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13/10/2017

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Smart Technologies and Products for Textile and Apparel Industry – Vilnius – 19/10/2017

New developments for functional textile carried out in the frame of electrospun textile material

University of Haute-Alsace (UHA) Ecole Nationale Supérieure d’Ingénieurs Sud-Alsace (ensisa)

Laboratoire de Physique et Mécanique Textiles EA 4365 (LPMT) 11, rue Alfred Werner – 68093 Mulhouse CEDEX – France

e-mail : [email protected]

1

Dominique C. Adolphe, Laurence Schacher, Nabyl Khenoussi

Elham Mohsenzade, Neda Shah-Hosseini, Sliman El Muhamed

Aurélie Oertel, Ahsan Nazir


Where are we?

F CH

D

Mulhouse

Bâtiment Lumière

Paris Strasbourg

Bâtiment Werner

Suisse

Mail Central UHA

2


35 research staff

38 PhD Students

6 adm. + techn. staff

Who are we ?

The Laboratoire de Physique et Mécanique Textiles

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What are our specialties? 3 thematics and 9 axes

4

Characterization Advanced Mechanical and Physical Characterizations Sensory analysis and Garment characterizations

Functionalization

Physico-chemical functionalization for textile Materials Mechanical and physical functionalization of textile Materials thanks to

electrospinning processes

Processes and Products

Elaboration, study and modelling of mechanical behaviour of fibers and yarns

Elaboration and mechanical behaviour study of textile complex structures

Elaboration and mechanical behaviour study of composite materials Elaboration and mechanical behaviour study of textile biomaterials Elaboration of the instrumented textiles


Human hair is 200 times bigger in diameter than an average typical nanofiber

www.elmarco .com

Why nano web are studied?

5

•Human hair

•Pollen grain

•Nanofibers

1000x magnified


The smaller the fiber diameter

H. SCHREUDER-GIBSON et al. J. Adv. Mater. 2002, 34


6

The smaller the pores of the nonwovens are

D. Hussain et al. Polymer, 2010 , 51.

The bigger the specific surface area is

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Mass reduction

What is the mass of polymer needed to link the Earth to the Moon thanks to a filament with a 100nm diameter?

Earth Moon

Solution: Polymer Mass = V ρ = (πr2L) ρ

= π(50 nm)² (380,400 km) (1 g/cm3) ≈ 3 g


Nanofibers Applications

Tissue engineering

Wound dressing

Medical application

Drug delivery

Cosmetics Filtration

Protective clothing

Material reinforcement

and many others


8


The LPMT nano-spinning group

9

Prof. Laurence SCHACHER

Prof. Dominique ADOLPHE

Nabyl KHENOUSSI Ass. Prof.

Sliman EL MUHAMED Ass. Prof. HEI

Aurélie OERTEL Newly Doctor

(05/2017)

Elham MOHSENZADEH PhD Student

Neda SHAH HOSSEINI PhD Student

Ahsan NAZIR Ass. Prof. NTU

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The LPMT nano-spinning group

7 Ph.D. Thesis (4 defended)

10 Masters

22 Projects defended (Master level)

11 Publications 61 International oral conferences

10


Outline Electro spinning principle

Development of the electrospinning booth

Study of electro spinning parameters

Product developments Normal nano filaments

Functionalized nano-filaments

Object developments

Complex structure developments

Conclusions

11

Smart Technologies and Products for Textile and Apparel Industry – Vilnius – 19/10/2017 12

How to produce Nanofibers?

Nabyl Khenoussi, Contribution à l'étude et à la caractérisation de nanofibres obtenues par électro-filage, PhD thesis, LPMT, 2010 Amir H. HEKMATI, Elaboration and physical and mechanical characterization of electrospun nanowebs, PhD thesis, LPMT, 2011

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Process Production Advantages Disadvantages

Drawing Laboratory Very fin nanofibers Discontinuous process

Template synthesis Laboratory Tailoring fiber diameter by tailoring of template

Special templates

Phase separation Laboratory Minimum equipment requirement

Only some polymers

Self-assembly Laboratory Very fin nanofibers Very difficult process

Island-in-the-sea Industrial Control fiber diameter Expensive, only some polymers

Melt blown Industrial High productivity Expensive, only some polymers

Forcespinning Industrial Cost effective Solvents may cause corrosion

Electrospinning Industrial Cost effective High voltage

How to produce Nanofibers?


