preparation conductive nylon 6 nanofiber for medical application

16. - 18. 10. 2013, Brno, Czech Republic, EU

PREPARATION CONDUCTIVE NYLON 6 NANOFIBER FOR MEDICAL APPLICATION

*Laleh MALEKNIA ,Ramin KAYALI,Majid MONTAZER

Department of Textile Engineering-Islamic Azad University-South Tehran Branch *[email protected]

Abstract

Conductive Nano fiber use in make of nerve matrix and help us for persuasion nerve with weak electricity

flow to injured limb. In this study, Due to the high flexibility and high elongation nylon 6 and High strength

nylon 6 in front of some chemicals such as acid and weak base chosen for the initial substrate and matrix.

first nylon6 nano fiber electrospinning in different concentration , distance and voltage. Next Carbon nano

tubes due to the high strength and electrical conductivity and other unique properties are used as filler , nano

fiber covered with acid functionalized , single wall carbon nano tube . for survey of diameter and morphology

of nylon 6 nano fiber and quality of pervade carbon nano tube in nano fiber, use FESEM (field emission

scanning electron microscopy). For study of conductive property, electrospin web transform to single fiber

then conductive property Measured by ohmmeter.Study of result display , average of diameter nano fiber is

97 nm and average of electrical resistance is 51.84 Ω .

Keyword: nylon 6 - SWNT – electrospinning – nano fiber – conductivity

1. INTRODUCTION

1.1 Composite nylon 6 and carbon nanotube

Different ways is for used carbon nanotubes in the production of nylon 6 nanofibers . In some articles to the

web of nylon 6 and the carbon nanotube without forming any strong link between nylon 6 and carbon Nano

tubes are mentioned and nylon 6 and carbon Nano tubes alone together, and the only link between them can

be linked is the physical link. In other articles for chemical bonding between nylon 6 and carbon nanotubes,

before or During the manufacturing process, the work is done. In general, the methods employed in the

production of carbon nanotube nano-fibers, nylon 6 is as follows:

Using carbon nano-tubes before spinning

Using carbon nano-tubes in spinning

Using carbon nano-tubes after spinning

In the first way carbon Nano tubes with the percentages ditinct used in the synthesis of polymers Nylon 6

and Polymer chains and nanotubes are engaged and It is also possible to create chemical bonds. In the way

using nano tube in spinning process , Nylon 6 and the carbon nanotube with a certain percentage dissolved

in the common solvent and spinning. In the end way Nylon 6 is spinning next saturate in carbon nano tube

solution. For chemical bonding between nylon 6 and carbon nanotubes need to functionalized CNT.

functionalized CNT is two type , acid functionalized CNT and amin functionalized CNT. (–OH) Group is

formed on the surface of acid functionalized CNT and (- NH2) Group is formed on the surface of amin

functionalized CNT.

mailto:*[email protected]


In the articles different, on the properties of composition Nylon 6 and the carbon nanotube research has

been done. With the addition of carbon nanotubes to the nylon strength and initial modulus increases and

elongation decreases. With increasing the amount of carbon nanotubes, properties more changes .

1.2 Nylon electrospinning:

Factors affecting the electrospinning are two parts, changeable and unchangeable are classified. some of

Changeable Factors is as follows:

Molecular weight, molecular weight

distribution and molecular structure of the

polymer

Spinning solution properties (surface

tension, viscosity and conductivity, etc.)

Potential difference

Feed rate

The distance between the nozzle and the

collector

Each of these parameters have significant effects on the nano-fiber manufacturing. In nylon electrospinning,

Each parameter has a certain range. With increasing concentration or molecular weight nylon6 , Diameter of

nanofibers increases and With increasing Potential difference ,Diameter of nanofibers decrease and With

increasing Feed rate , Diameter of nanofibers increases and With increasing The distance between the

nozzle and the collector Diameter of nanofibers decrease. With decreasing diameter of the nano-fibers are

torn. electrospinning parameters have influence on each other. For achieve the desired electrospinning Web

, Range of parameters must be observed.

