Journal of Composite Materials

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Multifunctional polymer composites: Antibacterial, flame retardant, radar absorbing and self-healing
Hsngl Yilmaz Atay and Erdal elik
Journal of Composite Materials published online 27 August 2014
DOI: 10.1177/0021998314549613
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JOURNAL OF
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M AT E R I A L S

Article

Multifunctional polymer composites:

Antibacterial, flame retardant, radar
absorbing and self-healing

Journal of Composite Materials

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DOI: 10.1177/0021998314549613
jcm.sagepub.com

Husnugul Ylmaz Atay1,2 and Erdal C

elik1,2

Abstract
Multifunctional materials are able to respond to environmental stimuli by exhibiting particular changes in some of their
properties. Desired properties can be combined to create a new item with composite materials due to their suitability
for achieving multi-functionality with the best characteristics of different materials. In this study, the aim is to further the
investigations of these types of materials and to advance the molecular understanding of novel multifunctional materials
for applications across different scientific disciplines. Regarding the production of multifunctional materials, four types of
materials were added to the polymer matrix to obtain the following properties: antibacterial, radar absorbing, selfhealing, and flame retardant. In this research, an epoxy dye was converted to a multifunctional material which is capable
of performing multiple functions. In order to reinforce an epoxy dye, Ag nanoparticles, huntite/hydromagnesite minerals,
barium hexaferrite particles, and chitosan were utilized for multifunction property. By adding those materials to the
polymer matrix with different loading level, different types of coated samples were obtained. Subsequently, the samples
were characterized by antibacterial tests, flame-retardant tests, radar absorbing tests, and self-healing tests besides other
characterization tests; FTIR, SEM, XRD, scratch, surface profilometer, etc. It was concluded that these materials
exhibited a synergetic beneficial effects.

Keywords
Multifunctional materials, antibacterial, flame retardant, radar absorbing, self-healing

Introduction
Multiple primary functions are capable of performing simultaneously or in sequence in multifunctional
material systems. These kinds of materials and functions, especially in between sub-systems, have been
developed to improve system performance by reducing
redundancy. Depending on the process, any property
can be given to the material that does not have this
feature such as mechanical, electrical, appearance,
structure, composition, and response. They are typically improving performance and meet the needs and
structural features embedded into the system to
change in a positive sense. This is to ensure that the
integrity of the evolution of the micro/nano-scale level
of their materials, systems, equipment, and structures
are created by integrating technologies from dierent
disciplines.1 Structural performance impact of such
materials have tremendous potential future by reducing
size, weight, cost, power consumption, and complexity
while improving eciency, safety, and versatility.2

The development of multifunctional materials can

enable to produce completely new or improved products including Nanomaterials, including advanced
materials, polymers, super/metallic alloys, and ceramic
materials for special applications.3 Integrating multifunctional materials into the structures may be able to
give real-time monitoring of the losses in the system, for
example, fatigue cracks or degradation of structural
connections.4
Composite materials, because they can be combined to create a new item, are ideally suited for
1
Department of Metallurgical and Materials Engineering, Dokuz Eylul
University, Tnaztepe Campus, Izmir, Turkey
2
Center for Fabrication and Applications of Electronic Materials (EMUM),
Dokuz Eylul University, Tnaztepe Campus, Izmir, Turkey

Corresponding author:
Husnugul Ylmaz Atay, Department of Metallurgical and Materials
Engineering, Dokuz Eylul University, Tnaztepe Campus,
Izmir 35160, Turkey.
Email: hgulyilmaz@gmail.com

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multi-functional materials to achieve the best characteristics of dierent materials. Accordingly, the reinforced materials and more functions are integrated in
the basic structural features of these composites to perform other functions.5
Numerous examples of materials that serve multiple
functions can be seen in nature. The human skin, for
instance as seen from Figure 1, consists of many layers
of cells, each of which contains oil and perspiration
glands, sensory receptors, hair follicles, blood vessels,
and other components with functions other than providing the basic structure and protection for the internal organs. These structures have evolved in nature
over eons to the level of seamless integration and perfection with which they serve their functions. Scientists
now seek to mimic these material systems in designing
synthetic multifunctional materials using physics,
chemistry, and mathematics to their advantage in competing with the unlimited time frame of natures evolutionary design process.2
An example of synthetic multifunctional material is
layered double hydroxides. Leroux et al.6 produced
layered double hydroxides based on the brucite
(Mg(OH)2) structure, with part of the divalent metals
isomorphically replaced by trivalent metals, inducing
positive charges in the layers that are compensated
for by interlayer hydrated anions. When intercalated
with dyes, layered double hydroxides act not only as
ller materials for synthetic polymers but also as multifunctional materials that are capable of conferring additional properties on the polymeric matrix, such as
color, transparency, photo/ultra violet (UV) and thermal stability, and ame-retardant capability.6
Another example is a novel multi-action nanober
membrane containing four active components, each
playing a dierent role in the membranes excellent
antibacterial function. Using an electro spinning technique, a new kind of free-standing antibacterial membranes have been prepared, which contain silver, silver
bromide, titanium dioxide, and hydroxyapatite as four