Electrospinning Process - Principle

Pump

syringe

E = High Voltage

+ - collector

1

2 3

1 : Taylor Cône 2 : Simple Jet 3 : Electro-splaying

Attraction to the collector

Repulsion in the polymer + + + + + + + + +

Nabyl Khenoussi, Contribution à l'étude et à la caractérisation de nanofibres obtenues par électro-filage, PhD thesis, LPMT, 2010

14


Photography of the droplet under electrostatic field

Courtesy of Dr. Darrell Reneker, Univ. Akron

Electrospinning process – Principle

15

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Study of Taylor cone


1960 Taylor : formation of a cone a the tip of the needle where the jet is initiated

Taylor : = 49,3° (spheroidal approximation)

Yarin : = 33,5° (hyperbolic approximation)

Jet stability Nonwoven Homogeneity

Taylor cone and jetting from liquid droplets in electrospinning of nanofibers - Yarin A.L., Koombhongse S.- Journal of Applied Physics, Vol. 90, No. 9, (2001)

Bending instability in électrospinning of nanofibers - Yarin A.L., Koombhongse S. – Journal of Applied Physics, Vol. 89, No. 5, pp 3018-3026, (2001)

16


Reneker D. & Yarin L., Polymer, 49, 2008.


17

Taylor cone


Solution parameters

• Concentration • Viscosity • Conductivity • Polymer type

Process parameters

• Applied voltage • Collecting distance • Feed-rate • Kind of needle

Ambient parameters

• Relative humidity • Ambient temperature

Electrospinning parameters

Electrospinning Process - Parameters

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Needed components

How to build a Electrospinning Booth

Electrospinning Booth

19

• Syringe • Needle

• Controlled pump

• Collector • Security device

• High voltage power supply


The first Setup …. 2005

L. Barberou : Master Projet - 2004–2005

20

Collector Pump High Voltage Source

Syringe

Security device


The first nano web …. 2005

L. Barberou : Master Projet -2004 – 2005

21

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Second Setup 2007

L. Dumée – B. Perron : Master Projet - 2006 – 2007

22

Collector

Pump High

Voltage Source

Traveling Syringe

Security device


Collector system (modular)

Automatic motion system

Needle

Needle orientation system

Pump Secured booth

High voltage system

23

Third Setup - 2007

Alireza SAIDI : Master Thesis - 2006 – 2007


To scale-up the lab developments

Purchase of Nanospider™ NS 1WS500U - 09/2013

24

Aurélie OERTEL: Ph.D. Works - 2012 – 2016

Purpose : Scale up the developments carried out in at a laboratory scale Transfer them to industry

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How it is working ? Principle : Needleless electrospinning

25

Film : El Marco Company


Solution parameters

• Concentration • Viscosity • Conductivity • Polymer type

Process parameters

• Applied voltage • Collecting distance • Feed-rate • Kind of needle

Ambient parameters

• Relative humidity • Ambient temperature

Electrospinning parameters

Study of Electrospinning Parameters

26


Study of Electro Spinning parameter for PVA

Rosista IVANOVA : Master Thesis - 2005 – 2006

N needle voltage Distanc

e

Flow

rate

conce

ntratio

n

Time N needle Voltage distance Flow

rate

conce

ntratio

n

time

18.2 1.1 15 17.5 50 9 30 17.3 0.9 20 18.5 50 9 30

17.2 0.9 15 18.5 50 9 21 15.3 0.7 15 18.5 50 6 20

15.2 0.7 15 22.5 70 6 21 15.1.2 0.7 15 22.5 50 6 30

15.1.1 15.8 1.2 20 18.5 50 6 20

15.7.2 1.1 15 18.5 50 6 30

15.6 0.9 15 18.5 50 6 25 15.5 0.9 15 22.5 50 6 11

15.4 0.7 20 22.5 50 6 23 12.8 0.7 20 18.5 50 13.5 7

12.2.2 0.7 20 22.5 40 6 14 12.2.1 0.7 20 22.5 40 6 14

12.13 0.7 20 22.5 50 9 30

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Study of multi syringes device

Equipotential et Field lines for 2 needles

Field line for 4 needles in circle. Profile view.

