Applied Surface Science 317 (2014) 131–139

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Chemical, mechanical and antibacterial properties of silver

nanocluster/silica composite coated textiles for safety systems and
aerospace applications
S. Ferraris a,∗ , S. Perero a , M. Miola a , E. Vernè a , A. Rosiello b , V. Ferrazzo b , G. Valletta b ,
J. Sanchez c , M. Ohrlander c , S. Tjörnhammar d , M. Fokine d , F. Laurell d , E. Blomberg e,f ,
S. Skoglund e , I. Odnevall Wallinder e , M. Ferraris a
a
Politecnico di Torino, Torino, C.so Duca degli Abruzzi 24, 10129, Italy
b
Aero Sekur S.p.A., Aprilia (LT), via delle Valli 46, 04011, Italy
c
Bactiguard AB, Biblioteksgatan 25, Box 5070, SE-10242, Stockholm, Sweden
d
KTH Royal Institute of Technology, Department of Applied Physics, Roslagstullsbacken 21, SE-106 91 Laserphysics, Stockholm, Sweden
e
KTH Royal Institute of Technology, Div. Surface and Corrosion Science, Drottning Kristinas väg 51, SE-100 44, Stockholm, Sweden
f
SP Technical Research Institute of Sweden, Chemistry, Materials and Surfaces, Box 5607, SE-114 86, Stockholm, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: This work describes the chemical, mechanical and antibacterial properties of a novel silver nanoclus-
Received 20 June 2014 ter/silica composite coating, obtained by sputtering, on textiles for use in nuclear bacteriological and
Received in revised form 30 July 2014 chemical (NBC) protection suites and for aerospace applications.
Accepted 30 July 2014
The properties of the coated textiles were analyzed in terms of surface morphology, silver concen-
Available online 4 August 2014
tration and silver release in artificial sweat and synthetic tap water, respectively. No release of silver
nanoparticles was observed at given conditions.
Keywords:
The water repellency, permeability, flammability and mechanical resistance of the textiles before and
Antibacterial coating
Sputtering
after sputtering demonstrated that the textile properties were not negatively affected by the coating.
Silver nanoclusters The antibacterial effect was evaluated at different experimental conditions using a standard bacterial
Textiles strain of Staphylococcus aureus and compared with the behavior of uncoated textiles.
Protective garments The coating process conferred all textiles a good antibacterial activity. Optimal deposition conditions
were elaborated to obtain sufficient antibacterial action without altering the aesthetical appearance of
the textiles.
The antibacterial coating retained its antibacterial activity after one cycle in a washing machine only
for the Nylon based textile.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction accessories used in the production of safety systems designed for

Bacterial contamination is a problem for several applications
such as medical devices and everyday life surfaces and objects
used by the general public [1–5]. Applications in which this prob-
lem often is underestimated are protection garments for nuclear
bacteriological and chemical (NBC) protective suits, health mon-
itoring vests, antiseptic storage containers, and all related textile
∗ Corresponding author. Tel.: +39 0110905768; fax: +39 0110904624.
E-mail address: sara.ferraris@polito.it (S. Ferraris).
harsh environments.
The newly developed NBC suit consists of a novel concept of
a multi-layered antibacterial, permeable NBC protective textile. It
can be used in emergency escape life-vests with integrated res-
piration and anti-flash textiles, or be integrated with conductive
and/or anti-electrostatic textiles for a new generation of personal
protective equipment (PPE) for fire-fighters, chemical and mining
rescuers.
The elaboration of enhanced, stable and anti-septic textiles for
applications in safety systems, designed for harsh environments, is
of extreme importance as they should protect the user from infec-
tions or improve the security and well-being of personnel operating