active components. In this antibacterial membrane,

each component serves a dierent function: apatite as
the adsorption material for capturing bacteria, silver
nanoparticles as the release-active antibacterial agent,
silver bromide nanoparticles as the visible-sensitive and
release-active antibacterial agent, and titanium dioxide
as the UV-sensitive antibacterial material and substrate
for other functional components.7
It is developed a structural model of a protein nanoparticle which has the key role of protein-nanoparticle
interactions in nanomedicine and nanotoxicity. Highly
selective protein adsorption, added to the fact that
particles can reach subcellular locations, results in signicant new potential impacts for nanoparticles on protein interactions and cellular behavior.8
In this study, it has been tried to develop a multifunctional material containing four active components
as mentioned earlier. One of the components of silver is
investigated for its antimicrobial property. It has been
used as an anti-bacterial agent by civilizations throughout the world for thousands of years. It was employed
as a germicide and antibiotic long prior to the development of modern pharmaceuticals. A large number of
investigations about silver can be seen in the literature.
Sondi and Salopek9 reported antimicrobial activity of
silver nanoparticles against E. coli as a model for gramnegative bacteria. Butkus et al.10 studied the synergistic
eect of silver ions and UV radiation on a RNA virus,
which can eciently enhance the eectiveness of UV
radiation. Yamanaka et al.11 investigated the antibacterial ecacy of silver ions using E. coli as a model
organism with the help of energy-ltering transmission
electron microscope (TEM), two-dimensional electrophoreses, and matrix-assisted laser desorption ionization-time-of-ight mass spectrometry. They conclude
that bactericidal action of silver ions is basically
caused due to the interaction of silver ions with ribosome and the suppression and expression of enzymes
and proteins necessary for ATP production. Pal et al.12
investigated the antibacterial properties of silver

Figure 1. Illustration of the many integrated functions within the human skin.2

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nanoparticles of dierent shapes and found that the

antibacterial ecacy of silver nanoparticles is shape
dependent. Shrivastava et al.13 reported synthesis of
silver nanoparticles in the size range of 1015 nm and
its dose-dependent eect on the gram-negative and
gram-positive microorganisms.
Huntite hydromagnesite mineral was used for its
ame-retardant property. Although this mineral has
been found in the last century and its ame-retardant
property has recently been studied, there are a few
investigations in the literature. Fernandez et al.14 studied it as a non-halogenated ame-retardant ller in a
28% vinyl acetate content poly (ethylene-co-vinyl acetate) matrix. The solid was characterized by X-ray uorescence and the crystalline phases determined by X-ray
diraction were composed predominantly of Mg(OH)2
and calcium and magnesium carbonates. They used
ame retardants including magnesium hydroxide to
develop halogen free ame retardant compounds
based on ethylene vinyl acetate for wire and cable applications. Cone calorimeter and limiting oxygen index
(LOI) results showed that cross-linking aects not
only the mechanical properties, but also ame retardancy. Haurie et al.15 used synthetic hydromagnesite in
combination with aluminum hydroxide and compared
it with commercial ame retardants such as magnesium
hydroxide and natural hydromagnesite huntite in a
polyolen system of low-density polyethylene/ poly(ethylene-co-vinyl acetate). They showed that synthetic
hydromagnesite could be an alternative solution to the
use of MH in non-halogenated ame retardant systems
in ethylene vinyl acetate. Morgan et al.16 used magnesium carbonate, and hydromagnesite/huntite blends
were combined with ethylene vinyl acetate and tested
for ame retardancy eectiveness with the cone calorimeter. They reported some polymerclay (organically
treated montmorillonite and magadiite) magnesium
carbonate ame-retardant results which showed that
the nanocomposite yielded mixed results.
Barium hexaferrite mineral was used for its microwave-absorption property. There are some investigations about this mineral in the literature. To illustrate
this, Aksit et al.17 produced fabrics with microwaveabsorbing properties in broad band. For this purpose,
the cotton fabrics were coated with polyaniline by using
chemical oxidative polymerization method. They concluded that microwave absorber for a textile material
can be successfully produced by this process. Jotania
et al.18 investigated the preparation of W-type hexaferrite particles with the composition BaCa2Fe16O27 by
micro emulsion and a stearic acid solgel method
with/without surfactant at various sintering temperatures. A simple solgel method in the presence of different types of surfactants as well as in a micro
emulsion system is used for the preparation of

