Copyright © 2009 American Scientific Publishers Journal of

All rights reserved Biomedical Nanotechnology

Printed in the United States of America Vol. 5, 1–6, 2009

Inherently Colored Antimicrobial Fibers

Employing Silver Nanoparticles
T. V. Sreekumar∗ , Arunashish Das, Lal Chandra, Anurag Srivastava, and K. U. Bhasker Rao
DMSRDE, Defence Research and Development Organization (DRDO), G T Road, Kanpur, UP 208013, India

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.

1. INTRODUCTION AgNO3 concentration was increased from 1 to 4.5 wt%.

With the increase in particle size a clear red shift was also
Textile fibers are in need of both color and antimicro- observed in the absorption spectrum. The antimicrobial

bial property.1 Coloring involves several steps collectively
known as the dyeing process where the fabric is soaked
in the dye bath at various temperatures and pressures.
Many organic dyes are carcinogenic in nature and there
is a growing consciousness towards avoiding azo based
dyes.1 Most commonly used method of imparting antimi-
crobial property to textiles involves use of chemical fin-
ishes. The processes (of dyeing and chemical finishing)
are tedious; consumes high energy; expose workers to haz-
ardous chemicals and many a times raise environmental,
health and ecological concerns. Silver (Ag) nanoparti-
cles are demonstrated to generate various colors2 and are
reported to have strong antimicrobial property.3–5 Several
methods are reported in the literature to produce silver
nanoparticles of various shapes such as cubes,6 spheres,7
8
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
the type of reducing agent, reducing agent concentration,
silver nitrate (AgNO3  concentration etc. In one report,
the average size of hexagons and spheres increased with
increasing hydrazine (reducing agent) content.2 It was also
reported that the size of nanoparticles was influenced by
the initial AgNO3 concentration.8 The average Ag par-
ticle size was increased from 6.8 to 13.6 nm when the
∗
Author to whom correspondence should be addressed.
RESEARCH ARTICLE
activity of silver ions has been well established.3 In recent
years silver has been used in a variety of medical applica-
tions ranging from wound dressing to urinary catheters due
to its inherent antibacterial properties.11
12 These unique
optical properties13 and biomedical applications14 of metal
nanoparticles, specifically silver nanoparticles were the
inspiration of using silver nanoparticles in fibers as reported
in this paper.
In this study we have exploited both the properties
(color as well as antimicrobial property) of silver nanopar-
ticles by in-situ nanoparticle synthesis and solution spin-
ning of the polymer dope containing the nanoparticles to
produce a variety of colored acrylic fibers having antimi-
crobial effect without using any conventional dyes and
chemical finishes.
2. EXPERIMENTAL DETAILS
2.1. Synthesis of Polymer
Dimethylformamide (DMF), Acrylonitrile (AN), Methyl
Acrylate (MA), Itaconic Acid (IA) and Azobisisobutyro-
nitrile (AIBN) were obtained from commercials sources.
DMF, AN, MA and water were distilled before use.
Acrylonitrile copolymer, acrylonitrile-methyl acrylate-
itaconic acid, P(AN/MA/IA:96/3/1), were synthesized in
a four necked reactor using solvent-water suspension