http://dx.doi.org/10.1016/j.apsusc.2014.07.196
0169-4332/© 2014 Elsevier B.V. All rights reserved.
132 S. Ferraris et al. / Applied Surface Science 317 (2014) 131–139
in difficult areas (war, natural disaster, third world countries, etc.),
in which garments are worn for long time-periods.
Other plausible fields for exploitation of antibacterial coatings
are in aerospace applications, in garments for astronauts that spend
long time periods in closed environments, and to preserve anti-
septic conditions of textiles (e.g. parachute and airbag subsystems)
installed on interplanetary exploration probes, thus avoiding pro-
liferation of bacteria from Earth or the external environment [6].
As an example, the next ESA ExoMars exploration mission will land
an exploration rover on the surface of Mars, for which all materials
and surfaces must be sterilized and sterile conditions maintained
throughout the whole mission. Parachutes and airbags, typically
made of textiles, are currently sterilized to reduce microbial charge
by employing a dry heat microbial reduction process with ther-
mal cycles at 126 ◦ C for 35 h. The possibility to provide such items
with a thermal resistant, long lasting anti-septic coating will allow
multiple uses, and increase the efficiency of the exploration mis-
sion.
Silver antimicrobial activity and ability to inhibit poly-
microbial/fungal colonization are well documented [7], even
though the mechanism(s) still are debated [8]. In addition to its
broad spectrum antibacterial activity silver presents a low bac-
terial resistance. This feature is extremely important considering
the increasing development and spreading of bacterial resistance
to antibiotics, as recently evidenced by international communi-
cations [9]. Several techniques such as sol-gel [10], chemical and
physical vapor deposition [11], silver absorption on zeolites [12],
biological synthesis [13] and ion exchange [14] have been explored
to generate antibacterial coatings on different textile substrates.
The fabrication methods of antimicrobial textiles are classified in
two main categories; (a) addition of the antimicrobial agent to the
fiber prior to its spinning or extrusion, and (b) post-treatment of
the fiber or fabric during stages of finishing. Examples of commer-
cial products fabricated using these methods are; (i) silver-coated
polyester (Polyethylene terephtalate, PET) and cotton yarns, pro-
duced via the patented (Silvertech) in situ photo-reduction process
of silver clusters [15,16] in which silver is deposited via silver
nitrate impregnation in a water/alcoholic solution, (ii) nanostruc-
tured silver films of different thickness deposited on surfaces of
polypropylene by magnetron sputtering [11], (iii) nanosized silver
deposited on cellulosic and synthetic fabrics by colloidal processes
[17], and (iv) antibacterial polymer textile fabric prepared by sur-
face functionalization using RF-plasma or vacuum-UV, followed by
immersion in AgNO3 solutions of different concentration and sil-
ver reduction at a given pH using a weakly reducing agent [18].
Technologies such as Agiene® , Agion® and Trevira Bioactive® are
available on the market to provide antibacterial functionality to
textiles [19–21].
A novel antibacterial silver nanocluster/silica composite coating
has recently been developed possible to deposit by means of RF co-
sputtering on several substrates including glasses [22–24], metals
and polymers [25,26]. The technique allows the thermal, chemical
and mechanical stability of silica to be combined with the antibac-
terial characteristics of silver. According to literature findings are
its main advantages, compared with other coatings, (i) its one-step
coating process, (ii) its production without solvents or toxic chemi-
cals, (iii) the lack of nanoparticle manipulation, (iv) the embedment
of silver nanoclusters in a silica matrix, (v) its suitability for large
scale production, (vi) its possibility to coat selected areas on almost
any substrate, (vii) its possibility to tune the silver concentration
and coating thickness, and (viii) its high thermal and mechanical
stability, as evidenced in [26].
The aim of this paper is to present the chemical, mechanical,
and antibacterial characteristics and performance of a novel silver
nanocluster/silica composite coating applied on innovative textiles
for use in nuclear bacteriological and chemical (NBC) protection
suites, health monitoring vests, antiseptic storage containers and
textile accessories for aerospace applications.
2. Experimental
2.1. Materials and coating
The study comprises three different textiles; (i) a white Nylon
fabric PIA-44378D,Type I (denoted “Nylon”) used in parachutes
and airbag subsystems and for use in aerospace environments,
(ii) a black textile with active carbon (woven fabric: 59% cotton,
41% polyester; activated carbon spheres; non-woven fabric: 100%
