Академический Документы
Профессиональный Документы
Культура Документы
Here we are reporting a novel method of producing inherently colored antimicrobial fibers employ-
ing silver nanoparticles. Without using undesirable dyes and chemical finishes, colors as well as
antimicrobial properties have been imparted in textile grade acrylic fibers through silver nanoparti-
cles, in such a way that these properties become inherent part of the fibers. The motivation behind
silver nanoparticles is their unique optical properties as well as biomedical applications. A compos-
ite solution of polyacrylonitrile copolymer containing silver nanoparticles, synthesized in-situ, was
converted into fibers using solution spinning technique. The fibers, so formed, have in-built silver
nanoparticles in size ranging from 20–120 nm. Colors ranging from red to blue could be prepared
by varying the silver concentration, aggregate size and process. The antibacterial efficacy of the
fiber was as high as 94.3% against Escherichia coli.
Keywords: Acrylic Fiber, Colored Fibers, Silver Nanoparticles, Antimicrobial Textiles.
RESEARCH ARTICLE
bial property.1 Coloring involves several steps collectively activity of silver ions has been well established.3 In recent
known as the dyeing process where the fabric is soaked years silver has been used in a variety of medical applica-
in the dye bath at various temperatures and pressures. tions ranging from wound dressing to urinary catheters due
Many organic dyes are carcinogenic in nature and there to its inherent antibacterial properties.11 12 These unique
is a growing consciousness towards avoiding azo based optical properties13 and biomedical applications14 of metal
dyes.1 Most commonly used method of imparting antimi- nanoparticles, specifically silver nanoparticles were the
crobial property to textiles involves use of chemical fin- inspiration of using silver nanoparticles in fibers as reported
ishes. The processes (of dyeing and chemical finishing) in this paper.
are tedious; consumes high energy; expose workers to haz- In this study we have exploited both the properties
ardous chemicals and many a times raise environmental, (color as well as antimicrobial property) of silver nanopar-
health and ecological concerns. Silver (Ag) nanoparti- ticles by in-situ nanoparticle synthesis and solution spin-
cles are demonstrated to generate various colors2 and are ning of the polymer dope containing the nanoparticles to
reported to have strong antimicrobial property.3–5 Several produce a variety of colored acrylic fibers having antimi-
methods are reported in the literature to produce silver crobial effect without using any conventional dyes and
nanoparticles of various shapes such as cubes,6 spheres,7 8 chemical finishes.
hexagons,2 rods,9 aggregates etc.10 The optical properties
of silver nanoparticles depend strongly upon the particle
size and shape.2 5 The particle size and shape depends on 2. EXPERIMENTAL DETAILS
the type of reducing agent, reducing agent concentration, 2.1. Synthesis of Polymer
silver nitrate (AgNO3 concentration etc. In one report,
the average size of hexagons and spheres increased with Dimethylformamide (DMF), Acrylonitrile (AN), Methyl
increasing hydrazine (reducing agent) content.2 It was also Acrylate (MA), Itaconic Acid (IA) and Azobisisobutyro-
reported that the size of nanoparticles was influenced by nitrile (AIBN) were obtained from commercials sources.
the initial AgNO3 concentration.8 The average Ag par- DMF, AN, MA and water were distilled before use.
ticle size was increased from 6.8 to 13.6 nm when the Acrylonitrile copolymer, acrylonitrile-methyl acrylate-
itaconic acid, P(AN/MA/IA:96/3/1), were synthesized in
∗
Author to whom correspondence should be addressed. a four necked reactor using solvent-water suspension
Ram
polymerization technique at 55 C under nitrogen atmo- without adding hydrazine hydrate. The decomposition of
sphere. The reaction medium was a mixture of dimethyl AgNO3 to form Ag in the fiber was carried out by heat
formamide and water. Azobisisobutyronitrile (1 wt% with treatment of the fiber at 150 C over the heater plate.
respect to monomer feed) was used as the initiator.
The details of the synthesis procedures are reported 2.4. Fiber Characterization
elsewhere.15
Transmission Electron Microscopy (TEM) analysis was
2.2. Synthesis of Silver Nanoparticles performed with Tecnai G2 TEM machine supplied by Field
Emission Instrument (FEI), USA, operated at 200 kV.
AgNO3 and hydrazine hydrate (N2 H4 · H2 O) were used as UV-Vis spectra of the acrylic fibres were recorded
received from commercial sources. In a standard experi- in the absorption mode using Perkin-Elmer Lamda 19
ment 12 g of PAN copolymer was dissolved in 100 ml of UV/VIS/NIR spectrometer. The fiber mechanical properties
DMF to obtain a transparent solution. In a separate vial were measured using Favimat single fiber testing machine
0.5% AgNO3 (w.r.t PAN copolymer) was dissolved in 5 ml supplied by Textechno, Germany. The gauge length and
of DMF. The two solutions were mixed together by con- testing speed used were 25 mm and 10 mm/min respec-
RESEARCH ARTICLE
stant stirring. In this procedure four dope solutions were tively. Antimicrobial tests were conducted at Bombay Tex-
prepared with 0, 0.5, 1 and 3% AgNO3 with respect to tile Research Association (BTRA), Mumbai, using ASTM:
PAN. The Ag+ ions of AgNO3 were reduced to metallic sil- E2149-01 test method. This test was conducted by shak-
ver using equivalent amount of hydrazine hydrate (N2 H4 · ing samples in a concentrated bacterial suspension for a
H2 O). Thus, Ag contents in the solutions were approxi- one hour contact time. The suspension was serially diluted
mately 0, 0.3, 0.6 and 1.9%. both before and after contact and cultured. The number of
organisms in the suspension was determined and the per-
2.3. Acrylic Fiber Spinning cent reduction was calculated based on initial counts on
pure PAN control sample.