J. Biomed. Nanotechnol. 2009, Vol. 5, No. 1 1550-7033/2009/5/001/006 doi:10.1166/jbn.2009.40 1

 Inherently Colored Antimicrobial Fibers Employing Silver Nanoparticles
Ram
Rollers
1st coag. bath 2nd coag. bath
Fig. 1. Schematic diagram of the fiber spinning set up.
polymerization technique at 55  C under nitrogen atmo-
sphere. The reaction medium was a mixture of dimethyl
formamide and water. Azobisisobutyronitrile (1 wt% with
respect to monomer feed) was used as the initiator.
The details of the synthesis procedures are reported
elsewhere.15
2.2. Synthesis of Silver Nanoparticles
AgNO3 and hydrazine hydrate (N2 H4 · H2 O) were used as
received from commercial sources. In a standard experi-
ment 12 g of PAN copolymer was dissolved in 100 ml of
DMF to obtain a transparent solution. In a separate vial
0.5% AgNO3 (w.r.t PAN copolymer) was dissolved in 5 ml
of DMF. The two solutions were mixed together by con-
RESEARCH ARTICLE
stant stirring. In this procedure four dope solutions were
prepared with 0, 0.5, 1 and 3% AgNO3 with respect to
PAN. The Ag+ ions of AgNO3 were reduced to metallic sil-
ver using equivalent amount of hydrazine hydrate (N2 H4 ·
H2 O). Thus, Ag contents in the solutions were approxi-
mately 0, 0.3, 0.6 and 1.9%.
2.3. Acrylic Fiber Spinning
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
using the small scale spinning system manufactured by
Bradford University Research Ltd. DMF/water volumetric
ratios in the coagulation baths (baths 1 and 2) and drawing
bath (bath 3) were 60/40, 10/90, and 0/100, respectively.
The temperature of the two coagulation baths was maintai-
ned at 30  C. The drawing bath temperature was maintained
at 100  C. An in-line heater plate was used for fiber drying
which was maintained at 130  C. There was no fiber draw-
ing in the two coagulation baths. Fiber was drawn between
2nd and 3rd rollers in boiling water, and was allowed to relax
during the drying process over the heater plate. The first
take-up roller speed (1 m/min) and the winder speed
(5 m/min) were set in such a way that the final draw ratio
for each composite fiber was 5. Fibers were also produced
from PAN/AgNO3 (PAN:AgNO3 = 99:1) dope solutions
2 J. Biomed. Nanotechnol. 5, 1–6, 2009
Sreekumar et al.
Heater plate
Washing cum To Winder
drawing bath
without adding hydrazine hydrate. The decomposition of
AgNO3 to form Ag in the fiber was carried out by heat
treatment of the fiber at 150  C over the heater plate.
2.4. Fiber Characterization
Transmission Electron Microscopy (TEM) analysis was
performed with Tecnai G2 TEM machine supplied by Field
Emission Instrument (FEI), USA, operated at 200 kV.
UV-Vis spectra of the acrylic fibres were recorded
in the absorption mode using Perkin-Elmer Lamda 19
UV/VIS/NIR spectrometer. The fiber mechanical properties
were measured using Favimat single fiber testing machine
supplied by Textechno, Germany. The gauge length and
testing speed used were 25 mm and 10 mm/min respec-
tively. Antimicrobial tests were conducted at Bombay Tex-
tile Research Association (BTRA), Mumbai, using ASTM:
E2149-01 test method. This test was conducted by shak-
ing samples in a concentrated bacterial suspension for a
one hour contact time. The suspension was serially diluted
both before and after contact and cultured. The number of
organisms in the suspension was determined and the per-
cent reduction was calculated based on initial counts on
pure PAN control sample.
3. RESULTS AND DISCUSSION
3.1. Nanoparticle Formation
The in-situ synthesis of the Ag nanoparticle is based on
the fact that both AgNO3 and polyacrylonitrile dissolve in
DMF which is a common solvent. Upon reduction with
hydrazine hydrate AgNO3 will be converted to metallic Ag
particles. The viscous polymer gel (Dope) does not allow
the nanoparticles to coalesce easily and the particles get
kinetically stabilized. The spinning of the fiber needs to
be conducted as soon as possible as the chances of coa-
lescence can not be ruled out with time. Figure 2 shows
three typical TEM micrographs of PAN containing low
(0.6%) medium (3.0%) and high (6.0%), Ag concentra-
tions. For transmission electron microscopy (TEM) analy-
sis, the samples were prepared by directly depositing the
Sreekumar et al. Inherently Colored Antimicrobial Fibers Employing Silver Nanoparticles
(a)
200 nm
(b)
200 nm
(c)
500 nm
Fig. 2. TEM images of PAN/Ag composites containing (a) 0.6%,
(b) 3% and (c) 6% Ag concentration.
dope solutions containing silver nanoparticles over copper
grids and further coagulating in a solution of 60:40 DMF
and H2 O. The image consists of particles of various sizes
and shapes. The different shapes present in the PAN/Ag
composites are spheres, hexagons and a few rods. The
average size of a sphere ranges from 20 to 25 nm and the
larger spheres are aggregates of smaller ones. The size of
the hexagons is about 120 nm and the length of the rod is
about 75 nm. Although, the number and aggregate size of
the silver particle have increased by increasing the concen-
tration of AgNO3 , the size of individual spherical particle
J. Biomed. Nanotechnol. 5, 1–6, 2009
Fig. 3. EDX Spectrum of PAN/Ag composite. Electron diffraction spec-
trum is given in the inset.
seems to be unchanged. The presence of Ag was further
confirmed by EDX analysis which shows that the crystals
are made of silver (Fig. 3). EDX and electron diffraction
were carried out by concentrating the beam over a hexago-
nal silver crystal. In the electron diffraction pattern (Fig. 3
inset), the angle between two shortest vectors connecting
the central sport is about 60 , however, the expected angle
for crystalline silver is 70.5 . Similar observations were
made by other researches also17 and mentioned that this
RESEARCH ARTICLE
type of structure is still under investigation.
3.2. Colored Fiber Formation
Figure 4 shows various colored fibers obtained after the
wet spinning of PAN dopes containing silver nanoparti-
cles. Figures 4(a) to (d) are fibers obtained by changing
the concentration of the Ag in the fiber. Thus fibers with a
series of colors could be produced by incorporating differ-
ent quantities of Ag. Figure 4(a) is the neat acrylic fiber
with no silver content which is white in color. By incor-
porating 1.9% silver nanoparticles bluish grey fiber was
obtained (Fig. 4(b)). Above this Ag content, the color of
the fiber did not change from bluish grey. However, with
decrease in the Ag content the color of the fiber shifted
from blue to red side of the spectrum. Figure 4(c) shows
fiber produced form a PAN spinning dope solution contain-
ing 0.6% silver nanoparticles. This fiber has brown shade.
Fiber containing 0.3% Ag is shown in Figure 4(d). This
fiber has a yellow-orange shade. Figure 4(e) shows fiber
produced from PAN/AgNO3 (PAN:AgNO3 = 99:1) dope
solution. In this case the dope solution containing PAN
and AgNO3 was directly spun into the coagulation bath
without reducing the salt with hydrazine hydrate, while
the Ag nanoparticles were generated by thermal reduc-
tion at 150  C over the heater plate. The residence time
over the heater plate was about 10 seconds. The reduction
3
 Inherently Colored Antimicrobial Fibers Employing Silver Nanoparticles Sreekumar et al.

