Fluorocarbon Coatings Via Plasma Enhanced Chemical Vapor Deposition of 1H,1H,2H,2H-perfluorodecyl Acrylate - 2, Morphology, Wettability and Antifouling Characterization

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Fluorocarbon Coatings Via Plasma EnhancedChemical Vapor Deposition of 1H,1H,2H,2H-perfluorodecyl Acrylate - 2, Morphology,Wettability and Antifouling Characterizationa

Virendra Kumar,* Jerome Pulpytel, Hubert Rauscher, Ilaria Mannelli,Francois Rossi, Farzaneh Arefi-Khonsari

V. Kumar, J. Pulpytel, F. Arefi-KhonsariLaboratoire de Genie des Procedes Plasmas et Traitement deSurface, Universite Pierre et Marie Curie, ENSCP,11 rue Pierre etMarie Curie, 75231 Paris cedex 05, FranceFax: (þ33) 1 44276813; E-mail: [email protected]. KumarRadiation Technology Development Division, BARC, Trombay,Mumbai 400085, IndiaH. Rauscher, I. Mannelli, F. RossiInstitute for Health and Consumer Protection, EuropeanCommission Joint Research Centre, Ispra, Italy

a Part 1: cf. ref. [34]

Low surface energy fluorocarbon polymer coatings were prepared via plasma enhanced chemicalvapor deposition (PECVD) of 1H,1H,2H,2H-perfluorodecyl acrylate (PFDA) in a low pressureinductively excited RF plasma. The influence of plasma parameters, such as, deposition time,continuous wave (CW) and pulse modulated (PM) plasma mode, plasma power and plasma dutycycle (DC) on morphology and wettablity of the PFDA was investigated using field emissionscanning electron microscopy (FESEM) and contact angle (CA) measurement techniques. Theplasma mode, plasma power and pulse duty cycle played a pivotal role in tailoring the surfacemorphology, wettability and the surface energy of the PFDA coating. The water CA hysteresisvalues for PFDA coatings suggested the wetting characteristics of the coating satisfying Wenzelmodel of nanostructured solid-water wetted contact. Athin conformal PFDA coating transformed a super-hydro-philic Whatman filter paper into a super-hydrophobicand oleophobic surface, which has industrial appli-cations for development of durable, stain resistanceand liquid repellent papers. The antifouling propertyof PFDA coatings investigated by quartz crystal micro-balance (QCM) exhibited the protein repellent behavioragainst three model proteins namely, ovalbumin (OVA),human serum albumin (HSA) and fibrinogen (FGN).

Plasma Process. Polym. 2010, 7, 926–938

� 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonline

Introduction

Low surface energy surfaces having hydrophobic and

oleophobic characteristics are highly desirable for various

applications, such as biocompatible surfaces, antifouling

coatings, durable, waterproof and stain resistant paper,

textiles and wood, low dielectric constant material for

microelectronics, etc.[1–3] Fluorocarbon polymers are the

suitable candidates for these applications due to their

unique properties, such as high thermal stability, excellent

library.com DOI: 10.1002/ppap.201000038

Fluorocarbon Coatings Via Plasma Enhanced Chemical Vapor Deposition of 1H,1H,2H,2H-perfluorodecyl Acrylate - 2 . . .

chemical resistance, low friction coefficient, superior

weatherability, oil and water repellence, low flammability,

low dielectric constant, etc.[4–7]

Non-specific adsorption of proteins and associated

biofouling is one of the most significant limitations to

the end point utility of several biomaterial and marine

devices.[8] A large number of existing and emerging

biotechnological applications suffer from biofouling pro-

cess; including contact lenses, catheter tubes, blood

contacting devices, implant devices, biosensors, microflui-

dics and drug delivery systems. The adsorption of proteins

onto a biomaterial surface initiates a cascade of events

involved in biofouling process, including the biofilm

formation, that can ultimately result in inflammation,

infection and rejection of the material/implant causing

extra pain and medical cost to the patient.[8,9] In fact, the

primary mechanism in the attachment of microorganisms

to surfaces involves conditioning of the material surface by

protein adsorption from the biological fluid or protein and

glycoprotein secreted by the microorganism.[10–12] Marine

devices also suffer from the bio-fouling resulted from the

undesired accumulation of colonizing organisms, e.g.,

bacteria, cyanobacteria, algae, etc. The undesirable accu-

mulation of biomass on a ship hull leads to increased

weight and higher hydrodynamic drag resulting in lower

operational speeds and increased fuel consumption.[13]

Therefore, the development of efficient protein-resistant

coatings has great industrial relevance to the production of

antibiofouling surfaces.[14–19] The surface-free energy,

wettability and mechanical properties of the coating play

a vital role in defining the extent to which a surface can

resist biofouling or facilitate fouling release.[20–22] In this

regard, the potency of fluoropolymers[17,23,24] and silicone

elastomers,[25] which have emerged as the most promising

candidates, has been explained in terms of their inert-low

surface energy and interesting mechanical properties.[21,26]

In general, the conventional wet deposition methods of

fluoropolymer coatings involve various chemicals and

solvents and suffer from processing difficulties, such as

poor adhesion of coatings to the substrate due to the inert

nature of fluorocarbons and poor control over the thick-

ness.[27–33] On the other hand, the dry and solvent free

plasma enhanced chemical vapour deposition (PECVD) or

plasma polymerization process does not suffer from the

processing difficulties mentioned before, and offers a better

and effective process to deposit fluorocarbon coatings on

any substrate with good adhesion and better control over

thickness, chemistry, morphology and final properties of

the coatings.[34–40] Majority of the literature on the

fluorocarbon polymer coatings by PECVD process targeted

for different applications involve saturated low molecular

weight precursors, namely CF4, C2F6, C3F8, C3F6O, CH2F2,

CHF3, CF3CHF2 and C4F8.[41–48] For example, Vaswani et al.