2. EXPERIMENTAL

2.1 Materials experiment

Granules of nylon 6 with molecular

weight 30000

Chloroform, Merck

Formic acid %98, Merck

Single-wall carbon nanotubes,

Research Institute of Petroleum

Industry, Iran

2.2 Equipment

acid functionalized CNT

amin functionalized CNT

Fig. 1 Connecting nylon 6 with functionalized CNT


electrospinning Devices , model ES1000

field emission scanning electron

microscopy

DSC, METTLER TOLEDO Company

Ultrasonic, hielscher up400s

Ohm meter, MITZU MP-5000

2.3 Experiment method

2.3.1 Preparation of Nylon 6 solution for electrospinning

First solution with different concentrations of nylon 6 (15%, 18% and 20%) was prepared with formic acid as

the solvent for nylon 6, Then each solution electrospinning by different distances and voltages and Constant

feed rate. Nozzle to collector distance of 10, 13 and 15 cm and a voltage of 17, 20 and 25 kW was

adjusted,11 samples are prepared and Samples are coded.

Table1.Samples are coded

C1 (%) C2 (%) C3 (%)

15 18 20

d1 (cm) d2 (cm) d3 (cm)

10 13 15

V1 (v) V2 (v) V3 (v)

17 20 25

F = 0.09 (ml/hr)

S1: C2V2d1 S6:C3V2d1

S2:C2V1d3 S7:C3V1d3

S3:C2V2d2 S8:C3V2d2

S4:C2V3d3 S9:C3V2d3

S5:C2V2d3 S10: C3V3d3

To study the nanostructure and morphology of the nanofibers FESEM images of the samples are taken and

For study of The thermal properties and Effect of concentration of nylon while the remaining parameters are

Stable, the DSC test were taken from 3 samples.Then, all the Web Nylon 6 dipped in a solution of carbon

nanotubes. Web by turning to string , electrical conductivity of the sample is measured.

2.3.2 Preparation of carbon nanotubes

For cleaning and activation Carbon nanotubes, Carbon nanotubes in a mixture of sulfuric acid and nitric acid,

respectively, which were combined to the ratio of 1 to 2, Boil for 2 hours. then , Single-walled carbon

nanotube with two different percentage 0.1% and 0.3% was dissolved in chloroform. For dispersion of

nanotubes use ultrasonic for 2 hours. Then, for the same conditions, the same amount of dissolved carbon

nanotube and chloroform was poured into 11 different bath. Each nylon web is placed inside a bath for 15

minute. This is done separately for solution 0.1% and 0.3% ,Of the 22 samples, Of the 22 samples, 12

samples were selected to study the morphology and microstructure and sample FESEM were prepared. Web

becomes into yarn by hand and electrical resistivity of the samples was measured with an ohm meter.

2.4 Results and its discussion

2.4.1 The morphology of nylon nanofibers

FESEM images of the samples prepared with 3 different concentrations and 3 different voltage with a

constant feed rate and distance can be concluded that The average diameter of the nanofibers decreases

with increasing voltage. Reducing the diameter of the nanofibers Due to the orientation of the


macromolecular chains of nylon 6 with Towards the Nano Fiber Production and It is because of the

increased tension. Web uniformity first increases and then decreases, also with study of FESEM image can

say With increasing concentration, the diameter of the nanofibers generated voltage rises That the results

obtained matches by other studies results.

S11 S2 S5 S4 S7 S9 S10

Fig. 2 FESEM images of the samples prepared with 3 different concentrations and 3 different voltage, from

left to right increases voltage and from up to down increases concentration

Can be seen by study the thermal test Crystallites initially increases and then decreases with increasing

concentration and Tg and Tm samples is consistent with Nylon 6 , could say the voltage used and the

concentrations used , Optimum voltage is 20 Kv and the optimal concentration is 18%.