L. Dumée – B. Perron : Master Projet - 2006 – 2007

28


a = 1,3795

R2 = 0,9936

a = 3,8552

R2 = 0,999

a = 2,7955

R2 = 0,9946

1

10

100

1000

10000

1 10 100

Concentration polymère (% massique)

|hsp|

PA-6

C**

Ce

Study of Solution parameters : PA Rheological analysis



Study of concentration/viscosity PAN Rheological analysis

a = 4,4021

R2 = 0,999

a = 2,7116

R2 = 0,9994

a = 1,3328

1

10

100

1000

10000

1 10 100Concentration polymer (% weight/weight)

|hsp|

PAN

(% massique)

Ce

C**


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To summarize

Solution parameters: Concentration/Viscosity

Diluted regime Polymer beads

Entanglement Critical Concentration

Branched Filaments and beaded filaments

Concentrated regime Stable spinning

Homogeneous morphology


(d)

(a) (b)

(c)

9 kV -Electrospinning is initiated - Non-beaded nanofibers

10 kV -Typical Taylor cone - More uniform nanofibers

11 kV - Very small Taylor cone - Beads-on-string

12 kV -Taylor cone recedes into needle - Beads & beads-on-string

Jalili et al. Iran. Polym. J. 14, 2005

Studied case

15 wt% PAN in DMF

Voltage: 9-12 kV

Distance: 15 cm

Feed-rate: 1 ml/h

32

Study of process parameters : Influence of applied voltage


5 cm

7.5 cm

15 cm

Case studied

15 wt% PAN in DMF

Voltage: 10 kV

Distance: 5, 7.5 & 15 cm

Feed-rate: 2 mL.min-1

33

Jalili et al. Iran. Polym. J. 14, 2005

Study of process parameters : Collecting distance

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DOE to determine the optimal conditions for electrospinning PAN/DMF solution

34

Material ES Mechanism DOE Runs Validation

Runs Inputs Constants Results

PAN

Needle based

FF 27 4

Concentration; wt% (9, 11.5,

14)

Distance; cm (15, 20,

25)

Voltage; KV (10,

12, 14)

Sol. Flow rate (0.2

mm/hr)

Needle diameter (0.7

mm)

3 optimized

samples

RS

(CCD) 20 4

Concentration; wt% (9, 11.5,

14)


25)

Voltage; KV (10,

12, 14)

Sol. Flow rate (0.2

mm/hr)

Needle diameter (0.7

mm)

Needleless RS

(CCD) 20 4

Concentration; wt% (5, 7, 9)


25)

Voltage; KV

(30,35,40)

Carrier sp (200 mm/s)

Substrate sp (0

mm/min)

Air flow (80/130

mm/hr)

Time (10 min)

1 optimized

sample

Ahsan Nazir, Modelling and Optimization of Electrospun Materials for Technical Applications, PhD thesis, LPMT, 2016


Optimal conditions for electrospinning PAN/DMF solution

35

Effect of Input Parameters on nanofiber diameter and its distribution: Prediction models

Material Output ES

Mechanism DOE Model R-sq

PAN

Fiber Diameter

Needle

FF Y = -2587.92 + 309.731 C 83.79%

RS (CCD)

Y = 1546.23 - 392.928 C + 28.3737 C2

88.43%

Needleless RS

(CCD) Y = 598.220 - 225.317 C + 9.66554 D + 23.253 C2

76.83%

Fiber Diameter Distribution

Needle

FF YSD = -971.178 + 72.603 C + 29.2342 V

55.83%

RS (CCD)

YSD = -2491.41+ 64.7471 C + 94.3108 D + 179.792 V - 8.71139 D×V

53.02%

Needleless RS

(CCD)

YSD = 648.951 - 206.320 C + 16.958 C2

54.19%



Production of nano webs

36

Mean Diameter 310 nm St. Dev., 62 nm

Mean Diameter 332 nm St. Dev., 71 nm

X 1000 X 1000

X 5000 X 5000


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Development of products

Our research is concentrated on Functionalized products ○ Functionalized with carbon nano tubes