bariumcalcium hexaferrite particles. It has been

observed that the type of surfactant plays a crucial
role in deciding the morphology of the particles. The
magnetic studies carried out using a vibrating sample
magnetometer showed that low coercivity was found in
the presence of surfactants. Mozaari et al.19
prepared a series of barium hexaferrite nanoparticles
(BaO.nFe2O3) with dierent n values by the solgel
method, using goethite and bicarbonate as raw materials. The results show that the samples have nonzero
coercivities, which shows the particle size is not less
than the critical size of Ba ferrite and then are not
super paramagnet.
Chitosan was used for its self-healing property.
Inasmuch as self-healing is a new trend in material
science, there are a few literature knowledge about
this subject. White et al.20 reported of a completely
autonomous man-made self-healing material. They
reported an epoxy system containing microcapsules.
These microcapsules were lled with a liquid-thermosetting monomer. If a microcrack occurs in this
system, the microcapsule will rupture and the monomer will ll the crack. Ghosh and Urban21 reported
the development of polyurethane networks that exhibit self-repairing characteristics upon exposure to
ultraviolet light. The network consists of an oxetanesubstituted chitosan precursor incorporated into twocomponent polyurethane. Upon mechanical damage
of the network, four-member oxetane rings open to
create two reactive ends. When exposed to ultraviolet
light, chitosan chain scission occurs, which forms
crosslinks with the reactive oxetane ends, thus repairing the network. Yoon et al.22 synthesized self-healing
polymeric materials with branched architectures and
reversible cross-linking functionalities at the periphery
of branches by atom transfer radical polymerization
(ATRP). Poly(n-butyl acrylate) grafted star polymers
were prepared by chain extension ATRP from crosslinked cores comprised of poly(ethylene glycol diacrylate). They demonstrated the suitability of grafted
multiarm polymer architectures as building blocks of
self-healing polymeric materials and pointed to the
importance of low intrinsic viscosity of material and
high accessibility of functional groups responsible for
healing.
The aim of this study is designing a material to
accomplish multiple performance objectives in a single
system to respond the required needs as mentioned earlier; antibacterial, ame retardant, radar absorbing,
and self-healing. An epoxy dye was converted to multifunctional material which is capable of performing multiple functions. In order to reinforce the epoxy dyes, Ag
nanoparticles, huntite and hydromagnesite minerals,
barium hexaferrite particles, and chitosan were used.
By adding those materials to the polymer matrix with

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dierent loading levels and by coating the substrates,

dierent types of coated samples were obtained.
Subsequently, the samples were characterized by antibacterial tests, ame-retardant tests, radar-absorbing
tests, and self-healing tests, besides other characterization tests; FTIR, SEM, XRD, scratch, surface prolometer, etc.

Experimental
Preprocessing
Ag nanoparticles were synthesized by a reduction reaction as described by Yan et al.23,24 and summarized
here. An aqueous solution of silver nitrate and an aqueous solution of a non-ammonia reducing agent were
mixed to form a nanosilver particle-containing solution
at room temperature. Glucose was used as a reducing
agent in this study wherein silver nitrate and glucose
were in the ratio of about 2:1 by weight. It is reported in
Binitha et al.24 that with this method, the fabricated Ag
nanoparticles have a diameter between 1 and 100 nm.
On the other hand, according to Binitha et al.,24 glucose reductant together with urea stabilizer makes size
of silver particles low in the range of 45 nm for better
catalytic activity. Briey, a nitrate solution was mixed
with a 10 mL aqueous solution of glucose. The silver
nitrate was reduced to metallic silver by interacting with
glucose (where the glucose itself was oxidized to gluconic acid). Water used for solutions was distilled.
Stirring was performed for 15 min at room temperature
and Ag ions were reduced, and additionally gluconic
acid and nitric acid were formed as the other products
of the reaction. The solution had been stirred repeatedly until it became stabilized and approximately after
an hour some dark color appeared. At this point, Ag
nanoparticles were chemically stable in the solution.24
After the huntite/hydromagnesite minerals is
crushed and ground to get ner fractions, the powders
were ground again from micron-scale powders to nanosize particles in a high energy ball milling machine
(Fritsch Premium line Pulverisette 7 model) at the
rate of 800 rpm at room temperature for 15 min in air.
Barium hexaferrite powders were synthesized
through solgel method.17,25 Preprocessing and synthesis of the powders were described in Aksit et al.17 in
detail and briey summarized here, and barium ferrite
powders with atomic scale were prepared by using the
citrate solgel process (Figure 8). Used precursors were
barium nitrate (Ba(NO3)2, Aldrich) and ferric citrate
mono hydrate (C6H5FeO7.H2O, Fluka), chelating
agent was citric acid monohydrate (C6H8O7.H2O),
and pH regulator was ammonium hydroxide
(NH4OH). The solutions were vigorously mixed by
magnetic stirrer until the transparent solution was

obtained. Ammonium hydroxide was added until the

solution reaches a pH value of 7 at room temperature
and then mixed by magnetic stirrer. Thus it was aimed
to provide homogenous suspension and stable pH condition in the solution after whole solution preparation.
The solution was kept in water bath at 80 C for 15 h.
Therefore, the water in the solution was gradually
removed and wet gel with high viscosity was obtained.
The wet gel was treated at 180 C for 15 h in Nuve
KD400 oven (Nuve, Inc., Ankara, Turkey) to prepare
a dry gel. The dry gel was exposed to a pre-sintering
process at 550 C for 6 h to evaporate impurities
and then was sintered at 1000 C for 5 h in an ash
oven in air.17
Chitosan (MW 150 kDa, degree of deacetylation
84.5%) was purchased from Sigma (St. Louis, USA).
Chitosan were dissolved completely in acetic acid solution (3% by v/v) under stirring. Then, they were stirred
in an ultrasonic cleaner. Finally, the colloids were stirred for 20 min in air by using magnetic balls and homogenous colloids were obtained.

