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CHAPTER 2
LITERATURE REVIEW
2.1 Introduction
nanoscale level has gained ever more attention during the last decade. These new
hybrids can be considered as the composite in which at least one phase is of below
100-nm size. The polymer –clay nanocomposites first reported in the literature by
nanofillers such as precipitated silica, silica alumina, silica beads, cellulose whiskers,
zeolites, natural and synthetic modified silicates (Insitu method)[2-4]. Clays are
intensively used in nanocomposites. The layered silicates (natural clay) like mica,
laponite, fluorohectorite can be synthesized. Most of the recent studies have focused on
the use of natural clay from smectite family “Montmorilonite” because of its layer charge
density [5-7]. It is most widely used nanofiller. Montmorillonite contains in the addition
varying amount of crystobalite, zeolites, quartz, felspar, Al2O3 identically found suitable
in high cutting tools, high surface area support catalyst, tribological materials, heat sinks
There are number of techniques currently available for the synthesis of nanoparticles of
oxides and non oxides, these include laser ablation[9], microwave plasma synthesis[10],
these techniques are based on the particle size, distribution morphology, purity and
degree of agglomeration .Spray pyrolysis produces the particle size near to 10 nm.
Narrow size distribution is not possible in majority of technique. Nanoparticles less than
agglomerate. Chemical vapor condensation gives particle size 3-50 nm and its
utilized as filler to create high performance materials assuring better homogenity, higher
synthesized the nanoparticles with the help of microemulsion process. One of the
principal problem in using PTFE as filler is difficulty of adhesion with other materials. He
also developed the microemulsion polymerization together with various “core shell”
techniques which permits to obtain materials for the optimal use as high performance
filler.
mean particle size in the range from 5 to 20 nm .The products may be oxides, nitrides,
with a layer of second ceramic or a polymer. The resulting material is found to be the
mixtures in the low pressure flames, specially designed burner is used to achieve a flat
flame. Metal organic precursors introduced along with the fuel /air mixture experience
complete and uniform decomposition, thereby yielding a uniform synthesis of SiO2, TiO2
and Al2O3 nanophases. The product of ball milling of the magnetic and amorphous silica
(40-mole % Fe3O4) for an extended period of time in closed vessel has been
investigated by Koch et al [17]. It is found that the milling induces an extensive reduction
and magnesia system are prepared with sol gel technique. The temperature evolution
of hydrolyzed zirconium, titanium, and magnesium until they form the corresponding
nanocystalline oxides [18]. Al2O3 ceramics are important structure ceramics but α-Al 2O3
is stable phase after calcination at high temperature, which easily promotes the growth
of grain powder and makes it difficult to get in nanoform, and other reason is Al 2O3
particles get agglomerated during dehydration process. Considering the problem Wang
which nanoscale α-Al2O3 powder with of size 10 nm can be obtained. Its calcination
chemicals such as Ag, ZrO2 and Ba, TiO2 etc., the nanometer sized titania particles
have been prepared by chemical reaction between TiCl4 solution and ammonia in the
anatase and
grew selectively in the (001) direction with a diameter of about 4 nm and length of about
40 nm. Acetic acid played an important role in the oriented growth of nano-TiO 2
whiskers [20]. New development in the synthesis of nanometer scale TiO2 particles
ultrasonic method was used to disperse the nanoparticles in epoxy, thus this method
eliminates the need of solvent without sacrificing the ease of processing [21].
rutile phase is influenced by the synthesis condition. Most of the literatures show that
powders or powders with the anatase phase. [22-24 ]. At present there are few studies
[25-26] have investigated gas phase synthesis of Titania by TiCl4 oxidation in presence
of dopants. Ocana et. al.[27] obtained rutile TiO2 powder at 98 oC, using 3M TiCl4, for
measuring it’s IR and Raman spectra, but did not comment on fabrication method
production. Terwilleger et. al.[28] prepared the rutile phase TiO2 powder with an
average grain size < 20 nm by doping with small amount of Sn, which is the mixture of
Manufacturing of TiO2 is possible with simplified and low cost continuous process, in
addition the Titania powder of anatase phase was prepared without calcination, with
particle size 4 nm reported by Zhang et. al. [29]. Nano structure materials with well
defined size are generally used in the catalyst and the chromatographic separation
processes. Brinker et al [30] described the production method for silica with the help of
rapid aerosol process. The evaporation of solvent during aerosol generation induces
controlled meso-and macro-porosity [31]. Various routes used for production of the
matrices for mediated control of CaCO3, K2CO3, CdS, CaSO4 Ca3(PO4)2, Mg(OH)2 which
are synthesized using matrix mediated growth technique like polyethylene oxide,
Nanostructure materials of perovsketite type oxides, LaMnO3, and LaCO3, have been
prepared by Min Chen et al [42]. They have used three different methods such as sol
gel, precipitation and amorphous complexometry observed the effect of the synthesis
methods on structure and catalytic activity, and tried to optimize the catalytic activity
of CO oxidation of LaMnO3.