○ Functionalized with inorganic particles

On shape products ○ Round shape with random orientation

○ Flat shape with organized orientation

○ Sandwiched structure

37


Functionalized products

The properties of the nano web can be enhanced in terms of

• Electrical properties

• Surface properties

• Adsorption properties

38

b ) 5% PAN/1% NTC d ) 5% PAN/1% NTC

10 µm 2 µm

10 %wt. Na-MMT 3,200x

2µm By embedding nanosize particles


Improvement of electrical property

Nano particles embedded : Multi wall carbon nano tube

39

Provides by Arkema Company

SBET (m2/ g)

C %

H %

N %

S %

Al %

Fe %

254 92.18 0.71 0.18 0.3 3.81 1.96

These Maafa – University of Haute-Alsace 2006

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Improvement of electrical property

How to include nano particles into nano filaments ?

How to avoid the aggregates ?

How to obtain a homogenous dispersion ?

40

Define a special procedure to achieve the dispersion


Stirring

70 °C for 24 h

(mPAN) g PAN

Ultrasonication bath

37 kHz, 50 °C for 30 min

Variables Filler mass fraction

0.2 0.4 0.5 0.7 1.0 1.5 wt%

High shear mixing

Ultra-Turrax® T25

18,000 rpm /30 min

(mfiller) g filler +

20 ml DMF

Preparation of PAN/MWNT dispersions

MWNT/DMF

PAN/MWNT/DMF

0.2 0.4 0.5 0.7 1.0 1.5%

Sliman Al Mohamed, Study and Development of Nonwovens Made of Electrospun Composite Nanofibers, PhD thesis, LPMT, 2015


Nonwoven of PAN/MWNT composite nanofibers

0

200

400

600

800

1000

1200

1400

PAN

0% MWNT

PAN

1.9% MWNT

PAN

3.8% MWNT

PAN

4.7% MWNT

PAN

5.6% MWNT

PAN

7.4% MWNT

PAN

9.2% MWNT

Mean

nan

ofib

er

dia

mete

r [n

m]

11.5 kV

13 kV

14.5 kV

PAN + 1.9 % MWNT PAN + 3.8 % MWNT PAN + 4.7 % MWNT PAN + 5.6 % MWNT

42

Incorporation of MWNT yields thinner nanofibers

Morphological observations


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Topographical Analysis PAN/MWNT using AFM

43

PAN PAN + CNT

AFM photo –ENSISA - Dr. Wang – Dr. Le Huu

Nabyl KHENOUSSI -Ph.D. Works - 2007 – 2010

Nonwoven of PAN/MWNT composite nanofibers Morphological observations


g = 1.3 ± 0.1 mm

A = (a + g) (b + g) = 364.6 mm2

P = 2( a + b + 2g) = 76.4 mm

a

b

Customize the electrode regarding the existing standard and the size of the samples

44

g

Electrode

holder made of

polycarbonate

Electrode № 3

Electrode № 2

Electrode № 1

P

A

Characterization of electrical properties Measurement of electrical resistance



Surface resistance (Rs)

Volume resistance (Rv)

Measurement of electrical resistance

45

Characterization of electrical properties

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0 kPa 0.5

kPa

0.9

kPa

1.3

kPa

1.7

kPa

2.2

kPa

2.6

kPa

Characterization of electrical properties

Influence of applied mechanical pressure

Without applied loads

With applied loads Measurement of electrical resistance

46


Measurement of electrical resistance

1,E-12

1,E-10

1,E-08

1,E-06

1,E-04

0 1,9 3,8 4,7 6,5 9,2 13

Vol

ume e

lect

rica

l co

nduc

tivi

ty

[S/m

]

MWNT mass fraction [wt%]

Increase the volume electrical conductivity by six order of magnitude

1,E-15

1,E-13

1,E-11

1,E-09

0 1,9 3,8 4,7 6,5 9,2 13

Sur

face

ele

ctri

cal

cond

ucti

vity

[S/s

quar

e]

MWNT mass fraction [wt%]

47

In the limit of used concentration, no surface electrical percolation threshold is observed.