polyamide; 280 g/m2 ) (denoted “Black”) used to absorb danger-
ous chemicals, and (iii) a camouflage Suit Tissue “Defender M,
210 g/m2 ” (65% Lenzing FRTM [27], 25% Para-aramidic fiber, 10%
polyamide) (denoted “Camouflage”) used in NBC (Nuclear, Bacteri-
ological, Chemical) suits.
The textiles were coated with the silver nanocluster/silica com-
posite coating by means of a RF co-sputtering process (Microcoat
MS450), using silver- (Sigma–Aldrich 99.99% purity) and silica
(Franco Corradi S.r.l. 99.9% purity) targets. The coating was applied
via a co-deposition process applying 200 W to a 6 in. silica target,
and 1 W (in pulsed DC mode) to a 1 in. silver target. All process
parameters are given in Table 1. Details on the nanocluster/silica
composite coating are given elsewhere [22–26].
2.2. Physical, chemical and mechanical properties
Coating morphology and composition were analyzed for all
coated textiles by means of field emission scanning electron
microscopy and energy dispersive X-ray spectroscopy, FEG-SEM-
EDS (QUANTA INSPECT 200, EDAX PV 9900, Zeiss SUPRATM 40).
Compositional analyses of the outermost surface (a surface area
of approximately 1 mm2 ) of coated Nylon and Camouflage textiles
were performed by means of X-ray photoelectron spectroscopy,
XPS (Kratos AXIS UltraDLD , Kratos Analytical, Manchester, UK) using
a monochromatic Al X-ray source.
Overall surface topographies of the coated Camouflage and
Nylon textile surfaces were investigated by means of tapping mode
atomic force microscopy, AFM (Digital Instruments Dimension
3100), imaging of 1–8 ␮m2 large areas.
Coating thicknesses (on glass substrate) were determined by
means of stylus profilometry (TenkorTM P16, US).
The total amount of silver in the coating was determined for
each textile by means of atomic absorption spectroscopy (AAS) (air-
acetylene flame, Varian AA240FS) after extraction in 20 mL heated
(100 ◦ C) nitric acid (HNO3 )/and fluoric acid (HF) mixtures (10%
HNO3 /0.1% HF) for 2 h. The determination limit varied between 0.5
and 2.0 mg/L in the measured range.
The amount of released silver in solution (non-precipitated) was
determined using atomic absorption spectroscopy (PerkinElmer
AAnalyst 800) upon exposure in artificial sweat, in compliance
with the EN1811 standard [28] (NaCl (5.0 g NaCl/L, 1.0 g urea/L, and
1.0 g lactic acid/L), and in synthetic tap water (0.099 g CaCO3 /L),
0.033 g NaCl/L, and 0.0298 g Na2 SO4 /L), respectively. Coated sam-
ples (approximately sized 1 cm × 1 cm) were immersed with an
area/solution volume ratio of 1 cm2 /10 mL for 2, 4, 24 and 168 h
at dark conditions at 37 ◦ C and pH 6.5 for artificial sweat (deter-
mination limit – 0.5 ␮g/L), and at pH 7.5 for synthetic tap water
(determination limit – 0.5 ␮g/L). Triplicate coated samples and one
uncoated sample were exposed for each time period and solution.
Parallel measurements of the released amount of silver from
the coated textiles (by means of AAS, air-acetylene flame, Varian
AA240FS) were made after soaking in tap water and artificial sweat
respectively at 37 ◦ C (stirring conditions – 10 rpm). The samples
 S. Ferraris et al. / Applied Surface Science 317 (2014) 131–139
Table 1
Different sputter conditions applied to coat the Black-, Nylon- and Camouflage textiles.
Sputtering deposition time Period (s) Duty cycle
(min) (s)
A 120 12 1 450
B 120 6 2
C 120 6 1
D 15 6 2
were soaked for 1, 2, 3, 4, 6, 24, 96, 288, and 432 h in 5 mL of artifi-
cial sweat and synthetic tap water, respectively. About 5 mL of the
supernatants was collected for each time period. The total volume
of 5 mL was restored after each time point by adding fresh solution.
The formulation for artificial sweat followed the ISO 3160-2 proto-
col (20 g/L NaCl, 17.5 g/L NH4 Cl, 5 g/L acetic acid, 15 g/L lactic acid,
pH adjusted to 4.7 by NaOH).
The potential release of nanoparticles from the coated textiles
was assessed by applying photon cross correlation spectroscopy,
PCCS (NanoPhox, Sympatec, Germany) measurements after 0.5, 2
and 24 h of immersion in artificial sweat and synthetic tap water,
respectively. Triplicate measurements were made on duplicate
samples of each textile at 25 ◦ C. Standard latex samples (20 ± 2 nm)
(Sympatec) and blank samples were tested prior to analysis to
ensure the accuracy of the measurements.
Tensile strength measurements of coated and uncoated textile
samples (25 mm × 300 mm) were performed using a Zwick Z100
instrument operating at 300 ± 10 mm/min and 20 ± 3 s to fracture.
Tear strength measurements (Dynamometer Acquati G, serial FZ-
004; 65/88) were in addition made for the coated and uncoated
Camouflage textile in compliance with the ASTM D-5587 standard
[29].
Coated and uncoated Nylon and Camouflage textiles were char-
acterized in terms of flammability (FAR.25.853) [30], permeability
(UNI EN ISO 9237) [31], water repellency (ISO 4920) [32] and tensile