reagents are used. Ammonium carbonate has also been used as precipitating reagent
which leads to unusual rod shape morphology, flow injection technique has been
developed to synthesize nanophase particles of zinc oxide. The average particle size of
ZnO obtained using the injection flow technique was of approximately 20 nm, while the
Ultrafine, equiaxed and monodipserse oxide particles with the average grain diameter
in the range of 1-10 nm have been prepared by Colinet et al [44] by two step chemical
approach; the chemical reduction of metallic salts obtained by activated sodium hybrids
amounts of O2-N2 gas. Such particles are easily, quantitatively and reproducibly,
Polymer –clay interactions have been actively studied during sixties and the early
properties and the thermal resistance as compared with pristine matrix and at low clay
content (4 wt %). Since then the polymer –clay composites have been divided in the
three general types; i) Conventional composite where the clay acts as a conventional
between the clay layer and iii) Delaminated nanocomposites where 1nm thick layers are
dispersed in the matrix forming a monolithic structure on the microscale. Clay contains
the negatively charged layered silicates bound with metal cations such as Na+ or Ca++.
The clays are initially modified and then used. Modifications are done with the help of
surfactants, swelling agents to improve the surface properties of the polymers. Number
of authors have studied the systems of the polymer –clays such as clay polyimide [45],
clay-PP, [46-49],Na+ MMT clay Poly(vinyl alcohol) [50], smectic clay poly(methyl
composites are achieved in two ways either by using the functionalised PP and
common MMT clay or by using neat /unmodified PP and a semi fluorinated organic
modification for silicates. All the hybrids can be formed with solventless melt
intercalation or extrusion. Small addition less than 6 % of the nanoscale inorganic filler
improves the properties such as the tensile characteristics high barrier properties better
Zr, Ti and Ti-Zr mixed oxides pillared montmorillonite (PILC) has been prepared
by Das et al [61]. MNT was used as a starting material and before pillaring, it was
subjected to exchange with Na+ ions, finally the additions of the respective samples
were treated with chlorides. They have used the prorled MNT-Ti samples for the
nitration reactions as the solid catalyst are generously employed. it was subjected to
exchange with Na+ ions, finally the additions of the respective samples were treated with
chlorides. They have used the prorled MNT-Ti samples for the nitration reactions as the
Two terms (Intercalation and exfoliation) are use generally used to describe the two
assembled, well ordered multi layered structure where in the extended polymer chains
are inserted in to the gallery spacing between parallel individual silicate layers
The delaminated structure result when the individual silicate layers are no longer close
enough to interact with the adjecent layers. In the delaminated cases the interlayer
spacing can be of the order of the radius of gyration of the polymer, therefore the
silicate layers may be considered well dispersed in the organic polymers. The silicate
structure. Both of these hybrid structures can also coexist in intercalated in the polymer
matrix; this mixed morphology is very common for composites based on smectite
silicates and clay minerals. X-ray diffraction measurements can be used to characterize
these nanostructures. Diffraction peaks in the low angle region indicate the d spacing
disordered nanocomposites shows no peaks in this region due to the loss of structural
registry of the layers and the large d spacing (> 100 nm)
characteristic is that the presence of the polar group of MAH-g-PP affects dispersion of
the clay layers in the composite and that is why it enhances the properties. Jog et al [62]
behavior of PP-clay system. And found that the PP/clay system exhibits a disordered
Ph.D.Thesis, Mr. Shriram Shaligram Sonawane, U.D.C.T. N.M.U., Jalgaon Page
29
Literature Review
structure from by XRD patterns. The thermal degradation temperature increases from
270 to about 330 0C. DMA shows the significant improvements in the storage modulus.