Electrical percolation behavior


0

5

10

15

20

25

30

0,5 0,9 1,3 1,7 2,2 2,6

Vol

ume R

esi

stiv

ity

(ρv)

(MΩ

.cm

)

Applied pressure (kPa)

PAN + 4.7% MWNT

PAN + 6.5% MWNT

PAN + 9.2% MWNT

PAN + 13% MWNT

48

Volume electrical resistivity Applied pressure

Development of pressure sensors of low amplitude

Measurement of electrical resistance Influence of the pressure applied


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Porous glasses

Porous gels

Ultra-large pores zeolites

Pillared layered solids

(Clays)

Zeolites

Pore diameter (nm) 0.5 1 5 10 50 100

M i c r o p o r e s M a c r o p o r e s M e s o p o r e s

Improvement of the surface properties

Na-MMT

49

2 50

Behrens P, Adv. Mater. 5, 1993

Embedment of Na-montmorillonite layered silicate


Microstructure

50

Bergaya F & Lagaly G, Handbook of Caly Science, Elsevier, 2013

Improvement of the surface properties Embedment of Na-montmorillonite layered silicate


High aspect ratio

High specific surface area : ~ 800 m2/g

Cation exchange Substituting compensating cations by organophilic ones

Miscibility with hydrophobic matrices

Expanding the interlayer space

Na+ cations Organic onium cations Silicate layers

51 Pavlidou S & Papaspyrides D, Prog. Polym. Sci. 33, 2008

Properties


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Synthetic Na-MMT

Supplied by Pôle Matériaux à Porosité

Contrôlée, IS2M UMR CNRS 7361 -Université

de Haute-Alsace

Synthesized by sol-gel method

Aggregates of Na-MMT

Average size: 3.3 ± 1.3 µm

52

Reinholdt M, Miehé-Brndlé J. et al. Eur. J. Inorg. Chem. 2001



PAN/Na-MMT/DMF

Stirring

70 °C for 24 h

(mPAN) g PAN

Ultrasonication bath

37 kHz, 50 °C for 30 min

Variables Filler mass fraction

2 3 5 wt%

High shear mixing

Ultra-Turrax® T25

18,000 rpm /30 min

(mfiller) g filler +

20 ml DMF

Na-MMT/DMF

Preparation of PAN/Na-MMT dispersions



PAN/Na-MMT

nonwoven in

C16TMA Cl of

0.002 mol/L

Stirring

2h / 25 °C

Centrifuging

15,000 rpm

Washing with

distilled water

Drying

12 h / 60 °C SAXS

Cation exchange of PAN/Na-MMT composite nanofibers

54

Improvement of the surface properties

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5 %wt. Na-MMT 3,200x 2µm 0 %wt. Na-MMT 3,200x 2µm


11.5 kV

55

Nonwoven of PAN/Na-MMT composite nanofibers Morphological observations





13 kV

56






14.5 kV

57



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0

200

400

600

800

1000

PAN PAN

5% MMT

PAN

10% MMT

PAN

19% MMT

Nan

ofib

er

avera

ge d

iam

ete

r [

nm]

11.5 kV

13 kV

14.5 kV

58

Incorporation of Na-MMT yields thinner nanofibers The higher the mass fraction, the thicker the nanofibers are

Nonwoven of PAN/MWNT composite nanofibers Morphological observations



0 10 20 30 40 50 60 70

Abso

lute

Int

ens

ity

Position 2ϴ (°)

Na-MMT powder

PAN at 11.5 kV

PAN +19% Na-MMT at 11.5 kV

(060)

(110)

(130)

(001)

17° PAN equatorial

peak

59

No change in PAN crystallinity

Na-MMT layers are slightly intercalated

Nonwoven of PAN/Na-MMT composite nanofibers Structure observations - WAXS



3 4 5 6 7 8 9 10

Abso

lute

Int

ens

ity

Position 2ϴ (degree)

PAN/NaMMT as-produced nanofibers

CTMA-treated PAN/MMT nanofibers

(001)

(001)

Na+

C16TMA+

9.7 Å

5.2 Å

60

The interlayer space of Na-MMT is still accessible

Nonwoven of PAN/Na-MMT composite nanofibers Structure observations – Evaluation of the interlayer distance - SAXS


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The interlayer space of Na-MMT is still accessible for all PAN/Na-MMT composite nanofibers

61

Nonwoven of PAN/Na-MMT composite nanofibers Structure observations – Evaluation of the interlayer distance - SAXS