properties (UNI EN ISO 13934-1, ASTM D 5035-95) [33]. Six sam-
ples of each textile (sized 50 mm × 300 mm, speed of execution:
100 ± 10 mm/min, distance between fixtures: 200 ± 1 mm) were
investigated. The properties of the Nylon and Camouflage textiles
were further investigated after a non-standard washing cycle in a
domestic washing machine.
2.3. Bacterial inhibition tests
The inhibition halo (Kirby Bauer test for antibiotic sensing) test
on Staphylococcus aureus (ATCC 29213), following the NCCLS M2-
A9 standard [34], and the parallel streak method (AATCC 147) [35]
to assess bacteriostatic activity, were performed on coated and
uncoated textiles.
To assess the survival capacity of bacteria (S. aureus- approx.
108 bacterial cells/mL), viability tests were performed on the Nylon
textile for different time periods up to 30 days in synthetic tap
water and for the Camouflage textile in artificial sweat up to 30
days. Bacteria-containing fluids exposed for different time peri-
ods and synthetic solutions were incubated on agar plates to
enable comparison of the degree of survival, an indirect measure
of the remaining antimicrobial capacity of the coated textiles after
immersion in artificial sweat and synthetic tap water, respectively.
Adhered bacteria were removed after 4 h at 37 ◦ C and counted using
a cell density meter (Biowave Biochrom WPA CO 8000, Biochrom
Ltd).
The Bac-Light RedoxSensor green Vitality kit (from Molecu-
lar probes, Invitrogen Detection Technologies) was used to study
the viability effect of S. aureus, 106 cells/mL, in contact with the
coated Nylon and Camouflage textiles. The assay allows measure-
ments of the bacterial oxidation-reduction activity that involves the
133
Coating thickness Ag/(Ag + Si) mass Ag/(Ag + Si) mass Ag/(Ag + Si) mass
(nm) ratio Black ratio Nylon ratio Camouflage
0.30 0.24 0.24
450 0.54 0.68 0.59
450 0.40 0.41 0.61
50 0.54 0.66 0.66
electron chain catabolic/anabolic pathways and xenobotic com-
pounds mechanisms. The extent of the reductase activity is a
measure of living bacteria, and the bacterial cell membrane
integrity a measure of dead bacteria.
The inhibition halo test and the FEG-SEM characterization were
repeated after water repellency, permeability and washing tests on
the Nylon and Camouflage textiles.
3. Results and discussion
3.1. Surface morphology and composition
Different sputter conditions were applied on all textiles, Table 1.
The coating thickness varied from 50 to 450 nm (determined by
means of profilometry) and the Ag/(Ag + Si) mass ratio from 0.30
to 0.66 (measured by means of EDS). The mass ratio was varied
by changing the duty cycle applied on the silver target during
the entire deposition time period, Table 1. This illustrates that the
coating thickness and composition can be tailored for a given appli-
cation. Most data is in the following only presented for D-coated
samples, the condition used to avoid excessive darkening of the
coated textiles (Fig. 1).
Representative FEG-SEM images of the coated (sputtering
condition D) Nylon (top) and Camouflage (bottom) textiles are pre-
sented in Fig. 2.
Both textiles revealed a relatively homogenous distribution of
silver particles in the silica matrix of the coating (visualized as white
particles of higher average atomic number), also verified with EDS
point analyses (data not shown). Compositional area analysis by
means of EDS (␮m depth information) and XPS (nm depth infor-
mation) showed coatings of similar or slightly higher amounts of
silver compared with silicon (as silica) with Ag/(Ag + Si) mass ratios
of 0.66 ± 0.07 (EDS) and 0.50 ± 0.04 (XPS), respectively for the Cam-
ouflage textile, and 0.66 ± 0.01 (EDS) and 0.72 ± 0.01 (XPS) for the
coated Nylon textile. Less spatial compositional variations were
hence observed for the coated Nylon textile compared with the
Camouflage textile.
Overall topography measurements of the coated Nylon and
Camouflage textiles were made using AFM, Fig. 3. The investiga-
tion showed variations in surface roughness on a nm-scale. The
Nylon surface was slightly rougher (RMS = 9.66 nm) compared with
the Camouflage textile (RMS = 4.71), which may be related to a
substrate effect. The topography of the Camouflage coating was
similar to findings for coated reference surfaces of stainless steel
(RMS = 3.74 nm), indicating that it is mainly the Ag/silica coating
that is imaged.
3.2. Mechanical, thermal and wettability properties
The coating process did not alter the uncoated textile prop-
erties such as flammability, water permeability, repellence and
tensile characteristics. Since this antibacterial coating previously
has demonstrated to be thermal resistant up to 450 ◦ C [22–24], the
dry heat microbial reduction process (126 ◦ C for 35 h) is expected
to be totally safe for these coated textiles.
134 S. Ferraris et al. / Applied Surface Science 317 (2014) 131–139