have reported the applications of plasma polymerized


� 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

fluorocarbon coatings from CF3CHF2 and C4F8 precursors for

enhancement of barrier properties and hydrophobic

characteristics of paper and regenerated cellulose sur-

faces.[48] However, recently, great attention has been paid

to produce fluorocarbon polymer coatings by plasma

polymerization of high molecular weight organic precursor

molecules containing polymerizable unsaturated acrylate

group with perfluoroalkyl pendant chain due to their

exceptional properties such as fast polymerization, require-

ment of mild processing conditions and hydrophobic as

well as oleophobic (i.e., liquid repellent) characteristics. The

extraordinary properties of these precursors are attributed

to the presence of acrylate group and the peculiar chemical

architecture of the perfluorocarbon polymer chains.[29,49,50]

Some of the examples of these precursors include

1H,1H,2H,2H-perfluorodecyl acrylate (PFDA),[34,51,52]

1H,1H,2H,2H-perfluorooctyl acrylate[53] and 1H,1H,2H-per-

fluoro-1-dodecene.[54,55] The majority of the applications of

the fluorocarbon coatings depend on the surface energy and

wettability of the surface, which is governed by the

topography and the morphology in addition to the chemical

composition of the coating. Surfaces with regularly aligned

and closely packed CF3 groups have been reported to exhibit

surface energy of 6.7 mJ �m�2, which is well below the 18–

20 mJ �m�2 value for polytetrafluoroethylene (PTFE).[28,36]

The main challenge is to preserve the chemical archi-

tecture of the precursor molecule in the plasma polymer-

ized coating to the maximum extent possible with tailor

capability of the surface morphology and wettability of the

coating.[37,51,54] In our earlier study, we have shown by

spectroscopic techniques that plasma polymerized PFDA

coating with wide range of chemistries could be produced

by varying plasma process parameters.[34] In the present

work, we have investigated the influence of plasma

parameters on the morphological and surface wettability

of the plasma polymerized PFDA coatings. Most of the

research works, carried out on plasma deposited perfluor-

oalkyl acrylate coating, have been targeted mainly to

achieve the low surface energy surfaces with liquid

repellent properties.[51–57] To the best of our knowledge,

no study has been aimed to explore the protein repellent

characteristics of plasma polymerized PFDA coatings.

Therefore, the objective of the present study has been

focused on the antifouling (i.e., protein repellent) as well as

the liquid repellent applications of the plasma polymerized

PFDA coatings.

Experimental Part

Materials

1H,1H,2H,2H-perfluorodecyl acrylate (PFDA) precursor

(CH2¼CH�COO�CH2CH2(CF2)7CF3, purity¼ 97%, Molecular weight

(M)¼518.17, Sigma–Aldrich, France) was used as received without

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V. Kumar, J. Pulpytel, H. Rauscher, I. Mannelli, F. Rossi, F. Arefi-Khonsari

further purification. Argon gas (Air Liquide, France, purity> 99.9%)

was used as a carrier gas. Thermanox cover slips (Nalge Nunc

International, Thermo Fisher Scientific, USA) and polished silicon

wafers (100) (Siltronix) were used as coating substrates. Whatman

quantitative filter paper grade 50 (Pore size 2.7mm, 97 g �m�2) were

procured from Sigma–Aldrich France. Three test proteins, namely,

ovalbumin (OVA, Sigma–A5503), human serum albumin (HSA, 30%

solution, Sigma-A6909) and fibrinogen (FGN, lyophilized Fraction I,

Type I, human, Sigma-F3879) were diluted in 10 mM PBS (pH 7.4) to a

final concentration of 50mg �mL�1 and used for quartz crystal

microbalance (QCM) analysis.

Plasma Deposition Setup

1H,1H,2H,2H-perfluorodecyl acrylate (PFDA) polymer coatings

were fabricated in a low pressure inductively excited radio

frequency-tubular quartz plasma reactor system (5 cm diameter,

40 cm length, base pressure of 3� 10�2 mbar). The schematics of

plasma deposition setup and technical details of the process have

been provided in our earlier work.[34] The flow rate of the precursor

was controlled by flow rate of carrier gas (i.e., Ar), which was

regulated and measured by electronic mass flow controllers (MKS

instruments). Prior to each experimental run, the reactor was

scrubbed and cleaned with detergent, organic solvents and dried

using a compressed air. The plasma reactor system was

reassembled and cleaned further with 20 W Ar plasma discharge

at 0.5 mbar pressure for 30 min. PFDA coatings were deposited at

working pressure of 0.5 mbar, precursor temperature of 65 8C,

precursor flow rate of 0.44 sccm, Argon flow rate of 20 sccm, unless

otherwise mentioned.

Coating Characterization Techniques

Field Emission Scanning Electron Microscopy (FESEM)

The morphology and thickness of the plasma polymerized coatings,

prepared under different plasma process conditions, were inves-

tigated by using FESEM. FESEM images were taken using Zeiss Ultra

55 FEGSEM with GEMINI Column on gold metallized PFDA coating

surfaces by sputter coating (Cressinton sputter coater-108 auto).

Electrons with accelerating voltage of 5 and 6 kV were used to

obtain the FESEM images. The thicknesses of the coatings were

measured from the cross-sectional images of fracturing PFDA

coatings deposited on silicon wafers.

Atomic Force Microscopy (AFM)

An atomic force microscope NTEGRA PRIMA from NT-MDT

was used to examine the topography and roughness of the

plasma polymer coatings deposited onto silicon wafer substrates.

The microscope was operated in semi-contact mode. All of the

AFM images were acquired at room temperature (�24 8C) in air

and are presented as unfiltered data. ‘NOVA’ SPM Software

was used for data acquisition and data processing. The average

surface roughness (Ra) values were derived from (10mm�10mm)

AFM images.