(a) (b) (c) (d) (e)

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
the fiber immediately changes from colorless to reddish
over the heater plate. The fiber was colorless, similar to
Figure 4(a), before heat treatment.
One of the most interesting aspects of metal nanopar-
ticles is their optical properties associated with their size
and shape. These optical effects are due to the changes in
surface plasmon resonance, the frequency at which con-
duction electrons oscillate in response to the alternating
electric field of incident electromagnetic radiation. It has
been reported that only metals with free electrons such
as Au, Ag, Cu and alkali metals possess plasmon reso-
nance in the in the visible spectrum, which give rise to
different colors.18 The optical properties not only depend
on the individual particle size and shape but also depend
strongly on the surrounding medium and distance between
RESEARCH ARTICLE
observed in the visible region. In Figure 5, the curves due
to blue, brown and orange were obtained after subtract-
ing the contribution of pure acrylic fiber from the original
curves so that the effect of base polymer is nullified. In the
350–600 nm range of wave length no well resolved peak
is observed, except a very wide hump. Generally a single
sharp peak is observed for uniform particle size with nar-
row distribution.5 Most authors have reported sharp peaks
due to spherical particles at ∼400 nm (Refs. [5, 21]) and
nano rods at ∼570 nm.9 In the present case no such sharp
peak is observed in the visible region except two sharp
peaks in the UV region at ∼220 nm and ∼300 nm. It may
be noted that the absorbance intensity of colored fibers in
the visible region is higher than that of the control pure
PAN fiber.

neighboring metal nanoparticles.19 In our case this distance

depends on the concentration of silver nanoparticles used
during the dope preparation. With increase in concentra-
tion the particles come closer and the resonance energy
will be different for different PAN/Ag compositions. At
lower concentrations (particles far apart) the resonance
energy will be high which leads to interaction in the blue
region, resulting in to a fiber with color in the red side
of the spectrum. On the other hand at higher concentra-
tions of silver nanoparticles due to low resonance energy
the interaction will be with longer wave length (red side)
allowing the eyes to see the blue region.
This is a first time report that colored acrylic fibers are
prepared without adding any dye or pigment. In industry
colored acrylic yarns are prepared by dying the yarns using
cationic dyes. The positively charged dye ions attach them-
selves with the negatively charged comonomers present
in the polyacrylonitrile copolymer molecules.20 Using our
3.3. Mechanical Properties
The mechanical properties of colored fibers were found
similar to that of pure acrylic fiber and were not signifi-
cantly influenced by the presence of nanoparticles. Tenac-
ity of the fibers ranges from 3.0 to 3.5 g/den, modulus
of the fibers ranges from 40 to 80 g/den and elongation
ranges from 8 to 10%. Deformation starts at ∼1.5 g/den in
pure PAN and Ag impregnated acrylic fibers. These val-
ues are comparable to the commodity textile fibers. Gen-
erally by incorporating fillers of micron size in the fiber,
mechanical properties, especially tenacity and elongation,
reduces. This is because these fillers act as weak linkages
1.4 Brown
1.2
1
Absorbance (au)