Fig. 1. Differences in surface morphology of the Black textile as a result of different sputtering parameters (B–D, A is the uncoated textile) given in Table 1.

Fig. 2. FEG-SEM backscatter images of the coated Nylon (top) and Camouflage (bottom) textiles. Silver particles in the silica matrix are seen as white areas in C and F. Particles
of higher average atomic number provides a stronger signal when recording backscattered electrons.

Fig. 3. AFM images of the overall topography of the coated Nylon (A) and Camouflage (B) textiles. Note: different z-scales.
 S. Ferraris et al. / Applied Surface Science 317 (2014) 131–139 135

Wettability results by contact angle measurements showed
hydrophobic surfaces of low wettability with angles of 117 ± 3◦ and
136 ± 3◦ , for the Nylon and Camouflage textile, respectively.
Yield strengths (when deformation occurs) of 443 N (450 N for
non-coated samples) and 940 N (960 N for non-treated samples),
were determined for the coated Nylon and Camouflage textiles,
respectively. Typical force (N)/displacement (mm) curves for the
coated and uncoated textiles, independent on material, are given
in Fig. 4 and exemplified for the Nylon textile (B).
Tear strength tests were made on coated and uncoated Cam-
ouflage textiles. Even though the test results for coated samples
(50.1 N) were lower than for uncoated samples (63.3 N), most prob-
ably due to a slight reduction in surface flexibility after sputtering,
their properties complied with existing tear strength requirements
(Aerosekur private communication) for this kind of textiles (tear
strength > 30 N).
3.3. Chemical and antibacterial properties
Bacteria inhibition zones, typically sized 3–4 mm, were formed
for all coated textiles, independent on sputtering parameters, see
Table 1. This is illustrated in Fig. 5 with inhibition halo findings
on coated textiles of Nylon, Camouflage and Black. The results are
illustrated for condition B as the halo was most pronounced for
these coating conditions, however evident for all conditions. The
slightly smaller halo observed for the Camouflage textile was due
to incomplete adhesion to the agar plate. Inhibition halo tests evi-
denced good antibacterial activity for all coated textiles according
to [36,37].
Concomitant streak method investigations (isolation of discrete
colonies) with S. aureus and the coated textiles (sputtering con-
dition B) confirmed the ability of the coating to limit bacteria
proliferation. Areas of interrupted bacterial growth underneath

Fig. 4. Tensile strength test (A) and results (force (N)/displacement (mm) curves) illustrated for coated and uncoated Nylon textile (B).

