

Appendix




50



51



49

Appendix




50



51



50



51



51



Documents

Vapochromic Coordination Polymer Immobilization Techniques ...summit.sfu.ca/system/files/iritems1/19228/etd20197.pdf · a transformer’s insulating materials. Current methods of