Fabrication of composite materials

Epoxy dye has been used as a composite matrix that is
known as polyepoxide, a thermosetting copolymer
formed from the reaction of an epoxide resin with
polyamine hardener. The resin consists of short
chain polymers with an epoxide group at either end.
Epoxy resin is produced from a reaction between epichlorohydrin and bisphenol-A. The hardener consists
of polyamine monomers, triethylenetetramine.26,27
For multifunctional properties, epoxy composite
dyes were prepared by adding Ag nanoparticles for
antibacterial characteristics, huntite/hydromagnesite
powders for ame-retardant property, barium hexaferrite powders for the radar-absorbing behavior, and
chitosan colloids for the self-healing property at dierent ratios into the paint matrix. Additive amounts and
the ratio of the multifunctional composites are given in
Table 1.
According to the characterization tests, dierent
types of substrates such as plastic, glass, and metal
were used for multifunctional composite coatings.
First of all, pure dye coating was obtained as a control
sample. Then, it was started to add dierent kinds of
additives with dierent amounts. By concentrating the
composite matrix with the additives, each composite
sample of dierent concentration was utilized to scrutinize the concentration dependency.

Characterization
Prior to coating process, obtained Ag solutions were
subjected to some characterization tests. Atomic

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absorption spectroscopy was used for the estimation of

the quantity of Ag ions, DNS method for estimating
the glucose quantity, pH meter for determining the
activity of hydrogen ions, turbidimeter to determine
dissolution of the particles in the solution, and particle
size analyzer was used for estimation of the size of Ag
nano-powders. The phase analysis of minerals and
composites were performed by using a Rigaku D
(Max-2200/PC Model XRD) X-ray diractometer at
40 kV, 20 mA with a monochromatic CuK irradiation
(wavelength, l 0.15418 nm) by both 2 mode and
2 scan mode with a scan speed of 8 /min. The microstructural cross-sectional areas of polymeric composite
materials were examined by using a JEOL JJM 6060
SEM with an EDS attachment. Size factors and wettability properties were examined in the composites
using SEM-EDS. FTIR (Perkin Elmer) absorption
spectra of the composite materials were only measured
over the range of 4000 to 400 cm1 at room temperature. FTIR (Perkin Elmer Spectrum BX) spectra of
composite materials were recorded to determine the
organic components in the samples. The proles of
the composite samples surfaces were investigated with
a surface prolometer Mitutoyo SJ-301 in order to
quantify the roughness. The device measures a surface
as the surface is moved relative to the contact prolometers stylus; this notion changes with the emergence
of numerous non-contact prolometer techniques.
Adhesion properties of the composite coatings were
measured by using Shimadzu Scanning Scratch Tester
SST-W101 equipped with a standard o-line Zeis metallographic microscope. Critical force (Wc) value, at
which the coating is removed from the substrate, was
determined with an optical microscope. After micro
hardness value of metal substrate was converted to
Brinell Hardness (H) from Vickers Micro hardness by

using Standard Hardness Conversion Tables for Metal,

the adhesion strength (F) of the coatings was calculated
as MPa unit by using equation (1)28
Fh

R2 HWc
Wc

i1=2

The agar disc diusion method was employed for the

determination of antimicrobial activity of silver-loaded
coating specimens (in size of 2.4  2.4 mm) against
S. aureus ATCC 6538P, a Gram-positive bacterium
and E. coli ATCC 12228, a Gram-negative bacterium
(NCCLS, 1997). Briey, test bacteria were grown in
Muller Hinton Broth (MHB) at 37 C for 18 h and a
suspension of the test bacteria was spread on solid
media plates containing MHA. After duration of 2 h,
silver-loaded polymer coatings were placed in the center
of inoculated plates and incubated at 37 C for 24 h. At
the end of the incubation period, the plates were
inspected for growth on and under silver-loaded coating samples, as well as for the presence or absence of
growth in a halo around the samples. The width of the
halo was measured across the center line of the sample,
both horizontally and vertically. An average of these
two values was then taken to give an estimate of the
antimicrobial activity of the samples as shown in equation (2) (Figure 2). Each experiment was repeated for
three times.
Inhibition Radius r1 r2=2

Barium
Huntite/
Ag
nanoparticles hydromagnesite hexaferrite Chitosan
Code of
(%)
(%)
(%)
the samples (%)

0.05
0.1
0.2

0.05
0.1
0.2

10
10
20
30
10
10
20
30

5
5
10
20

5
5

0.05
0.05
0.1
0.2
0.01
0.01
0.05
0.1

Flame-retardancy testing of the composites was performed. There exist two types of ame-retardant tests;
LOI and UL94. A LOI test machine measures the minimum concentration of oxygen in a owing mixture of
oxygen and nitrogen that will just support aming
combustion of a material initially at room temperature.

Table 1. Description of the multifunctional composite samples

by percentage.

AMF 0
AMF 1
AMF 2
AMF 3
AMF4
BMF 1
BMF 2
BMF 3
BMF 4

Figure 2. Zone of inhibition in the agar plates.

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The ame-retardant composite coatings on plastic substrates are ignited and burns from the top downwards.
The rating or oxygen index is expressed in terms of this
volume percent oxygen concentration.29 The UL 94
technique is used in plastic industry according to
UL94 standardization. The material is conducted to
the ame in a specic angle and distance.
Extinguishing time of the ame and dripping ability
are measured.30 There are three dierent tests in UL
94; surface, vertical, and horizontal burns, as indicated
schematically in Figure 3.31 The samples are subjected
to ame for 3 min after the calibration process is completed (ame height: 12 mm, it is 23.5 s:  1 s to reach
from T1:100 C to T2:700 C). The used gas is propane
with 99.5% of purity.
The electromagnetic parameters of the composites
were measured with transmission/reection method in
the region of 812 GHz with a Network Analyzer
HP8720D. Figure 10 shows the setup schematically.
The network analyzer and coaxial line xture have
been calibrated. The incident power delivered by the
network analyzer and the reected and transmitted

(a)

power measured by the network analyzer are depicted

(Figure 4).17
To see the self-healing property of composites,
scratched coatings were analyzed with a Philips XL
30 S FEG Scanning Electron Microscope (SEM).
SEM images of each sample were taken at dierent
days and any improvements related with healing were
investigated by the time.