20% 18% 15%

Fig. 3 DSC graph from up to down decreases concentration

With increasing Distance of nozzle until collector polymer chains are stretched over a longer time and make

The fiber diameter decreases. With study of FESEM image can say Optimum Distance of nozzle until

collector is 13 cm.

S1 S3 S5 S6 S8 S9

Fig. 4 FESEM images of the samples prepared with 2 different concentrations and 3 Distance of nozzle until collector from left to right increases Distance and from up to down increases concentration

Sample 8

Sample 8, 0.9700 mg

Glass Transition

O nset -3.08 °C

Midpoint 32.33 °C

Inflect. P t. -1.82 °C

Inflect. S lp. -30.29e-03 Wg^-1°C ^-1

Midpoint A STM ,IEC 13.96 °C

Delta cp A STM ,IEC 1.977 Jg^-1K^-1

C ry stallinity 19.27 %

Integral -43.01 mJ

normalized -44.34 Jg^-1

O nset 209.47 °C

Peak 222.06 °C

Endset 229.59 °C

Wg^-1

-2

-1

0

1

°C0 50 100 150 200 250 300 350 400

ê xo

Sa mp le 8

1 3 .0 2 .2 0 1 3 1 7 :0 0 :5 4

ST AR e SW 1 0 .0 0

Ir a n Po ly me r & Pe tr o che mic a l i ns ti t ut e - The r ma l Ana l ysi s: M ETTL ER

Sample 3

Sample 3, 0.8700 mgGlass Transition

O nset 12.82 °C

Midpoint 38.68 °C

Inflect. P t. 25.67 °C

Inflect. S lp. -7.50e-03 Wg^-1°C ^-1



Integral -2.63 mJ


O nset 128.53 °C

Peak 141.33 °C

Endset 149.96 °C


Integral -34.23 mJ


O nset 210.27 °C

Peak 223.65 °C

Endset 231.47 °C

Wg^-1

-0.5

0.0

0.5

1.0

°C0 50 100 150 200 250 300 350 400

ê xo

Sa mp le 3

1 3 .0 2 .2 0 1 3 1 6 :5 6 :2 2

ST AR e SW 1 0 .0 0

Ir a n Po ly me r & Pe tr o che mic a l i ns ti t ut e - The r ma l Ana l ysi s: M ET TL ER

Sample 11

Sample 11, 0.9000 mg

Glass Transition

O nset 5.95 °C

Midpoint 36.14 °C

Inflect. P t. 20.50 °C

Inflect. S lp. -44.28e-03 Wg^-1°C ^-1




Integral -43.36 mJ


O nset 214.41 °C

Peak 224.69 °C

Endset 230.52 °C

Wg^-1

-3

-2

-1

0

1

2

°C0 50 100 150 200 250 300 350 400

ê xo

Sa mp le 1 1

1 3 .0 2 .2 0 1 3 1 6 :5 2 :3 9

ST AR e SW 1 0 .0 0

Ir a n Po ly me r & Pe tr o che mic a l i ns ti t ut e - The r ma l Ana l ysi s: M ETTL ER


2.4.2 Nylon 6 dipped in a solution of carbon nanotubes

As is clear from the FESEM images in each concentration of carbon nanotubes well have been distributed

on the surface of nylon 6 nanofibers and With increasing concentration of carbon nanotubes, can be seen

which gathering carbon nanotubes together has grown .

We can conclude that the purification process was carried out well . whatever diameter decreases, contact

Surface increasing and carbon nanotubes attract increasing.

2.4.3 Conductivity properties

Nylon 6 is a polymer insulator but with adding carbon nanotubes on web nylon6 , The final composition is

conductive. It can be concluded With measure the electrical resistance of the specimens with an ohm meter.