Contact Angle (CA) Measurement

Sessile drop CA values were measured using a video capture CA

apparatus (Digidrop GBX-3S system, France). For each measure-

ment, a 6mL droplet was dispensed onto the coating surface and the

CA was measured in a static as well as in a dynamic mode. The static

water contact angle (WCA) were measured just after the dispensing

the liquid drop on the surface and reported as an average (mean)

value� s (standard deviation), estimated from five individual CA

values measured per each sample. Surface energy of PFDA coatings

were estimated by static CA values measured for two probe liquids,

namely water and diiodomethane using Owen and Wendt

geometric mean Equation (1)[58]

1 þ cosuð Þg l ¼ 2 gdsgdl

� �1=2 þ gpsgpl

� �1=2h i

(1)

and

gs ¼ gps þ gds (2)

where u is the CA, gs and g l are the surface free energies of the solid

and liquid, respectively. The superscripts d and p refer to the

dispersive and polar components of surface energy, respectively.

Advancing CAs were measured by lowering the liquid droplet

towards the underlying surface until it just touched (without any

distortion of the circular shape) and measuring the CA while

increasing the volume of liquid drop until the CA remained

constant. Receding angle was measured by decreasing the

volume of the drop until the CA value remained constant and

the solid/liquid interface started to decrease.[59] The values

reported are the average value� s, estimated from five individual

measurements per sample. Water contact angle hysteresis (WCAH)

is defined as the difference between the advancing and receding

CAs. WCAH is originated by the presence of topographical and

chemical heterogeneities of the surface. The CA hysteresis is an

indication of the tendency of a liquid droplet to roll off across the

surface (i.e., in the case of low CAH value the droplet easily rolls off,

and vise versa). Two descriptions have been proposed for the

dependency of the wetting behavior on surface heterogeneity or

surface roughness: A very low CAH value for a rough surface

indicates the slippery behavior of composite rough surfaces (air

trapped in the grooves) satisfying Cassie–Baxter model, whereas,

high CAH value for a rough surface indicates the non-slippery

behavior of wetted rough surfaces satisfying the Wenzel

model.[53,60] Comparison of the Cassie–Baxter equation with the

Wenzel equation shows that the main difference between

composite (air trapped in the grooves) and rough surfaces is that

for most of finite CA values; the former predicts greater CAs relative

to the corresponding smooth surface, whereas this only holds true

in the latter case when CAs exceed 908CA on the flat substrate (i.e.,

less than 908 on a smooth surface gives rise to a smaller CA upon

roughening).[61]

Quartz Crystal Microbalance (QCM)

Recent studies have proven that the QCM-dissipation (QCM-D)

technique is very useful for the evaluation of surface-related

processes in liquids, including protein adsorption.[62–67] The QCM

instrument monitors resonating frequency change of the Au coated

DOI: 10.1002/ppap.201000038


sensor quartz disc due to the adsorption of protein molecules on it in

a time resolved manner. The change in the resonating frequency

(Df) of the sensor disc could be related to the mass change (Dm) of

the sensor disc due to adsorption or desorption of material using

Sauerbrey Equation (1).[68]

Fig(a)

Plasma

� 2010

Dm ¼ � C=n½ �: Dfð Þ (3)

where n is the overtone number and C is a mass sensitivity

constant. At 5 MHz, a frequency shift of 1 Hz corresponds to a mass

change of�18 ng � cm�2. Sauerbrey relation (1) is applicable to only

sufficiently thin and rigid adsorbed films.[67] However, the QCM

analysis has been widely used to obtain the adsorption behavior

and approximate mass of adsorbed protein on to various

substrates.[62,66] However, the trapped solvent molecules may

make the adsorbed protein layer soft, which influence the damping

of the quartz oscillation and the sensitivity constant of the sensor,

resulting in the error in the estimation of the deposited mass.

Therefore, we had already examined this aspect and found a low

dissipation shift (<0.1E-5 for HSA and OVA;<0.6E-5 for FGN) during

the protein adsorption process, which pointed out the formation of

a rigid protein layer where the viscoelastic effect was not

significant; allowing us to estimate approximate mass of absorbed

proteins using Sauerbrey equation. PFDA coatings were analysed

for their antifouling properties by measuring protein adsorption

using three different proteins, as a function of time in a continuous

flow mode using a Quartz crystal microbalance QCM-D E4

instrument (Q-Sense AB, Gothenburg, Sweden). All data presented

in this study correspond to the fifth overtone, which is less sensitive

to variations of the mounting conditions of different crystals.

Polished AT-cut and Au coated sensor quartz discs (14 mm in

diameter, 0.30 mm thick) with a fundamental frequency of 5 MHz

(Q-Sense AB, Gothenburg, Sweden) were used as substrate for PFDA

coatings for the QCM experiments. After assembling the sensor

quartz disc into the QCM, the plasma polymerized PFDA coated

surfaces were first exposed to 10� 10�3M PBS solution at pH 7.4, in

order to stabilize the system and obtain the base line. After that, the

protein solution with 50mg �mL�1 concentration in 10�10�3M PBS

was pumped continuously through the measurement chamber at a

flow rate of 20mL �min�1. The frequency changes due to adsorption

of proteins were monitored as a function of time. All QCM

adsorption experiments were performed at 25 8C� 0.02 8C in

duplicate.

ure 1. Field emission scanning electron microscopy (FESEM) imag10min (WCA¼ 1168), (b) 20min (WCA¼ 1218) and (c) 40min (WCA

Process. Polym. 2010, 7, 926–938

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Results and Discussion

Plasma Deposition Time

Plasma deposition time is an important parameter that

governs the properties of plasma polymerized coatings

such as, coating thickness, morphology and topography of

the coating. PFDA coatings were deposited for various

deposition times and their surface morphology and

wettability were investigated by FESEM and WCA mea-

surement techniques, respectively. We have reported

earlier that the coating thickness increases linearly with

the deposition time, whereas, the surface chemistry of

PFDA coating was not influenced by plasma deposition

time.[34] Figure 1(a–c) shows the FESEM micro-images of

surfaces of PFDA coatings prepared at three different

deposition times that revealed the influence of deposition

time on the surface morphology of PFDA coating. At lower

deposition time the PFDA coating showed less prominent

with less number of nano-particulate structures appeared

on the coating surfaces. The particulate surface morphology

gradually became more prominent with the increase in the

deposition time. The WCA of the PFDA coatings increased

with the increase in deposition time (Figure 1 caption).