Products Development

62

Valorization of the electro spun Know-How

Synthesis of the polymers Laboratory Chimie-Provence University of Aix Marseille

Electro spinning and shaped LPMT University of Mulhouse

In vivo and evaluation and specification sheet ISM - UMR 6233 Faculty of Sport’s Sciences Marseille

In vivo evaluation – Cellular test NICN - UMR 6184 Institut Jean Roche Marseille

2 mm 2 mm 10 mm

∅ = 1 mm

Nerve Guide development

Nabyl KHENOUSSI - Contribution a l'étude et a la caractérisation de nanofibres obtenues par électro-filage « application aux domaines medical et composite » Ph.D. works - 2010


Provide nerve guidance channels

Prevent target organ atrophy, degeneration

Avoid regeneration errors

Allow regeneration

over long distances

Bionic Technology, Australia

63

Products Development Nerve Guide development: Requirements

Nabyl KHENOUSSI - Ph.D. Works - 2010

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End to end reconnection Could be performed only for short nerve

gap (typically 5 mm)

For longer gap Excessive suture tension

Poor results

Peripheral regeneration errors

64

Products Development Nerve Guide development: Neurorhaphy



Mainly used when the inter-lesion distance

is larger (5-10mm)

Limitations • donor nerve size • nerve may not regenerate fully • tumor derived from nervous tissue

65 Nabyl KHENOUSSI - Ph.D. Works - 2010

Products Development Nerve Guide development: Autologous nerve graft


Tubular nerve guides made of natural or synthetic materials

Mainly used when the inter-lesion distance is less to 5mm

•Extracellular matrix (ECM) polymers purified from tissue such as collagen •Silicon tubes

Limitation : rigid /doesn’t allow nerve to grow / can induce inflammatory reactions

66

Products Development Nerve Guide development: Artificial Grafts


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Nerve guide specification

Dimensional specification

Biocompatility specification

Mechanical specification

67 Nabyl KHENOUSSI - Ph.D. Works - 2010


The nerve guide has to present the following dimension

∅ = 1 mm

0,2 mm

2 mm 2 mm10 mm

∅ = 1 mm

∅ = 1 mm

0,2 mm

∅ = 1 mm

0,2 mm

2 mm 2 mm10 mm

∅ = 1 mm

2 mm 2 mm10 mm

∅ = 1 mmCaractère

diamètre

L e =

Ǿ

Ǿ

68

Products Development Nerve Guide development: Dimensional Specification


What kind of collector could be used ?


Use of synthetic materials

reproducibility of fabrication

calibrated geometric shape: length, diameter

Design criteria

biocompatible & biodegradable

suitable interior surface helping regeneration

guide for growing axons in the right direction

69

Products Development Nerve Guide development: Biocompatibility specification

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The collector has to be In cylinder shape

Conductive

Customized to facilitate the guide removing

Two possibilities could be envisaged Static drum

Rotating drum

70

Products Development Nerve Guide development: Design of the collector


Collector material

This material has to be easily processed

be conductive

be slippery (low friction coefficient)

Chosen material : Specific polymer charged with graphite

71



Rotating drum Good thickness homogeneity Oriented structure Heavy to handle

Chosen device : Static Drum

Static drum Random structure Easy to handle More difficult to manage the thickness

72


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Obtained Guides

73



Products Development Nerve Guide development: Obtained guides

Electrospinning conditions

• Tension: 9.8kV

• Distance needle/collector: 10cm

• Feedrate: 0.0707mL/h

• Needle diameter: 0.7mm

• Diameters : 250 - 400 nm



No superposition of the pick of the solvent (chloroform)

Residual rate of solvent lower than the accuracy of the measurement device

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

900 950 1000 1050 1100 1150 1200 1250 1300

Nombre d'onde (cm-1

)

Inte

nsité

PLA-b-PHEA (nanofibres)

Chloroforme

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

900 950 1000 1050 1100 1150 1200 1250 1300

Nombre d'onde (cm-1

)

Inte

nsité

PLA-b-PHEA (nanofibres)

Chloroforme

75

Products Development Nerve Guide development: IR Analyses of the biopolymer


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Bloc PLA Bloc PHEA

Polymers block

LPMT

CROPS

ISM


Products Development Nerve Guide development


LPMT


Products Development How to manage the filament orientation

Bibliographic reviews have highlighted the effect of the filament orientation on the cell growth

How the filament orientation can be customized ?