The fibres were spun using solution spinning technique on
a laboratory spinning machine (Fig. 1). The dope solutions
were converted to fibers by solution spinning process16 3. RESULTS AND DISCUSSION
using the small scale spinning system manufactured by 3.1. Nanoparticle Formation
Bradford University Research Ltd. DMF/water volumetric
ratios in the coagulation baths (baths 1 and 2) and drawing The in-situ synthesis of the Ag nanoparticle is based on
bath (bath 3) were 60/40, 10/90, and 0/100, respectively. the fact that both AgNO3 and polyacrylonitrile dissolve in
The temperature of the two coagulation baths was maintai- DMF which is a common solvent. Upon reduction with
ned at 30 C. The drawing bath temperature was maintained hydrazine hydrate AgNO3 will be converted to metallic Ag
at 100 C. An in-line heater plate was used for fiber drying particles. The viscous polymer gel (Dope) does not allow
which was maintained at 130 C. There was no fiber draw- the nanoparticles to coalesce easily and the particles get
ing in the two coagulation baths. Fiber was drawn between kinetically stabilized. The spinning of the fiber needs to
2nd and 3rd rollers in boiling water, and was allowed to relax be conducted as soon as possible as the chances of coa-
during the drying process over the heater plate. The first lescence can not be ruled out with time. Figure 2 shows
take-up roller speed (1 m/min) and the winder speed three typical TEM micrographs of PAN containing low
(5 m/min) were set in such a way that the final draw ratio (0.6%) medium (3.0%) and high (6.0%), Ag concentra-
for each composite fiber was 5. Fibers were also produced tions. For transmission electron microscopy (TEM) analy-
from PAN/AgNO3 (PAN:AgNO3 = 99:1) dope solutions sis, the samples were prepared by directly depositing the
(a)
200 nm
(b)
RESEARCH ARTICLE
type of structure is still under investigation.
Fig. 4. Acrylic fibres containing silver nanoparticles. (a) PAN/0% Ag, (b) PAN/1.9% Ag, (c) PAN/0.6% Ag, (d) PAN/0.3% Ag, and (e) PAN/0.6% Ag
where silver nanoparticles are produced by the thermal reduction of AgNO3 .
takes place at this short interval. In this case the color of observed in the visible region. In Figure 5, the curves due
the fiber immediately changes from colorless to reddish to blue, brown and orange were obtained after subtract-
over the heater plate. The fiber was colorless, similar to ing the contribution of pure acrylic fiber from the original
Figure 4(a), before heat treatment. curves so that the effect of base polymer is nullified. In the
One of the most interesting aspects of metal nanopar- 350–600 nm range of wave length no well resolved peak
ticles is their optical properties associated with their size is observed, except a very wide hump. Generally a single
and shape. These optical effects are due to the changes in sharp peak is observed for uniform particle size with nar-
surface plasmon resonance, the frequency at which con- row distribution.5 Most authors have reported sharp peaks
duction electrons oscillate in response to the alternating due to spherical particles at ∼400 nm (Refs. [5, 21]) and
electric field of incident electromagnetic radiation. It has nano rods at ∼570 nm.9 In the present case no such sharp
been reported that only metals with free electrons such peak is observed in the visible region except two sharp
as Au, Ag, Cu and alkali metals possess plasmon reso- peaks in the UV region at ∼220 nm and ∼300 nm. It may
nance in the in the visible spectrum, which give rise to be noted that the absorbance intensity of colored fibers in
different colors.18 The optical properties not only depend the visible region is higher than that of the control pure
on the individual particle size and shape but also depend PAN fiber.
strongly on the surrounding medium and distance between
RESEARCH ARTICLE
Fig. 6. Antimicrobial activity of fibres containing silver nanoparticles against Escherichia Coli. (a) PAN/0% Ag, (b) PAN/0.3% Ag, (c) PAN/0.6% Ag,
and (d) PAN/1.9% Ag.