PFDA coating prepared at 10 min deposition time (thick-

ness¼ 120� 15 nm) exhibited WCA¼ 1168, which

increased to 1218 and 1268 for deposition time of 20 min

(thickness¼ 290� 45 nm) and 40 min (thickness¼ 580�50 nm), respectively. The increase in the hydrophobicity of

PFDA coatings with the increase in plasma deposition time

was mainly attributed to the increase in the roughness and

the change in the surface morphology to rougher with

nanostructured particulate features [Figure 1 (a–c)]. The

dependency of particulate size on the plasma deposition

time has also been reported in literature.[69,70] Effect of

deposition time on surface structures, morphology and

wettability of plasma fluorocarbon coatings produced from

tetrafluoroethylene precursor have also been reported

earlier by other research groups.[71,72] They have found

that the surface morphology alters from nanostructured

es of PFDA coating surfaces prepared at different deposition time¼ 1268) (Ppk¼ 1W, ton¼ 25ms, toff¼ 75ms).


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particulate to complex micro/nano sized ribbon like

structures with the increase of thickness of coating and

plasma deposition times, which was also manifested by the

significant increase in the WCA values. These observations

showed that the plasma deposition time influenced the

coating thickness, surface morphology and wettability but

not the chemical composition of the PFDA coatings.[34]

PM Versus CW Plasma Mode

Influence of the plasma operation modes i.e., CW and PM

plasma discharge modes on the composition, surface

structures and morphology of different plasma fluorocar-

bon coatings have been reported by other research

groups.[71,72] Figure 2 shows the FESEM images of PFDA

coatings prepared under PM and CW plasma modes. It could

be seen that PFDA coatings deposited under PM plasma

mode exhibit particulate nanostructured morphology

(Figure 2a), whereas, the PFDA coatings prepared in CW

plasma condition exhibit smooth surface morphology

(Figure 2b). AFM analysis also revealed that the PFDA

coating prepared under PM mode exhibit higher roughness

(Ra¼ 22.3 nm) as compared to that prepared under CW

mode (Ra ¼ 0.5 nm) (AFM images not shown). Cicala et al.

have also reported the difference in the surface morphology

and roughness of fluorocarbon films obtained by CW and

PM plasmas fed with C2F4 precursor.[71] The difference in

the surface morphology and roughness of fluorocarbon

coatings produced in CW and PM mode was attributed to

the difference in the growth mechanism.[51,71] CW plasma

process deposits coatings under more energetic condition,

as the energy is continuously being fed to the system, which

gives rise to high plasma density generating energetic

species through out the treatment time that cause

fragmentation, polymerization initiation of precursors,

generation of reactive sites on the coating and surface

modification of coating via etching/ablation processes

giving rise to smooth coatings surface. On the other hand,

PM plasma operates at low total power input i.e., equivalent

Figure 2. Field emission scanning electron microscopy (FESEM) imacoatings prepared under CW and PM plasma mode (ton¼ 25ms, toff¼(b) CW-1W.



powerPeq conditions.[34,73] In PM plasma conditions, a more

ordered growth process occurs during plasma ‘off’ times

(toff), relative to complex processes during the highly

energetic plasma ‘on’ periods (ton). The lifetime of neutrals

(responsible for deposition/polymerization) is much higher

than those of the ions and electrons (responsible for surface

modifications by ablation/etching).[74] Therefore, PM

plasma process provides the control over the extent of

precursor fragmentation, coating degradation or surface

modification by varying ton/toff ratio, which regulates the

relative concentration of the ions and the neutrals during

the plasma off time. In PM plasma mode, the neutral radical

could stay longer and take part in the polymerization/

deposition process during plasma toff with minimal surface

modifications of coatings via etching/ablation caused by

ions, which was manifested by nanostructured rough

PFDA coatings.[75,76] In PM mode, upon reaching to a critical

number density of the radical species, rapid agglomeration

is triggered leading to the particulate morphology of the

coating.[77] However, in CW mode excessive secondary

products cause the partial pressure of precursor to drop to

an extent that precludes exclusive powder or particulate

formation. Moreover, in CW mode, the polymerization,

fragmentation and ablation processes take place simulta-

neously throughout the plasma discharge time leading to

smooth coating surface by competitive ablation and

polymerization (CAP) principle.[34] It could be concluded

that in CW plasma mode, the uniform and smooth film

growth resulted from the synergistic effect of deposition

and surface modification by etching/ablation of coatings.

On the contrary, the film growth in PM plasmas is mainly

governed by the growth of coalesced nuclei produced

during plasma off time, resulting in the rough and

particulate morphology of coatings.[72]

Table 1 shows static CA values and the surface free

energy for PFDA coatings on Thermanox, prepared

under PM and CW plasma modes using two test liquids

i.e., water and diiodomethane. The static CA values

are significantly higher for PFDA coatings prepared on

ges of the PFDA75ms) (a) PM-1W,

smooth Thermonox surfaces under PM

mode (PM-1W: ton/toff ¼ 10 ms/90 ms,

WCA¼ 126.58; CA of diiodomethane¼1058) as compared to that prepared under

CW mode (CW-1W: WCA¼ 107.08; CA of

diiodomethane¼ 93.08). The lower WCA

values (i.e., lower hydrophobicity) for

PFDA coatings prepared in CW mode as

compared to that prepared under PM

mode was attributed to de-fluorination

and lower CF2 and CF3, and incorporation

of oxygenated group in the PFDA coatings

prepared under CW plasma mode,[34] in

addition to the lack of surface roughness

(a smoother surface) in CW mode (FESEM

DOI: 10.1002/ppap.201000038

Table 1. Static CA of PFDA coatings on Thermanox coverslips andWhatman paper-50, and surface energy of PFDA coating surface depositedon Thermanox coverslips under different experimental conditions. (DC10: ton¼ 10ms, toff¼90ms, DC25: ton¼ 25ms, toff¼ 75ms, DC50:ton¼ 50ms, toff¼ 50ms, DC75: ton¼ 75ms, toff¼ 25ms).