Results and discussions

Additives
Using atomic absorption spectroscopy, Ag ion concentration in the obtained solution was estimated as
10%, which agrees with our estimation at the beginning. Depending on this result, it can be said that correct AgNO3 amount was calculated very well before
preparation of nano Ag.
Due to the fact that microorganisms use glucose
materials as food, their residue in solutions and coatings is not desired. Such a residue inuences

(b)

(c)

Surface Burn

Vertical Burn

Horizontal Burn

Doesnt ignite under

Self-extinguishing

Slow burn rating

hotter flame

UL 94 V-0 (best)

Takes more than 3 min.

UL 94 5VA

UL 94 V-1 (good)

to burn 4 inches

UL 94 5VB

UL 94 V-2 (drips)

Figure 3. Schematic of UL94 test requirements: (a) surface, (b) vertical, and (c) horizontal burn.31

Figure 4. Measurement setup with network analyzer and coaxial line fixture. Incident, reflected, and transmitted power at the
sample material.17

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antibacterial activities in the coatings. Thanks to this

reason, glucose determinations were performed to prepare Ag nanoparticles through DNS method. It was
estimated as 0% which is very good for further processing; the experiments were gone on to be produce antibacterial coatings.
Many chemical processes and properties, such as the
speed of a reaction and the solubility of a compound,
can also depend greatly on the pH of the solution. The
pH value of the obtained solution was determined as
4.80. While ramied structure having Ag nanoparticle
is randomly formed in acidic conditions, separated clusters are formed from the solutions showing basic characters. The nanoparticle with bigger size is generally
produced with the ramied structure. Owing to this
reality, the size of Ag nanoparticle can be changed by
altering pH values of the solutions. Upon decreasing
the size of Ag nanoparticle, its antibacterial activities
dramatically increase in the coatings.
Turbidity values of the solutions vary in the range of
0 ntu and 1000 ntu. It is interpreted that powder-based
precursors are completely dissolved as turbidity value
approaches 0 ntu and they are not dissolved and some
powder particles are suspended in a solution as it
approaches 1000 ntu. In this experiment, turbidity
value of the solutions was measured as 58.80 ntu.
Based on the turbidity value, it can be pointed that
AgNO3 powder is completely dissolved in the solutions.
The size and particle size distribution of Ag nanoparticles were determined using particle size analyzer
which uses light scattering techniques to measure the
hydrodynamic size of nanoparticles. Particle size distribution of the produced Ag nanoparticles was represented in Figure 5. According to size distribution
approximate, particle size was found to be in the
range of 39 nm and 128 nm, and the average particle
size was about 67.36 nm which is acceptable for antibacterial activities. The produced Ag nanoparticles can

be identied as monodispersed due to small particle size

distribution range.
The XRD pattern of huntite/hydromagnesite mineral powder is shown in Figure 6. It is found from
this result that the basic minerals are hydromagnesite
(Mg4(OH)2(CO3)3.3H2O), huntite (Mg3Ca(CO3)4), and
dolomite (CaMg(CO3)2) in the raw huntite/hydromagnesite mineral. The most striking feature of the powder
is that the main phases with high intensity are huntite
and hydromagnesite. An average mineralogical composition, based on XRD and chemical analysis data
of current ores, is as follows: huntite (46%), hydromagnesite (46%), magnetite (4%), aragonite (3%), and calcite (1%). This nding in the current study is similar to
Kirschbaums research.32
Figure 7 demonstrates SEM micrographs and EDS
analysis of huntite/hydromagnesite mineral particles.
It is seen from Figure 8 that huntite/hydromagnesite
mineral particles of 20 mm size possess irregular
shapes after the grinding process. EDS analysis
proved XRD result because Mg, Ca, C, and O elements were found in the huntite and hydromagnesite
mineral and there are some elements from ores as
impurities.
Figure 8 shows XRD pattern of BaFe12O19 powders
produced by the solgel process. The presence of
barium ferrite phase as a major phase and also a little
amount of iron oxide (Fe2O3) as a minor phase is
observed in the powders. No amorphous phase is indicated. We have a good agreement with Mali and
Ataie33 that the reaction was sucient for complete
conversion of the metal compounds to metal oxides.
This may a result of high sintering temperature
(1000 C). On the other hand, as the increase of heat
leads to particle growth, it needs to be decided an optimum sintering temperature. Such that in Figure 11,
observed narrow diraction peaks are due to an
increase in the crystallite size.33,19

1: Hydromagnesite - Mg4(OH)2(CO3)33H2O

100
25

Intensity (Count)

Intensity (%)

20

15

10

80
1

60

3
1

40
20

1 1 1

1 1
2

2
2

2
2 2

0
0
0,1

2: Huntite - Mg3Ca(CO3)4

1 3: Dolomite - CaMg(CO3)2

Average= 67.36 nm

10

100

1000

20

40

60

80

100

Two-Theta (deg)

10000

Size (nm)

Figure 5. Particle size distributions of Ag nanoparticles.