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27


C. Berger C. – F. Miallet ENSISA -Master Project – 2013-2014,


Bibliographic reviews


Different methods to influence the mat orientation :

- Collector shape

- Collector motion

- Collector speed

- Mat drawing

Photo: N.Khenoussi / LPMT

Électrospinning of Polymeric and Ceramic Nanofibers as Uniaxially Aligned Arrays – Li D., Wang Y., Xia Y., Nano Letters, Vol. 3, No. 8, pp 1167-1171, (2003)

80



Collector shape

Collector motion

Collector speed

Mat drawing

81


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How to obtain different collector shapes

• Machine the collector

• Use new construction tools

3D Printing Tool

82



3D printing process

l

L

e

d Ø

h

3D printer EDEN Objet E230V

83

Products Development How to manage the filament orientation: Structured collector

Neda Shah Hoseini- PhD Work – 2015-…


Semi spherical pillar

Semi spherical Holes

Grooves

Measurements in mm

84


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Adaptation of the

Topography

8 collectors

semi-spherical holes semi spherical pillar

grooves

85



8 specific collectors

86

Geometric characteristics of customized collectors

Collector N°

Height Transversal

step Longitudinal

step diameter/

width


Design [mm] [mm] [mm] [mm]

1 Cylindrical holes 0,7 2,1 2,1 0,05

2 Cylindrical holes 0,4 1,2 1,2 0,05

3 Cylindrical pillars 0,2 0,6 0,8 0,05

4 Cylindrical pillars 0,4 1,2 1,6 0,05

5 Stripes 0,2 0,6 0,6 0,05

6 Stripes 0,5 1,5 1,5 0,05

7 Hemispheric pillars 0,35 1,4 1,05 0,05

8 Hemispheric hole 0,55 1,65 1,65 0,05


CAD CAM 1st prototype

What is the limit of this technique?

Precision of the dimensions?

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Fixed parameters •Solution (PA6-6 + solvant) •Process •Environnement (T°, HR) Variables •Metallization •Lubricant

C. Berger C. – F. Miallet ENSISA Master Project – 2013-2014,

Products Development Electrospinning condition


Example of 0.7mm Hemispheric hole

Example of 0.35mm Hemispheric hole

Case of the Hemispheric holes



Example of 0.5mm stripes Example of 0.2mm stripes

Case of the stripes


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Example of 0.5mm pillar Example of 0.2mm pillar

Case of the Pillar



Pillar shape

Collector 3

Products Development Oriented filaments: Obtained Nanoweb


Aligned Non-Aligned Non-Aligned

Stripes geometry

Collector 5


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Hemispheric hole

collector 8



Aligned Non-Aligned

Aligned

Non-Aligned

95


Stripes geometry


A PA 66 15% 25kV 20 min B PA 66 15% 30kV 20 min C PA 66 15% 30kV 10 min D PA 66 15% 25kV 10 min

Blank

The filament orientation vs Cells growth

Aligned

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The sandwich structure

N.NJEUGNA - S. FENON – ENSISA Master Projet - 2005–2006

97

Nonwoven

Nano-web


Respiratory protection Need good mechanical strength to bear the resistance,

Fine porosity, Comfort properties

Material selected: PA-6

Sandwich structure Nonwoven/ nanoweb / Nonwoven

Industrial production

98


Products Development Respiratory protection : a sandwich structure


Characterization used SEM for morphology Respiratory Filter tester (EN 149+A1:2009) Moisture management tester (AATCC 195) Home made Moisture vapor permeability testing arrangement

(ASTM E96-95) SDL Atlas’ Air permeability tester (ASTM D737)


Products Development Respiratory protection : a sandwich structure

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S.N. C (%)

D (cm)

V (KV)

Cs (mm/s)

Ss (mm/min)

Af (m3/hr)

Dia. (nm)

SD Dia (nm)