Whatever Increase the amount of nanotubes and Diameter of nanofibers decreased and nylon6 web

uniformity increases , conductivity is increases.

sample S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11

0.1%

CNT 85 53.3 43.5 67.5 43 45 70 42.5 45 73.3 50.6

0.3%

CNT 76.6 50.25 41 50 39 46 51.2 35 33.75 50 49

LITERATURE

[1] F. J. Rodriguz-macias , Fully integrated single-walled carbon nanotube thermoplastic composites , UMI, 3122529,

2004,Houston,Texas

[2] L. YEO, J. FRIEND, Electrospinning carbon nanotube polymer composite nanofibers, Journal of Experimental

Nanoscience,Vol. 1, No. 2, June 2006,pp. 177–209

[3] R. Khare, S. Bose, Carbon Nanotube Based Composites- A Review, Journal of Minerals & Materials

Characterization & Engineering, Vol. 4, No.1 , 2005, pp 31-46.

[4] M. Biercuk, Shahal, C. Marcus, P. McEuen, Electrical Transport in Single-Wall Carbon Nanotubes, Carbon

Nanotubes Topics Appl. Physics 111, 2008,pp. 455–493

[5] X. Zhang, Studies on Single Wall Carbon Nanotubes and Polymer Composite Films and Fibers, Georgia Institute

of Technology ,2004

[6] Z. Liu, X. Sun, N.Nakayama, H. Dai, Supramolecular Chemistry onWater-Soluble Carbon Nanotubes for Drug

Loading and Delivery, American Chemical Society, VOL. 1 , NO. 1,2007,pp.50-56

[7] A. J. Saleh Ahammad, Jae-Joon Lee and Md. Aminur Rahman , Review, Electrochemical Sensors Based on

Carbon Nanotubes , Sensors, 9, pp. 2289-2319, 2009

[8] M. Meyyappan, Carbon Nanotubes Science & Applications, CRC Press, 2005.

[9] W. A. De Heer, W. S. Bacsa, A. Chatelain, T. Gerfin, R. Humphrey Baker, Nanocapillarity and chemistry in carbon

nanotubes, Science 268, 1995, Page 845.

[10] X. Zhang, Q. Guo and D. Cui, Recent Advances in Nanotechnology Applied to Biosensors, Sensors, pp 1033-

1053, 2009

[11] Neeta L. Lala , Velmurugan Thavasi and Seeram Ramakrishna , Article , Preparation of Surface Adsorbed and

Impregnated Multi-walled Carbon Nanotube/Nylon-6 Nanofiber Composites and Investigation of their Gas

Sensing Ability, Sensors , 9 , pp.86-101, 2009

Table 2 conductivity of sample with different concentration CNT


[12] Zheng-Ming Huanga, Y.-Z. Zhangb, M. Kotaki, S. Ramakrishna ,review , polymer nanofibers by electrospinning

and their applications in nanocomposites, Composites Science and Technology 63 , pp 2223–2253, 2003

[13] N. Vitchuli Gangadharan , Atmospheric Pressure Plasma-Electrospin Hybrid Process for Protective Applications,

Fiber and Polymer Science, 2011, North Carolina

[14] F. HUSSAIN , M. HOJJATI , Review , Polymer-matrix Nanocomposites, Processing, Manufacturing, and

Application , Journal of COMPOSITE MATERIALS, Vol. 40, No. 17 ,pp 1511-1575 , 2006

[15] S. S. OJHA, FABRICATION AND CHARACTERIZATION OF NOVEL SINGLE AND BICOMPONENT

ELECTROSPUN NANOFIBROUS MATS , TEXTILE ENGINEERING, 2007 , North Carolina

[16] S. Zhnag , Mechanical and Physical Properties of Electrospun Nanofibers, Textile Chemistry, 2009, North Carolin

[17] S,Hyun Lee, J.Woo Yoon, Continuous Nanofibers Manufactured by Electrospinning Technique, Macromolecular

Research, Vol. 10, No. 5, 2002,pp 282-285.