Figure 6. XRD pattern of huntite/hydromagnesite mineral

powder.

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Figure 7. SEM micrographs and EDS analysis of huntite/hydromagnesite mineral.

Figure 8. XRD patterns of BaFe12O19 powders.

Figure 9 shows morphology of BaFe12O19 powders

produced by the solgel process. It is interesting to note
here that the micrographs of the BaFe12O19 powders
illustrated the powders with platelet microstructure
with an average particle size of 10 nm in hexagonal
basal plane.17,19

Coated samples
Figure 10 shows FTIR spectra of the multifunctional
coated samples. It can be seen from the gure that the

chitosan exhibits main characteristic bands of carbonyl

(C O-NHR) and amine group (NH2) at 1450 cm1.
Nevertheless, this band can correspond to CH bending
from epoxy matrix. Huntite hydromagnesite and
barium hexaferrite powders are not organic minerals
and they cannot be indicated for FTIR. In the same
way, CH3COH group band can be observed at
748 cm1 related with the chitosan but this may come
from the epoxy, because the characteristic peaks of
epoxy indicate the formation of SiO, SiOSi, and
SiC at 751, 1084, and 1270 cm1, respectively.

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Table 2. Surface profilometer test results.
Surface roughness
values
Ra

Rt

Figure 9. SEM micrographs of barium hexaferrite powders.

Absorbance (%)

bmf4

bmf3

BMF1

BMF2

0.40
0.39
0.87
4.27
3.54
6.53

5.19
4.96

9.95
12.71

46.35
39.51

82.95
114.09

Table 3. Multifunctional composite coatings scratch test

results.
Sample codes

0.3
0.2
0.1
0.0
0.3
0.2
0.1
0.0
0.3
0.2
0.1
0.3
0.0
0.2
0.1
0.0
0.3
0.2
0.1
0.0
0.3
0.2
0.1
0.0
0.3
0.2
0.1
0.0

MF0

BMF1 BMF2 BMF3 BMF4 MF2 MF4 MF0

Critical Force
38.5 19.5 24.3 21.2 24.7 22.5 13.5
(mN)
Adhesion Strength 67.04 43.39 49.16 45.98 49.79 45.34 35.16
(MPa)

bmf2

Table 4. Decreasing percentage test results of multifunctional

composite coatings.
amf4

amf2

amf1

amf0

Si-O Si-O-Si Si-C

CH3. CH2

1000

2000

3000

4000

5000

Sample
codes

E. coli amount at
the beginning

E. coli amount
after 2 h

Percentage
decreasing

AMF 0
AMF 1
AMF 2
AMF 3
AMF4
BMF 1
BMF 2
BMF 3
BMF 4

9.105
9.105
9.105
9.105
9.105
9.105
9.105
9.105
9.105

79.104
75.104
68.104

46.104

12.2
16.66
24.44
100
100
48.88
100
100
100

Wavenumber (cm )

Figure 10. FTIR analysis of multifunctional composite samples.

The broad band due to the stretching vibration of

NH2 and OH group from chitosan can be observed
at 2950 cm1 but it may be related with epoxy alkyl
groups (CH3, CH2) stretching. The similar results
were reported elsewhere.34
Surface roughness of the multifunctional coatings
represented by the arithmetic mean value Ra and the
maximum roughness height Rt values were demonstrated in Table 2. These values can give the ideas
regarding the surface proles of the composite samples.
It can be seen that the samples do not have very good
smooth surfaces. Furthermore, some of the samples

could not be tested. This may be due to adding dierent

kinds of materials and powders into a liquid material.
Scratch test results of the multifunctional coatings
are denoted in Table 3. It can be pointed out that the
adhesion strength of the multifunctional composite
coating is higher than that of pure dye.
Decreasing percentage test results of multifunctional
composite coatings as coded in Table 1 are given in
Table 4. Ag nanoparticle content was in the range of
0.05%0.2% in the multifunctional coatings. Some
photographs of the tests are depicted in Figure 11.
According to those results, all composites showed
successful antibacterial behaviors. Notably AMF3,
AMF4, BMF2, BMF3, and BMF4 specimens

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AFTER FLAME

AMF2

AMF1

AMFO

BEFORE FLAME

AMF3

Figure 11. An example of antibacterial test results.

AMF0
AMF1
AMF2
AMF3
AMF4
BMF1

55 s
No flame
No flame
No flame
No flame
60 s (only the paint)
till 120 s
55 s (only the paint)
till 126 s
No flame
160 s

>180 s
No after
No after
No after
No after
No after

NOK
OK
OK
OK
OK
OK

BMF2
BMF3
BMF4

flame
flame
flame
flame
flame

No after flame

OK

No after flame
>180 s

OK
NOK

NOK: Not O.K.