Fig. 5. Inhibition halo zones on uncoated (bottom) and coated textiles (top, sputtering process B, Table 1) of Nylon, Camouflage and Black, respectively. Similar observations
were made for all sputter conditions, though with less pronounced halos.
136 S. Ferraris et al. / Applied Surface Science 317 (2014) 131–139

and along the edges of the investigated textiles also indicate
the antibacterial activity of the coating. All sputtering condi-
tions generated coatings of good antimicrobial activity. To avoid
an excessive darkening of the coated textiles, sputtering condi-
tion D was selected (the thinnest coating thickness and highest
Ag/(Ag + Si) mass ratio) for further investigations.
Hence, the survival of bacteria exposed to the coated material
was very low for both coated material exposed to artificial sweat as
well as to water. This demonstrates a high degree of antibacterial
efficiency on the surface throughout the 30-day soak period.
The Ahern test was performed to study the survival capacity
(viability) of bacteria (106 /mL) in contact with the coated Nylon
and Camouflage textiles immersed in tap water and artificial sweat
for 30 days, respectively. Changes in viability as a function of time
and corresponding changes in surface concentration of silver in the
coating are presented in Fig. 6. The survival of bacteria was very
low for both textiles and solutions and demonstrated a high degree
of antibacterial efficiency throughout the 30 day exposure period.
The silver content of the Camouflage coating was reduced from
less than 6 ␮g/cm2 to less than 1 ␮g/cm2 after 30 days in artificial
sweat. The viability of surface adhering bacteria was very low (less
than 6%) throughout the exposure period. Similar findings were
observed for the coated Nylon textile immersed in tap water with
a slight reduction of the silver content (from less than 6 ␮g/cm2 to
approximately 5 ␮g/cm2 after 30 days), and an a bacteria viability
in the zero (0) % range throughout the exposure period, despite a
minor reduction of silver in the coating. The low extent of adhering
bacteria are presented in SEM images in Fig. 7.
Both uncoated and coated unexposed textiles material showed
a low degree of bacterial surface adhesion. Larger colonies of bac-
teria were observed after both 1 and 30 days on the Nylon textile
compared with the Camouflage textile, Fig. 7C.
The same trend with a larger reduction of the total silver con-
tent in the coating of textiles exposed in artificial sweat compared
with tap water was also evident from parallel measurements of the
total amount of silver in solution released from the coated textiles
in closed vessels (without any addition of fresh solution after sam-
pling), Fig. 8, and compositional surface analyses by means of XPS
after exposure.
The amount of silver in solution released from the coated Cam-
ouflage textile upon exposure in artificial sweat up to one week
was significantly higher compared with corresponding quantity in
synthetic tap water, Fig. 8 (top). Most silver (80%) in the coating
remained at the surface after one week of exposure in artificial

Fig. 6. Silver surface concentration in the coating as a function of time in artificial sweat and synthetic tap water (left y-axis), and bacterial survival in percentage as a function
of time in artificial sweat and synthetic tap water (right y-axis). The Camouflage textile was soaked in artificial sweat (left) and the Nylon textile in synthetic tap water (right).

Fig. 7. FEG-SEM images of bacteria S. aureus on the Nylon textile after immersion in synthetic tap water (top) and the Camouflage textile in artificial sweat (bottom) for an
unexposed coated sample (A, D), and after 1 (B, E) and 30 days (C, F) of immersion.
 S. Ferraris et al. / Applied Surface Science 317 (2014) 131–139 137

Fig. 8. Amount of silver in solution released from coated the Camouflage textile in artificial sweat and synthetic tap water after 2, 4, 24 and 168 h (top), and from the Nylon
textile in artificial sweat after 2, 4, 24 and 168 h, and in synthetic tap water after 24 h (bottom).

sweat, either as non-dissolved silver particles in the silica matrix, Similar findings were evident for the Nylon textile. Only a few per-
and/or as precipitated silver chloride complexes. More than 95% of cent of silver was released, even for the longest time measured.
the silver content of the coating remained after one week in syn- The importance of exposed surface area/solution volume ratio
thetic tap water, in which precipitation of silver species is minor. on the released amount of silver was illustrated for the coated Nylon