[18] J.S. Jeong, S.Y. Jeon, T.Y. Lee, J.H. Park, J.H. Shin, P.S. Alegaonkar, A.S. Berdinsky, J.B. Yoo , Fabrication of

MWNTs/nylon conductive composite nanofibers by electrospinning , Diamond & Related Materials 15 , pp 1839–

1843, 2006

[19] M. Chowdhury and G. Stylios , Effect of experimental parameters on the morphology of electrospun Nylon 6 fibres

, International Journal of Basic & Applied Sciences IJBAS-IJENS Vol: 10 No: 06 , pp 116-131, 2010

[20] Gui-Bo Yin , Analysis of Electrospun Nylon 6 Nanofibrous Membrane as Filters , Journal of Fiber Bioengineering

and Informatic , JFBI , Vol. 3,No.3 ,pp 137-141, 2010

[21] E.Chiang Chen, T.Ming Wu, NONISOTHERMAL CRYSTALLIZATION KINETICS AND CRYSTALLINE

STRUCTURE OF NYLON6/FUNCTIONALIZED MULTI-WALLED CARBON NANOTUBE COMPOSITES, Material

Science and Engineering

[22] C.xil,Z.jia , Fabrication of Nylon-6/Carbon Nanotube Composites , journal of electronic materials , Vol. 35, No. 5 ,

pp 954-957 , 2006

[23] R. Haggenmuelle, F. Du, J. E. Fischer, K. I. Winey, Interfacial in situ polymerization of single wall carbon

nanotube/nylon 6,6 nanocomposites, Polymer, Volume 47, Issue 7, pp 2381-2388, 2006

[24] L. Li, C. Y. Li , C. Ni, L. Rong , B. Hsiao , Structure and crystallization behavior of Nylon 66/multi-walled carbon

nanotube nanocomposites at low carbon nanotube contents , Polymer 48 , pp 3452 3460 , 2007

[25] P. Chen, H.Sik Kim, and H.Joon Jin , Review ,Preparation, Properties and Application of Polyamide/Carbon

Nanotube Nanocomposite , Macromolecular Research, Vol. 17, No. 4, pp 207-217 , 2009

[26] X.Wang , P. D. Bradford, W. Liu , H. Zhao , Y. Inoue , J.-Paul Maria , Q. Li,F-Gwo Yuan, Y. Zhu , Mechanical and

electrical property improvement in CNT/Nylon composites through drawing and stretching , Composites Science

and Technology 71 , pp 1677–1683 , 2011

[27] Jaewon Choi, Dong Wha Park, and Sang Eun Shim , Notes ,Chemical Vapour Sensing Behaviors of Multi-Walled

Carbon Nanotube Adsorbed Electrospun Nylon 6,6 Nanofibers , Macromolecular Research, Vol. 19, No. 9, pp

980-983 , 2011

[28] In Yee Phang,J. Ma,L. Shen,T. Liu and Wei-De Zhang , Crystallization and melting behavior of multi-walled

carbon nanotube-reinforced nylon-6 composites , Polymer International , 55 , pp71-79 , 2006

[29] L. Li, B. Li, M. A. Hood, C. Y. Li, Carbon nanotube induced polymer crystallization: The formation of nanohybrid

shish–kebabs, Polymer 50 , pp 953–965 , 2009

[30] S. Lin a, Q. Cai, J. Ji, G. Sui, Y. Yu a, X. Yang a,Qi. Ma b, Y. Wei, X. Deng b,Electrospun nanofiber reinforced

and toughened composites through in situ nano-interface formation , Composites Science and Technology 68, pp.

3322–3329 , 2008

[31] A. Frenot, IoannisS. Chronakis, Polymer nanofibers assembled by electrospinning , Current Opinion in Colloid

and Interface Science 8 , pp 64-75 , 200

preparation conductive nylon 6 nanofiber for medical application

Documents