destroyed 100% of the bacteria after 2 h; all of those

mentioned samples had Ag nanoparticles. It was
observed that AMF1 and BMF1 samples destroyed
some bacteria due to presence of chitosan.
Flame-retardant test results of multifunctional
composite coatings as coded in Table 1 are shown in
Table 5. As may be seen from Table 1, huntite/hydromagnesite content changed between 10% and 30% in
the multifunctional coatings. As shown, except for the
control sample and BMF4, all composites seem to be
ame retardant. Inasmuch as BMF1 and BMF2 samples possessed 10% huntite hydromagnesite, they were
described as ame retardant but this amount might be
not enough for the excellent ame retardancy that similar results were obtained from the earlier studies. Note
that AMF4 and BMF4 samples had 30% huntite and
hydromagnesite. In spite of the fact that AMF4 sample
was an excellent ame retardant, BMF4 failed for this
application. This might be due to lack of barium hexaferrite. Thus, it can be expressed that barium

BMF1

Result

BMF2

After flame

BMF3

Flame starts at

BMF4

Plastic material

AMF4

Table 5. Flame-retardant test results of multifunctional

composite coatings.

Figure 12. Flame-retardant results of pure dye and

multifunctional coatings before flame and after flame testing.

hexaferrite redounded ame retardancy with huntite

hydromagnesite.
The photographs of multifunctional coatings before
ame and after ame are shown in Figure 12
indicating that the multifunctional composites exhibit

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8

(b)

(a) 100
Metal
AMF0
AMF1
AMF2
AMF3

60

AMF4
BMF1

40

BMF2
BMF3
BMF4

20

Absorber

0
8

10

11

12

Absorbance (%)

Absorption (%)

80

Frequency (GHz)

0
2
4
6
5
0
5
10
5
0
5
1
2
3
4
5
6
10
5
0
10
5
5
0
5
4
2
0
2
4
5
0
5
0
2
4
2
4
6
8

10

12

10

12

BMF4

BMF3

BMF2

BMF1

AMF4

AMF3

AMF2

AMF1

AMF0

Metal

Frequency (GHz)

Figure 13. Network analyzer test results of the multifunctional coatings (a) with and (b) without absorber.

ame-retardant behavior. It is obviously clear from

Figure 12 that even though pure dye coating (AFM0)
burned easily, multifunctional coatings strongly
showed ame-retardant properties. As shown from
Figure 12, AMF4 sample which contains 30% huntite/hydromagnesite mineral was an excellent ame
retardant owing to the synergic eect of barium hexaferrite. This behavior could not be observed in BMF4
sample which contains 30% huntite/hydromagnesite
mineral, thanks to lack of barium hexaferrite.
Figure 13 signies the absorption values versus the
frequency range of 614 GHz of the multifunctional
coatings. Here, barium hexaferrite content altered
between 5 and 20% in the multifunctional coatings.
Note that in this case, the highest absorption was
obtained from AMF4 which have the highest barium
hexaferrite amount (20%). The second one was AMF3
which have 10% barium hexaferrite as the radarabsorbing properties. AMF1, AMF2, BMF2, and
BMF3 (5%) are similar and again they have useful
absorption values.
As standard absorber is omitted in Figure 13(b), the
composite coatings absorption values can be seen in
detail. It can be normally seen that there was no any

absorbing activity in pure epoxy coating due to lack of

barium hexaferrite in the sample. However, in the
BaFe12O19 reinforced coating, there were signicant
absorbing activities. The radar waves absorbing properties of composites were substantially improved after
the loading of barium hexaferrite particles; the absorbing percentage increases with increasing additive content in the composite coatings.35 The highest absorbing
peak reaches 12.13% at 11.86 GHz with the sample
of BF20.
As mentioned earlier, BaFe12O19 has large magneto
crystalline anisotropy. Due to the spin orientations of
the Fe3 ions, the numbers of unpaired electrons
occurred in their 4 s and 3 d shells. Those not fully
lled shells lead to magnetic moment. On the other
hand, the magnetic moment of barium hexaferrite particles is related with not only the unpaired electrons,
but also the angular momentum which represents the
product of the bodys rotational inertia and rotational
velocity. These unique characteristics enhance largely
the microwave absorption performance of barium hexaferrite-reinforced composites.36
Figure 14 depicts SEM micrographs of the selfhealed multifunctional coatings after scratch testing.

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After 0 min

After 30 min

AMF0

AMF1

AMF2

AMF3

BMF1

BMF2

BMF3

reinforced samples, self-healing properties were

obtained just after 30 min, and no more improvement
has been found after that time.
Generally speaking from all gures, self-healing
property can be determined as branches of the tree
which ll and seal the open cracks. As, there is no
healing behavior in AMF0, chitosan rate is 0.00%, it
can be said that chitosans self-healing eect appeared
clearly with spanning the gap of a thin scratch. Epoxy
polymer composites at room temperature far below the
glass transition temperature tried to diuse across those
gaps. If this is a cross-linked network of epoxy composites working by the agency of chitosan, sample of
AMF0 also should have that kind of healing property.
This is important for the possible diusion processes.
On the other hand, the distinctions on the crack tips
were measured and written on the micrographs, and the
self-healing may not be determined according to those
values, because, as mentioned above, branches were
developed like the arms for a wound to heal. That is
to say, self-healing mechanism might be operated with
those branches.
The self-healing results agree with Kesslera et al.37
that partially cured poly (DCPD-dicyclopentadiene)
strands, which are bridging the cracks behind the
crack tips, were observed. Present on the surface are
several strands of poly(DCPD) that bridged the two
surfaces of the delamination before ultimately rupturing and collapsing in a folded lm on the fracture
surface.37 On the other hand, as it is explained in
detail in Wu et al.,38 the healing mechanism is similar
to molecular interdiusion method. This method is
that when two pieces of the same polymer are brought
into contact at a temperature, the interface gradually
disappears and the mechanical strength at the polymerpolymer interface increases as the crack heals
due to molecular diusion across the interface.
Visual healing of the fracture surfaces was found to
occur before a signicant recovery in strength was
achieved, with the interdiusion of numerous chain
segments being reported as the most likely healing
mechanism.38

Conclusions
Figure 14. Self-healing properties of multifunctional composite
coatings.