Fig. 9. Inhibition halo test with S. aureus for the Nylon (left) and Camouflage (right) textile after permeability and water repellency tests (top), and after one cycle in a
domestic washing machine (bottom).
138 S. Ferraris et al. / Applied Surface Science 317 (2014) 131–139
textile in both fluids. A lower area/solution ratio resulted in a higher
amount of released silver, Fig. 8 (bottom), which elucidates the
importance of system equilibrium of silver in solution and in the
coating.
A reduced amount of silver of the Camouflage coating upon
exposure in artificial sweat was also supported by XPS findings
for the outermost surface for which the mass ratio was reduced
from 0.50 ± 0.04 for the unexposed surface to 0.14 ± 0.02 after one
week in solution. No release of silver nanoparticles were observed
in solution either in synthetic tap water or artificial sweat after 0.5,
2 and 24 h of exposure (detection limit 100 ␮g/L in tap water and
500 ␮g/L in articifial sweat).
Changes in antibacterial activity of the Camouflage and Nylon
textiles (coated with sputtering condition D) were in addition
determined after permeability, water repellence tests and washing
in a domestic washing machine. The Nylon textile showed a signif-
icant inhibition halo (approximately 3 mm), Fig. 9a (left), i.e. good
antimicrobial properties, according to [36,37], after the permeabil-
ity and water repellency tests, whereas no inhibition halo was seen
for the Camouflage textile, Fig. 9 (top-right). A minor halo (<1 mm)
was observed for the Nylon textile after the washing cycle, Fig. 9
(top-left), the antibacterial activity can be classified as fairly good
according to [36,37]. No effect was observed for the Camouflage
textile, Fig. 9 (bottom-right).
FEG-SEM/EDS analyses confirmed the complete removal of the
coating on the Camouflage textile after the permeability and water
repellency tests, whereas the same tests did not significantly influ-
ence the coated Nylon textile (Ag/(Ag + Si) mass ratio of 0.57).
In agreement with antibacterial tests discussed above, the coat-
ing adhesion was definitely better on the Nylon textile compared
with the Camouflage textile. This is explained by high physical
interactions between polar amidic groups in Nylon and SiO2 that
enhances coating adhesion. Fluorine was detected on the non-
coated Camouflage textile surface, a remnant from the textile
treatment employed to hinder the adhesion of contaminants. How-
ever, its presence may influence the adhesion of the antibacterial
coating. The Black textile was not tested since its intended use
is non-relevant for the given conditions. As previously shown by
the authors, [26] the proposed technology to prepare antibacterial
coatings presents some advantages compared with others pro-
cesses on the market.
The proposed coating solution presents an improved resistance
to chemical and thermal stresses, obtained by silver nanoclusters
embedded in a silica matrix, compared with commercial antimicro-
bial textiles (i.e. Agiene® , Agion® and Trevira® Bioactive), which are
based on silver micron sized crystals, silver-doped zeolites and sil-
ver addition into the textile fibers. These improved properties can
provide a significant advantage for textile applications of intended
use in harsh environments such as in nuclear, bacteriological and
chemical (NBC) protection suites and for aerospace applications.
4. Conclusions
RF sputtering of an antibacterial silver nanocluster/silica com-
posite coating on textiles, for use in NBC protection suites and
for aerospace applications, resulted in coatings with a relatively
homogenous distribution of silver particles in a silica matrix.
By varying the sputtering parameters it is possible to tailor the
coating properties to match different requirements of antibacterial
activity and aesthetical appearance of the coated textiles.
The silver nanocluster/silica composite coating does not alter
the peculiar properties of uncoated textiles (e.g. flammability,
water repellency, tensile and tear resistance). A better adhesion of
the coating on nylon than on camouflage textiles has been observed
after water repellency and washing tests.
The release of silver ions in artificial sweat was significantly
higher than in synthetic tap water, showing the high importance
of the composition and pH of the solutions. No silver nanoparti-
cles were observed in solutions. All coated textiles revealed a high
antibacterial efficiency able to limit bacteria (S. aureus) prolifera-
tion up to 30 days of exposure in artificial sweat (the Camouflage
textile) and synthetic tap water (the Nylon textile), respectively. All
coated textiles showed a good correlation between a high amount
of silver remaining at the surface, and low bacterial adhesion and
viability.
Acknowledgements
This work was funded by REA within the European project (EU
Project-NASLA-FP7-SME-2010-1 (Project 262209)
Experimental help from Maria-Elisa Karlsson, KTH, is highly
appreciated.
Dr. M. Franchino and Prof. M. Avalle are kindly acknowledged
for performing mechanical tests on coated samples.
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