Sample Static contact angle (degree) Surface energy

Water Diiodomethane mN�m�1

Thermonox Paper Thermanox paper Total Polar Dispersive

(gs) (gps ) (gd

s )

PM-1W-DC25 123.5� 1.5 144.0� 1.5 100.0� 1.5 122.0� 2.0 8.6 0.1 8.5

PM-4W-DC25 111.5� 1.8 136.0� 1.8 93.5� 1.2 111.0� 1.5 12.3 1.1 11.2

CW-1W 107.0� 1.5 135.0� 2.0 93.0� 1.5 117.0� 1.5 13.4 2.0 11.4

CW-5W 102.0� 1.5 129.0� 1.7 84.5� 1.9 102.0� 1.3 17.6 2.3 15.3

PM-1W-DC10 126.5� 1.5 151.0� 1.5 105.0� 1.4 122.0� 1.9 7.3 0.2 7.1

PM-1W-DC50 113.5� 2.0 – 98.5� 1.5 – 10.4 1.2 9.2

PM-1W-DC75 110.0� 2.6 – 96.5� 1.6 – 11.6 1.7 10.0


and AFM analysis). The similar trend of static CA was

exhibited for PFDA coatings prepared on rough Whatman

paper (PM-1W: ton/toff ¼ 10 ms/90 ms, WCA¼ 1518;CA of diiodomethane¼ 1228) as compared to that

prepared under CW mode (CW-1W: WCA¼ 1358; CA of

diiodomethane¼ 1178). However, the CA values were

significantly higher for PFDA coatings on Whatman paper

as compared to that on Thermanox surfaces, due to the

micro-roughness of paper surface. The high CA values for

water and diiodomethane clearly revealed the water

repellent (hydrophobic) and oil-repellent (oleophobic)

characteristic of PFDA coatings. The surface energy of PFDA

coating was found to be greatly influenced by the

plasma operation mode (Table 1). The surface energy of

PFDA coating prepared under PM mode exhibits very low

surface free energy (PM-1W, ton/toff ¼ 10 ms/90 ms:

gs ¼ 7.3 mN �m�1, gps ¼ 0.2 mN �m�1, gds ¼ 7.1 mN �m�1) as

compared to that prepared under CW mode (CW-1W:

gs ¼ 13.4 mN �m�1, gps ¼ 2.0 mN �m�1, gd

s ¼ 11.4 mN �m�1).

There was an increase in both the polar as well as the

dispersive component of the surface

energy when PM mode is changed to

CW plasma mode, which is explained by

de-fluorination leading to the decrease in

CF2 groups in perfluoroalkyl chain, and

incorporation of polar groups in CW

plasma operation mode.[34]

Figure 3. Effect of plasma power on the surface morphology of the coatings preparedunder CW and PM plasma mode (ton¼ 25ms, toff¼ 75ms) (a) PM-4W, (b) CW-5W.

Plasma Power

The influence of plasma power was also

reflected in the surface morphology,

hydrophobicity and surface energy of

the PFDA coatings. FESEM images shown



in Figure 2 and Figure 3 clearly reveal that plasma power (in

both CW and PM mode) affect the surface morphology and

the distribution of nanostructures of PFDA coatings

surfaces. The surface morphologies of coatings alter from

rough morphology with dense and overlapped prominent

particulate nanostructures for PM-1W (Figure 2a) to

comparatively lesser rough morphology with very few

and less prominent particulate structures for PM-4W; it

seems the particles were embedded inside the polymer

coating film (Figure 3a). On the contrary, PFDA coating

prepared under CW at 1 W power (CW-1W) exhibited a

smooth surface with no particulate nanostructures

(Figure 2b), however, surprisingly, the increase in power

resulted in the formation of very tiny and well separated

nanoparticles (dust) on the surface for CW-5W (Figure 3b).

The deposition rate of plasma polymerized of PFDA coating

have been reported to decrease with the increase in plasma

power[51] due to the fact that at higher power conditions

species responsible for fragmentation and ablation (UV

radiation, ions or electron bombardment) dominate over


932


those responsible for polymerization/deposition (i.e., radi-

cals). In PM mode, at higher plasma power condition,

combinations of processes: (i) the overlapping of coalesced

nuclei, (ii) the entrapment of agglomerated particles in to

the polymer coatings and (iii) the simultaneous occurrence

of a secondary reaction process (degradation/ablation

process) along with polymerization process, were respon-

sible for the less prominent particulate surface morphology.

The degradation and ablation of PFDA coating at higher

power condition has been manifested by the decrease in

F/C ratio and CF2 group concentration,[34] and decrease in

the thickness of the coating with the increase in plasma

power (PM-1W: thickness¼ 600� 50 nm; PM¼ 4 W: thick-

ness¼ 400� 25 nm; CW-1W: thickness¼ 190� 25 nm; CW-

5W: thickness¼ 50� 15 nm). In CW mode the formation of

very tiny nanoparticles on the coating surface at higher

power condition could be attributed to the high plasma

energy density that leads to generation of large concentra-

tions of reactive species creating a favorable condition for

the gas-phase reactions between radicals and other

species.[77,78] The variation in the coating thickness only

cannot justify the difference in the surface morphologies of

PFDA coatings because the chemical composition was also

found to be different for coatings prepared under varying

power conditions.[34] Therefore, the difference in the

surface morphology may be attributed to the different

growth mechanism of PFDA coating prepared under

different plasma power conditions.

Table 1 shows the effect of plasma power on the static CA

and the surface free energy for PFDA coatings prepared

under PM and CW plasma modes. The static CA decreased

drastically with the increase in the plasma power for PFDA

coating deposited on Thermanox as well as on Whatman

filter paper prepared under CW and PM plasma mode. The

total surface free energy, polar component and dispersive

component of surface energy increased with the increase in

Table 2. Advancing (ua) and receding (ur) WCA and WCAH of PFDA coaunder different experimental conditions.