RESEARCH ARTICLE
increase in silver content in the fiber. The reducing trend were not altered by the incorporation of the nanoparticles.
for Staphylococcus aureus is also similar to Escherichia Thus more than one functional property could be achieved
Coli (picture not shown). The results of the antimicrobial without sacrificing the mechanical properties of the fiber.
study are illustrated in Table I. Staphylococcus aureus fre-
quently live on the skin or in the nose of a person. It Acknowledgments: The authors acknowledge Dr. B.
can cause a range of illnesses from minor skin infections, Sandeep, Dr. K. Muraleedharan of DMRL, Hyderabad
such as pimples, boils, folliculitis, furuncles, carbuncles, for their help in TEM analysis and Mrs. Debarati
scalded skin syndrome and abscesses, to life-threatening Bhattacharjee, Mrs. Sreeja Sreekumar for fruitful discus-
diseases, such as pneumonia and septicemia. Its incidence sions on fibers and antimicrobial properties.
is from skin, soft tissue, respiratory, bone, joint, endovas-
cular to wound infections. By incorporating 1.9% Ag more
than 90% of both the bacteria could be eliminated. Thus References and Notes
clothing made out of this fiber could act as a bio-protective
1. K. V. Datye and A. A. Vaidya, Chemical processing of synthetic
wear for kids, patients and even for doctors. This work fibres and blends, John Wiley & Sons (1984).
could give further opportunities in terms of water purifica- 2. M. Maillard, S. Giorgio, and M. Pileni, Tuning the size of silver
tion, clothing against biological warfare agents and medi- nanodisks with similar aspect ratios: Synthesis and optical properties.
cal textiles. J. Phys. Chem. B 107, 2466 (2003).
3. L. S. Nair and C. T. Laurencin, Silver nanoparticles: Synthesis and
therapeutic applications. J. Biomed. Nanotechnol. 3, 1 (2007).
Table I. Antimicrobial efficacy of the fibers containing various silver
4. A. Dove, R. Frederickson, and J. Hodgson, Bacteria with a silver
nanoparticle concentrations.
lining. Nat. Biotechnol. 18, 9 (2000).
Bacterial reduction percentage 5. S. Shanmugam, B. Viswanathan, and T. K. Varadarajan, A novel
single step chemical route for noble metal nanoparticles embedded
Ag content (%) Escherichia Coli Staphylococcus Aureus organic–inorganic composite films. Mat. Chem. Phys. 95, 51 (2006).
6. Y. Sun and Y. Xia, Shape-controlled synthesis of gold and silver
0 52 29
nanoparticles. Science 298, 2176 (2002).
0.3 54 36
7. Z. Zhang, L. Zhang, S. Wang, W. Chen, and Y. Lei, A convenient
0.6 56 43
route to polyacrylonitrile/silver nanoparticle composite by simulta-
1.9 94 92
neous polymerization–reduction approach. Polymer 42, 8315 (2001).
8. Z. Zhang and M. Han, One-step preparation of size-selected and to prevention of infection? J. Antimicrobial Chemotherapy 54, 1019
well-dispersed silver nanocrystals in polyacrylonitrile by simultane- (2004).
ous reduction and polymerization. J. Mater. Chem. 13, 641 (2003). 15. P. Bajaj, T. V. Sreekumar, and K. Sen, Production of high tenacity
9. Y. Sun, B. Gates, B. Mayers, and Y. Xia, Crystalline silver nanowires acrylic fibres. Chem Fibre Intern. 48, 308 (1998).
by soft solution processing. Nano Lett. 2, 165 (2002). 16. T. V. Sreekumar, T. Liu, B. G. Min, H. Guo, S. Kumar, R. H. Hauge,
10. L. A. Peyser, A. E. Vinson, A. P. Bartko, and R. M. Dickson, Photo- and R. E. Smalley, SWNT/PAN composite fibres. Adv. Mater. 16, 58
activated fluorescence from individual silver nanoclusters. Science (2004).
291, 103 (2001). 17. T. Klaus, R. Joerger, E. Olsson, and C. G. Gramqvist, Silver-
11. M. Bosetti, A. Masse, E. Tobin, and M. Cannas, Silver coated mate- based crystalline nanoparticles, microbially fabricated. Appl. Phys.
rials for external fixation devices: In vitro biocompatibility and geno- Sci./Microbiol. 96, 13611 (1999).
toxicity. Biomaterials 23, 887 (2002). 18. L. M. Liz-Marzan, Nanometals: Formation and color. Mater. Today
12. L. L. Woodyard, T. L. Bowersock, J. J. Turek, G. P. McCabe, and 7, 26 (2004).
J. DeFord, A comparison of the effects of several silver-treated intra- 19. T. Ung, L. M. Liz-Marzan, and P. Mulvaney, Optical properties of
venous catheters on the survival of staphylococci in suspension and thin films of Au@SiO2 particles. J. Phys. Chem. B 105, 3441 (2001).
their adhesion to the catheter surface. J. Control. Release 40, 23 20. P. Bajaj, Manufactured fiber technology, edited by V. B. Gupta and
(1996). V. K. Kothari, Chapman & Hall, London (1997).
13. R. J. Gehr and R. W. Boyd, Optical properties of nanostructured 21. Y. Ditrix, C. Bastiaansen, W. Caseri, and P. Smith, Oriented pearl-
optical materials. Chem. Mater. 8, 1807 (1996). necklace arrays of metallic nanoparticles in polymers: A new route
14. F. Furno, K. S. Morley, B. Wong, B. L. Sharp, P. L. Arnold et al., toward polarization-dependent colour filters. Adv. Mater. 11, 223
Silver nanoparticles and polymeric medical devices: A new approach (1999).