method hazardous organic dyes and pigments could be 0.8

avoided. In the present case, as silver nanoparticles could 0.6 Blue
be prepared in situ in the spinning dope, colored fibres Orange
0.4
could be produced in one step. This could reduce the total
production cost of the fiber. 0.2
Pure PAN
As discussed in the TEM results the composite fiber 0
200 300 400 500 600 700 800 900
consists of a mixture of Ag nanoparticles of different size – 0.2
Wavelength (nm)
and shape. This is further confirmed by UV-Vis absorption
spectroscopy of these fibers (Fig. 5) where a wide hump is Fig. 5. UV-Vis spectra of various acrylic fibres containing Ag.

4 J. Biomed. Nanotechnol. 5, 1–6, 2009

Sreekumar et al.
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.
and become points of stress concentration. However, in the
present case the particle sizes are in the order of nanome-
ters which could well fit in between the aligned or oriented
molecules.
3.4. Antimicrobial Properties
Antimicrobial properties of the silver nanoparticle embed-
ded fibers were investigated against Staphylococcus aureus
(Gram-positive), and Escherichia coli (Gram-negative)
using standard ASTM: E2149-01 test method for deter-
mining antimicrobial activity of immobilized antimicrobial
agents under dynamic contact conditions. Figure 6 shows
the growth of Escherichia Coli in the presence of normal
fiber and in the presence of fibers containing Ag nanopar-
ticles. Number of bacterial colonies gradually reduces with
increase in silver content in the fiber. The reducing trend
for Staphylococcus aureus is also similar to Escherichia
Coli (picture not shown). The results of the antimicrobial
study are illustrated in Table I. Staphylococcus aureus fre-
quently live on the skin or in the nose of a person. It
can cause a range of illnesses from minor skin infections,
such as pimples, boils, folliculitis, furuncles, carbuncles,
scalded skin syndrome and abscesses, to life-threatening
diseases, such as pneumonia and septicemia. Its incidence
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
clothing made out of this fiber could act as a bio-protective
wear for kids, patients and even for doctors. This work
could give further opportunities in terms of water purifica-
tion, clothing against biological warfare agents and medi-
cal textiles.
Table I. Antimicrobial efficacy of the fibers containing various silver
nanoparticle concentrations.
Bacterial reduction percentage
Ag content (%) Escherichia Coli Staphylococcus Aureus
0 52 29
0.3 54 36
0.6 56 43
1.9 94 92
J. Biomed. Nanotechnol. 5, 1–6, 2009
Inherently Colored Antimicrobial Fibers Employing Silver Nanoparticles
4. CONCLUSIONS
Fibers with different colors and antimicrobial activity
could be produced by using silver metal in nano size along
with polymer matrix of the fiber rather than using haz-
ardous dyes and biocides. In this study, we have shown that
many shades are possible just by varying the Ag concen-
tration or by slightly changing the process of fiber produc-
tion. No different dyes for different colors are required in
fibers and fabrics and this concept could make a difference
in textile dyeing and processing industry. The antibac-
terial property of the fiber is as high as 94.3% against
Escherichia coli. As silver nanoparticles get embedded
into polymer itself, they become inherent part of the fiber
and are expected to survive repeated wash cycles without
losing their efficacy. The mechanical properties of the fiber
RESEARCH ARTICLE
were not altered by the incorporation of the nanoparticles.
Thus more than one functional property could be achieved
without sacrificing the mechanical properties of the fiber.
Acknowledgments: The authors acknowledge Dr. B.
Sandeep, Dr. K. Muraleedharan of DMRL, Hyderabad
for their help in TEM analysis and Mrs. Debarati
Bhattacharjee, Mrs. Sreeja Sreekumar for fruitful discus-
sions on fibers and antimicrobial properties.
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