Experimental condition Substrate

PM-1W-DC25 Thermanox


CW-1W Thermanox

CW-5W Thermanox



PM-1W-DC25 Whatman paper

PM-4W-DC25 Whatman paper

CW-1W Whatman paper

CW-5W Whatman paper



the plasma power. The long perfluoroalkyl chains in PFDA

are responsible for showing very low polar and dispersive

interactions with polar and nonpolar liquids.[51] We have

reported that higher plasma power caused de-fluorination

of perfluoalkyl chain and incorporation of oxygenated polar

groups in the PFDA coating,[34] which was reflected here as

higher polar and dispersive surface energy. Moreover, PFDA

coatings prepared under PM plasma mode exhibited lower

surface energy values than those prepared under CW

conditions, which is attributed to higher chemical resem-

blance of coating to the monomer, higher F/C ratio and

higher roughness caused by particulate surface morphol-

ogy of PFDA coating prepared in PM plasma mode.

However, PFDA coatings prepared even at strong plasma

conditions (CW-5W) exhibited lower surface energy

(15.3 mJ �m�2) than that of PTFE coatings (18 mJ �m�2).[56,57]

Table 2 shows the advancing and receding WCAs and

water contact angle hysteresis (WCAH) of PFDA coatings on

Thermanox coverslip and Whatman paper prepared under

different plasma conditions. Similar to static CA, advancing

and receding CA showed lower values for higher power and

CW plasma conditions. The observed high WCAH value (358)for PFDA coating with highest roughness value

(Ra¼ 22.3 nm) prepared at PM-1W indicated that the level

of roughness is not sufficient for there to be a truly

composite interface (air-trapped) and so ruled out the

slippery-composite interface postulated by Cassie–Baxter

theory.[53] The wetting behavior satisfies the Wenzel model

of solid-water wetted contact, which predicts that surface

roughening decreases/increases the repellency of liquids

making a CA of less/greater than 908 on the corresponding

flat surface.[3,79,80] In PM plasma mode, the WCAH

decreased from 358 to 268 when the power is increased

from 1 to 4 W, whereas, in CW plasma mode, the WCAH

increased from 438 to 508when power is increased from 1 to

5 W. The particulate and rough morphology (for PM-1W)

tings on Thermanox coverslips and Whatman filter paper, deposited

ua ur WCAH

137.0� 1.6 102.0� 1.8 35

124.0� 1.4 98.0� 1.6 26

120.0� 2.1 77.0� 1.4 43

117.0� 1.0 67.0� 1.5 50

128.0� 1.6 94.0� 1.4 34

126.0� 1.9 85.0� 1.8 41

157.0� 2.0 140.0� 1.5 17

148.0� 2.1 122.0� 1.3 26

150.0� 1.6 122.0� 1.7 28

148.0� 1.8 111.0� 1.5 37

DOI: 10.1002/ppap.201000038


increased the actual surface area of

the coating surface in contact with the

liquid and, therefore, manifested as the

increased advancing CA (according to

the Wenzel theory) as compared to the

smooth surface in PM-4W and CW-1W

coatings. The decrease in the WCAH with

the increase in the power in PM mode is

attributed to the decrease in the surface

roughness that otherwise acts as a hurdle

for liquid to slide on the surface. More-

over, the higher WCAH for coatings

prepared in CW plasma mode is attrib-

uted to the polar interaction between the

water and the oxygenated polar groups

on coatings. The higher is the plasma

power in CW mode, the higher is the

concentration of polar groups generated

that eventually lead to higher WCAH

values.

Figure 4. Field emission scanning electron microscopy (FESEM) images of PFDA coatingsprepared under different DC of PM mode (Ppk¼ 1W) (a) DC¼ 10%, (b) DC¼ 25%,(c) DC¼ 50%, (d) DC¼ 75%, (e) CW (DC¼ 100%), (f) untreated silicone.

Pulse Plasma Duty Cycle (DC)

In PM plasma mode, at a fixed pulse

frequency, pulse DC governs the plasma

pulse characteristics such as ton/toff ratio

and equivalent power (Peq), and conse-

quently influences coating growth pro-

cesses (e.g., deposition, surface modifica-

tion), which is manifested by the

variation of chemical and morphological

characteristics of the polymer coat-

ings.[34,71,72,81] The influence of the DC

of the pulse plasma on surface morphol-

ogy of the PFDA coatings was revealed by

FESEM images of PFDA coating surfaces shown in Figure 4.

The size, density and distribution of the particulate

nanostructures of the PFDA coating surface altered with

the DC. At 10% DC small particulate structures in over-

lapped form appeared, but at 25% DC well separated, bigger

and prominent particulate surface morphology was

obtained. At 50% DC few particles and widely separated

but bigger globular structure with decreased particle

density appeared, and with further increase in DC, particle

size started decreasing and finally disappeared in CW (i.e.,

100% DC) conditions. In principle, increase in the DC of

plasma pulse leads the soft PM regime towards the strong

CW plasma regime (i.e., DC¼ 100%). At higher DC, higher

concentration of reactive species will be produced during

ton resulting higher probability of agglomeration of

coalesced nuclei, and higher fragmentation of the precursor

molecule and surface modification of the coatings, leading

to smooth surfaces.[34] The decrease in the coating thickness

with the increase in the DC of plasma pulse suggested the



contribution of ablation leading to the depletion of PFDA

coatings at higher DC (DC¼ 10%: thickness¼ 700� 40 nm;

DC¼ 25%: thickness¼ 600� 50 nm; DC¼ 50%: thick-

ness¼ 450� 50 nm; DC¼ 75%: thickness¼ 205� 25 nm;

CW (DC¼ 100%: thickness¼ 190� 25 nm). Therefore, the

gradual change in the surface morphology of PFDA coatings

may be attributed to the alteration of relative contribution

of deposition and ablation/etching under different DC

conditions.[45]

In order to rule out the effect of thickness on the surface

morphology of PFDA coatings prepared under CW and PM

mode, we have taken the cross-sectional FESEM images of

the PFDA films (Figure 5) and compared the surface

morphology of two films prepared under CW and PM

mode having almost comparable thickness values

(DC¼ 75%: thickness¼ 205� 25 nm; CW (DC¼ 100%: thick-

ness¼ 190� 25 nm). A clear difference can be seen not only

in the surface morphology but also in the bulk morphology

of the two films prepared under PM and CW plasma mode.