1 18 26.0 35 290 15 120 136 23

2 18 26.0 35 290 20 130 134 27

3 18 26.0 35 290 25 140 201 68

4 18 27.5 45 340 15 120 198 77

5 18 27.5 45 340 20 130 183 52

6 18 27.5 45 340 25 140 167 47

7 18 29.0 55 390 15 120 160 37

8 18 29.0 55 390 20 130 147 23

9 18 29.0 55 390 25 140 181 41

10 19 26.0 45 390 15 130 138 23

11 19 26.0 45 390 20 140 215 58

12 19 26.0 45 390 25 120 269 81

13 19 27.5 55 290 15 130 149 37

14 19 27.5 55 290 20 140 173 49

15 19 27.5 55 290 25 120 167 60

16 19 29.0 35 340 15 130 172 42

17 19 29.0 35 340 20 140 172 31

18 19 29.0 35 340 25 120 183 38

Products Development Respiratory protection : Experimental conditions


17% PA-6, 30 KV, 15 cm 20% PA-6, 30 KV, 15 cm

• Optimized PA-6 concentration range: 17%-20%.

• Samples produced at both extremes for getting different fiber diameters and pore sizes

Dia., 115 nm St. Dev., 14 nm

Dia., 152 nm St. Dev., 31 nm

Products Development Respiratory protection : structure observation (MEB)

1k 1k

10k 10k



Addition of PA-6 nanowebs drastically improved filtration efficiency of filters

confirmed by lower penetration of paraffin mist In some cases penetration decreased up to 100%, w.r.t filter without nanoweb

102

0

20

40

60

80

100

120

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18Decr

eas

e i

n par

affi

n pene

trat

ion

(%)

Sample Notation

Initial Penetration Maximum Penetration

Products Development Respiratory protection : Filtration efficiency

% of paraphin penetration vs. filter without nano-coating


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Addition of PA-6 resulted in higher pressure drop across the filters However, in some cases pressure drop fell within the acceptable range Hence, process can be fine-tuned to get the pressure drop within the allowed

limit, with much higher filtration efficiency

103

0

50

100

150

200

250

300

1 2 3 4 5 6 7 8 9 101112131415161718

Inc

reas

e i

n pr

ess

ure d

rop

(%)

Sample Notation

Inhalation at 30 L/min. Inhalation at 95 L/min.

0

50

100

150

200

250

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Sample Notation

Exhalation at 85 L/min. Exhalation at 160 L/min.

Acceptable value Optimized sample


Products Development Respiratory protection : Breathing resistance


Thermal conductivity increased with addition of nanowebs Due to increased density and filling of pores

Air permeability decreased Due to filling of pores of nonwoven media

104

30

32

34

36

38

40

0 2 4 6 8 10 12 14 16 18

Therm

al c

onduc

tivi

ty

((W

/cm

.ºC)

×10

4)

Sample Notation

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18Air

Perm

eab

ilit

y (m

m/s

ec.

)

Sample notation

Products Development Respiratory protection : Comfort properties

Thermal conductivity



Increased water vapour permeability was observed after addition of nanowebs May be attributed to availability of small capillaries that can increase the

evaporation due to higher spreading

105

1,700

1,750

1,800

1,850

1,900

1,950

2,000

2,050

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Wat

er v

apor

per

mea

bil

ity

((g/

s.m

m2)×

10

8)

Sample Notations

Products Development Respiratory protection : Comfort properties

Water vapour permeability


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Conclusions:

Electro spinning offers a huge range of potential applications

Cross fertilization working method is a key issue of the product development

Continuous researches have to be carried out in many field Polymer Collector Emitter (needle or needless)

106


Conclusions:

A special attention has to be paid on the Hygiene and Security issues

The medical applications and in particular tissue engineering is a big issue.

It requests: Special polymers

Special and/or complex structures

107


Thank you to all the contributors

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New developments for functional textile carried out in the frame of electrospun textile material

University of Haute-Alsace (UHA) Ecole Nationale Supérieure d’Ingénieurs Sud-Alsace (ensisa)

Laboratoire de Physique et Mécanique Textiles EA 4365 (LPMT) 11, rue Alfred Werner – 68093 Mulhouse CEDEX – France

e-mail : [email protected]

109

Dominique C. Adolphe, Laurence Schacher, Nabyl Khenoussi

Elham Mohsenzade, Neda Shah-Hosseini, Sliman El Muhamed

Aurélie Oertel, Ahsan Nazir

Documents

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