In these experiments, chitosan content varied in the

range of 0.010.2% in the multifunctional coatings.
As stated earlier, the micrographs were taken from
the samples in 0 min, 30 min, 7 days, 20 days, and 35
days after the scratching to examine the improvement
on healing from SEM machine. From all chitosan-

The production and technical applications of the multifunctional materials were investigated. An epoxy dye
was converted to multifunctional materials which are
capable of performing multiple functions; antibacterial,
ame retardant, radar absorbing, and self-healing.
Four dierent types of materials were incorporated
into polymer matrix with dierent grades and with different particle contents: for antibacterial property, Ag
nanoparticles; for ame-retardant characteristic, huntite and hydromagnesite minerals; for radar-absorbing

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behavior, barium hexaferrite particles; and for selfhealing property, chitosan. Fundamental structural
and functional properties of the materials were investigated to determine the eect of the additives concentration to the structure. To produce multifunctional
coating, Ag nanoparticles were synthesized by a reduction reaction. Huntite/hydromagnesite minerals were
ground to nanosize in a ball mill. Barium hexaferrite
powders were obtained by solgel processing. Chitosan
was used as a homogeneous colloid by using an acid
solution. Then, the obtained additives were added to
epoxy dye with dierent loading levels and the glass,
plastic, and metal substrates were coated with those
polymer composites. At the end of the characterization
and functional tests, generally it was found that almost
all composite coating samples depicted very good antibacterial, radar absorbing, ame retardancy, and selfhealing properties. In detail, regarding the antibacterial
property, even AMF0, AMF1, and BMF1 had no Ag
nanoparticles, and they demonstrated a little bit of antibacterial property. AMF0 was 12% and AMF1 was
16%, and these may come from epoxy dye itself.
BMF1 was 49% and this may come from chitosan.
All the other samples having Ag nanoparticles were
100% antibacterial value. Related with ame-retardant
property, apart from BMF4, all other samples showed
very good ame-retardant property. Although BMF4
had higher huntite/hydromagnesite quantity (30%),
ame retardancy results were not good. The reason
for this may be having very poor coating surface quality. For the radar-absorbing property, AMF4 was the
best absorber, which had 20% barium hexaferrite powders, AMF3 was the best after AMF4 which has 10%
barium hexaferrite powders, and the others having
barium hexaferrite showed radar absorbing property
lower than AMF4 and AMF3. Regarding the self-healing property, except for AMF0, which has not a chitosan colloid, all samples demonstrated self-healing
property. It was indicated that when the cracks were
narrow, self-healing activity was obtained better like
AMF3 and BMF2. Besides those functional experiments, it is indicated from the surface prolometer
test that increasing the mineral additive amount in the
coatings decreased the surface smoothness. In this
sense, if one of the samples needs to be selected for
the best, BMF2 can be chosen due to depicting all
four properties. Moreover, having 10% huntite hydromagnesite and 5% bariumhexaferrite, BMF2 has
smoother surface, is not heavy, and its mechanical
property will not be broken down due to having mineral powders.
It can be concluded that multifunctional polymer coatings with four dierent properties were successfully prepared from dierent kinds of materials. It was stated that
generally all properties were increased with increasing

additive loading levels. This was the same for monofunctional samples or multifunctional samples. Therefore, it
can be pointed out that even if they were used in the same
material, those four types of materials did not inuence
each other negatively. To examine the optimum loading
grades of the additives, one needs to look at the environmental conditions and the needs. According to the
requirements, the additive amounts can be determined.
The structural and functional experiment results discussed in this study show that after optimizing all parameters, it is possible to prepare prototype applications
of these materials. It is possible to give a material (such
as an aircraft) antibacterial, ame-retardant, radarabsorbing, and self-healing activities just by painting
that kind of composite dyes. To obtain better surface
quality, dierent kinds of additives can be attempted.
In addition, dispersants can be used to stabilize the
suspension of the additive particles in the polymer
matrix, and emulsiers can be used to bind the dierent
additive materials to the epoxy. This can allow the
materials to mix uniformly and prevent the polymer
composite in an emulsion from separating into layers.
In this manner, more homogeneous composite materials and smoother coating surfaces can be achieved.
Funding
The authors are indebted to the State Planning Foundation
_
_
(DPT, Ankara, Turkey), TEKNOBIM
Company (Izmir,
Turkey), VESTEL Company (Manisa, Turkey), LIKYA
_
MINELCO Company (Izmir,
Turkey), Izmir Institute of
_
Technology (Izmir, Turkey) and Dokuz Eylul University
_
(Izmir,
Turkey) for nancial and technical supports.

Conflict of interest
None declared.

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