Figure 5. Field emission scanning electron microscopy (FESEM) images of PFDA coatingsprepared under (a) DC¼ 75%, thickness¼ 205� 25 nm and (b) CW (DC¼ 100%), thick-ness¼ 190� 25 nm (Ppk¼ 1W).

934


Moreover, we have shown in our earlier study that the

chemical composition of the PFDA coatings also varied with

the change in plasma parameters i.e., CW and PM mode,

plasma power, DC (other experimental parameters are the

same).[34] These observations clearly suggest that the

coating thickness is not the parameter that governs the

surface morphology of the plasma polymerized PFDA

coating. Therefore, it can be concluded that the difference

in the surface morphology of PFDA coatings is attributed to

the difference in the growth processes involved in the

different plasma conditions.

The influence of DC on the surface wettability and

morphology of the PFDA coatings was revealed by gradual

decrease in the CA of water (from 126.58 for DC¼ 10% to

107.08 for DC¼ 100%) and diiodomethane (from 105.08for DC¼ 10% to 93.08 for DC¼ 100%) with the increase in

the DC of the plasma discharge (Table 1). It can be seen

that there is an increase in the total surface energy (from

7.3 mN �m�1 for DC¼ 10% to 13.4 mN �m�1 for DC¼ 100%)

as well as polar and dispersive component of surface

energy of the PFDA coating with the increase in the DC

of the plasma discharge (Table 1). The advancing and

receding CAs for water decreased and WCAH increased

with the increase in the DC of the plasma discharge

(Table 2), which is attributed to the increase in the polar

surface energy component and change

in the surface morphology.

Figure 6. Field emission scanning electron microscopy (FESEM) images of Whatmanpaper (a) untreated (b) PFDA coated (PM mode; ton¼ 25ms, toff¼ 75ms, Ppk¼ 1W).

Super-Hydrophobic Property of1H,1H,2H,2H-perfluorodecyl acrylate(PFDA) Coating on Paper

Figure 6 shows FESEM images of the

untreated and plasma polymerized

PFDA coated Whatman filter paper-50,

showing no structural damage to the

fibrous microstructure of paper. In addi-

tion, the ribbon like micro-fibrous mor-

phology of the paper was maintained



and even became more prominently

visible after the thin coating of PFDA,

which leads to quite higher CAs

(ua¼ 1578) (Table 2). The conformal thin

coating of PFDA on the super-hydrophilic

paper transformed it into a super-hydro-

phobic surface, due to the combined

effect of the presence of micro-roughness

of intrinsic fibrous structured of paper

and high degree of fluorination. The

superhydrophobic property of plasma

polymerized fluorocarbon coatings with

ribbon like nanostructured morphology

produced from C2F4 precursor gas have

been reported by d’Agostino and cow-

orkers.[73] Moreover, the static CA of 1228 for diiodo-

methane on PFDA coated paper revealed the oleophobic

property of the PFDA coatings, which is attributed

to the long perfluorinated carbon chain length contain-

ing CF2 and terminal CF3 groups present in the PFDA

coatings.[51,55]

The PFDA coated Whatman paper (PM-1W-DC25) exhi-

bits higher advancing and receding CA and lower WCAH

value (ua¼ 1578, uc ¼ 1408, WCAH¼ 178) as compared to

PFDA coated smooth Thermanox substrates (ua¼ 1378,uc ¼ 1028, WCAH¼ 358) (Table 2). However, the lowest

WCAH value of 178 found for Whatman paper at PM-1W-

DC25 conditions is quite high and therefore, the CA theories

suggest that the super-hydrophobic character of these

surfaces follow the Wenzel model of solid-water wetted

contact leading to sticking (non-slippery) behavior of

PFDA coated paper surfaces.[60,82] In principle, mere rough-

ness is not directly correlated to slippery super-hydro-

phobicity; rather the height and distribution of the

structures are more important factors for slippery super-

hydrophobicity. In general, structures with greater

height and lower density result in reduction of hysteresis,

which is an essential requirement to reach a Cassie–Baxter

regime showing a slippery character for self cleaning

applications.[82]

DOI: 10.1002/ppap.201000038

120001000080006000400020000-25

-20

-15

-10

-5

0

Untreated Au

PFDA coating

∆Fr

eque

ncy/

Hz

Time/s

(a)

-25

-20

-15

-10

-5

0

Untreated Au

PFDA coating

(b)

Time/s

∆Fre

quen

cy/H

z

120001000080006000400020000

120001000080006000400020000

-100

-80

-60

-40

-20

0

Untreated Au

(c)

PFDA coating ∆Fr

eque

ncy/

Hz

Time/s

Figure 7. Time-dependent QCM frequency responses of untreatedAu coated QCM crystal sensor and Au coated QCM crystal sensorcoated with plasma polymerized PFDA film (PM mode, DC¼ 25%,Ppk¼ 1W) when contacted with protein solutions (a) OVA, (b) HSAand (c) FGN. The arrow shows the point of injection of proteinsolution.


Protein Repellent Property of 1H,1H,2H,2H-perfluorodecyl acrylate (PFDA) Coatings

Low-surface-energy polymeric coatings, such as fluorocar-

bon coatings offer a potential means of inhibiting the

biofouling process by presenting a non-stick surface to

biofouling species.[83,84] Increased interest in this approach

was motivated by the observation that the well-known

gorgonian corals with low surface energy natural antifoul-

ing surfaces do not allow the colonization by marine micro-

organism.[85]

The protein repellent properties of the PFDA surfaces (PM

mode; ton¼ 25 ms, toff ¼ 75 ms, Ppk ¼ 1 W, thickness �50 nm) were analyzed by QCM in a continuous flow mode.

Three different proteins, namely, OVA, HSA and FGN in PBS

solution were injected individually and their adsorption

behavior was studied by monitoring frequency as a

function of time. QCM has been widely utilized as an easy

technique for online investigation of surface-related

processes in liquids, including protein adsorption.[62–67]

In the present study, we have used decrease in the

frequency as an approximate measure of the adsorbed

protein for making a comparison among the adsorption

levels of three different proteins on a same PFDA surface

under the identical conditions. Moreover, the dissipation

shift during the protein adsorption process were found to be

low (<0.1E-5 for HSA and OVA;<0.6E-5 for FGN), indicating

the formation of a rigid layer of proteins, which rules out the

significant influence of viscoelastic effect; allowing us to

compare the adsorption behavior of different protein

molecules on PFDA coatings and untreated Au surfaces.

The higher dissipation shift in case of FGN was attributed to

its higher adsorbed amount leading to thicker layers, which

can imbibe water molecules that make the protein layer

soft with a resulting damping of the quartz oscillation. In

fact, several reports are available on the estimation of

amount of proteins adsorbed by QCM using Sauerbrey

relation and the adsorption behavior of proteins on various

hydrophilic and hydrophobic surfaces, using Sauerbrey

equation.[62,86,87] Rickert have reported that despite the

high hydration of the protein layers, viscosity-induced

effects play a negligible role and that the frequency

decrease reflects primarily mass changes at the surface.[66]

Quartz crystal microbalance (QCM) frequency responses

of untreated Au coated quartz crystal and PFDA coated Au

coated quartz crystal for OVA, HSA and FGN are presented in

Figure 7a, b and c, respectively. For untreated as well as

PFDA coated QCM crystal surfaces, the frequency decreased

sharply immediately after injection of protein solutions due

to adsorption of protein molecules, after that the frequency

almost leveled off indicating the saturation of protein

adsorption. The initial fast decrease in resonance frequency

followed by second slower adsorption process indicated an

irreversible protein adsorption process that depends on the


� 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plasma-polymers.org 935

936


type of protein, number of available binding sites and

surface energy of substrates, which determines the final

coverage. Plasma polymerized PFDA coatings showed lower

adsorption of proteins as compared to gold surfaces, which

indicated the inert and protein repellent, i.e., anti-biofoul-

ing characteristics of PFDA coatings towards adsorption of

protein biomolecule. The extent of frequency change of

QCM sensor due to the adsorption of protein molecules

varied for different proteins, indicating different adsorp-

tion behavior of different proteins. From the QCM analysis,

it was observed that coating of PFDA on Au surfaces reduced

the protein adsorption by�50%, 70% and 17% for OVA, HSA

and FGN, respectively. Another interesting aspect of protein

repellent characteristics of surface is the kinetics of

adsorption. The kinetics of protein adsorption on untreated

Au coated QCM crystal was found to be faster than on PFDA-

coated Au coated QCM crystal. The adsorption kinetics of

OVA and HSA on PFDA coatings was slower as compared to

FGN. The variation in the adsorption kinetics and the

antifouling characteristics of PFDA coatings against differ-

ent protein molecules is attributed to the varying affinity of

the coating surfaces towards protein molecules, due to

difference in the surface-chemical properties of different

protein molecules. Another factor is the number of contacts

between the macromolecule and the substrate surface;

multiple contact formation leads to higher and stronger

adsorption. FGN being a hydrophobic and bigger protein

molecule (MW� 340 kDa) as compared to HSA

(MW� 66 kDa) and OVA (MW� 45 kDa) interacted with

substrate through hydrophobic interaction and offers

higher numbers of contact sites for adhesion, which leads

to faster and higher adsorption as compared to other

proteins.[88] Evans-Nguen and Schoenfisch have reported

that protein (FGN) adsorption could be substantially higher

on hydrophilic surface provided that the surface is

positively or negatively charged.[89] Similar results have

been reported by Choukourov et al. where they have also

found that the FGN adsorbs faster and in higher amount on

gold surface than on CF3-terminated SAM, which was

attributed to the influence of the surface charge present on

gold surface.[86]

Conclusion

The deposition time, CW and PM plasma mode, plasma

power and pulse DC play crucial role in tailoring the surface

morphology, CA and surface free energy characteristics of

the plasma polymerized PFDA coating. The plasma poly-

merized PFDA coating has been successfully utilized to

transform a super-hydrophilic surface of Whatman filter

paper into a super-hydrophobic and oleophobic surface due

to the conformal low surface energy thin PFDA coating with

high degree of fluorination complemented by the micro-



rough and fibrous microstructured morphology of paper.

Low-surface-energy PFDA coatings offer possible applica-

tions in paper industry for the development of water

repellent, oil repellent, stain resistance papers. The protein

adsorption study showed that PFDA coating exhibited

significant protein repellent behavior against three model

proteins namely, OVA, HSA and FGN, suggesting a potential

means of inhibiting the biofouling of material substrates by

presenting a non-stick surface.

Acknowledgements: ACTECO-EC project (515859-2) is acknowl-edged for financially supporting the work. Authors sincerely thankto Dr. D. Mataras, Dr. Ergina Farsari, PTL, University of Patras,Greece for AFM analysis, Dr. Reza Jafari from ENSCP, Paris,Dr. G. Giudetti from JRC, Italy and other partners of the project fortheir active support and discussion.

Received: March 20, 2010; Revised: June 11, 2010; Accepted: July8, 2010; DOI: 10.1002/ppap.201000038

Keywords: antifouling; fluorocarbon coating; 1H,1H,2H,2H-per-fluorodecyl acrylate (PFDA); hydrophobic; morphology; oleopho-bic; plasma enhanced chemical vapor deposition (PECVD); proteinadsorption; surfaces

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DOI: 10.1002/ppap.201000038

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