The intensity of the loss modulus peak is reduced, showing weak cooperative relaxation
silicates and polymer-mineral nanofillers exhibit the unique property profiles such as the
elevated heat distortion temperature combined with improved stiffness, strength, impact
coefficient, barrier against permeation of the gas and liquids rheological control and less
important aspect, Chow et al [64] have developed the predictive model which shows
that the tensile strength of a particulate-filled polymers which depends not only on the
volume fraction of the fillers and elastic moduli of two phases but also on the shape,
size and the interfacial adhesion of the filler particles and the matrix.
electrical properties. The need of the electrical and thermal conductivity of polymer
composites is in the electrical circuit boards and heat exchangers, Kripa et al [65] have
graphite system (semicrystalline matrix), investigators used the graphite systems with
different particle sizes and specific surface area. Intercalated version offers the reduced
flammability benefits, but with less improvement in the physical properties, this issue is
modified montmorillonite clay in glassy epoxy were prepared and studied by Zedra et al
and strain to failure; the fracture behavior appears to be most dramatically improved in
the intercalated systems. The fracture energy increment was reported by 100% with
clay concentration of 5 wt %.
The effect of Nylon–6 molecular wt on the mechanical and rheological properties of the
has been extensively studied by the Paul et al [54]. Tensile modulus and yield strength
were found to increase with increasing concentration of clay while the elongation at
break was found to be decreasing; Izode impact strength was found to be independent
of the increase of the clay content for lower molecular wt. polyamides. Capillary and
dynamic parallel plate data revealed sizeable difference in the level of shear between
each nanocomposite system, mechanism for exfoliation during the melt mixing is
Runt et al [61] Synthesized Polyurethane urea (PUU) with condensation reaction, and
comb polymers. They have invented significant reduction in the gas permeability with
concurrent property enhancement that could not be achieved with chemical modification
stiffness e.g. for the 20-wt % composite, by more than 300% and 30% respectively.
However, incontrast to conventional filled polymer systems, the increase in stiffness and
strength does not come at expenses of the ductility. A silica (Aeorsila200V) has been
Guyot et al[62]. It has been found that functionalised silica gives very high elongation at
break.
Liu et al [67] prepared composites by grafting -melt compounding using a new kind of
co-intercalation organophilic clay which had larger interlayer spacing than ordinarily
gives grafting reaction. Incorporation of silicate layers gives improvement in the storage
function of the silicate content has been studied by Mulhaupt et al [49]. Melt
fluorohectorite with octadecylammonium cation, it has been found that the Young’s
modulus has been increased five times with increasing content of the organophilic
silicate nanoparticles, the yield stress was increased in considerable value in the s-pp.
Due to formation of the aggregation of the nanoparticles and shear heating the melt
mixing of nanoparticles with high performance of the polymers is not possible. Jana et al
[68] investigated the feasible alternative solution to this problem, they used the lower
molecular weight polymer (epoxy) as reactive solvent and dispersing agent. They found
Nano TiO2-epoxy system has been developed by the Schelder et al [69], an ultrasonic
were processed at different loading, and exfoliated the exceptional strain to failure and
The γ-Fe2O3 nano particles coated with DBS and CTAB were prepared by Liu et al
[70] by microemulsion process, the coated samples with surfactant showed the
considerable enhancement in the nonlinear optical properties compared with their bulk
counter part.
The geometry and the orientation of the filler particles have significant influence on the
thermal conductivity of the composite material. Many of the theoretical treatments are
valid for only specific types of the filler particles and composite constructions, Bigg et al
[71] includes the theoretical calculations and the models predicted for the calculation of
the thermal conductivity of the spherical and the irregular shape fillers, long fibers and
flakes. Thermal conductivity and particle effect are not yet theoretically predicted.
PP/nanoparticle composite was found much higher than the conventional calcium
Dufaud et al [77]. This study characterizes the influence of the novel silica particles in
been investigated by Keis et al [73], photochemical studies were carried out on various
types of electrodes with controlled morphology of particle size and doping. The
monochromatic photon to current was recorded in the UV spectral region on bare ZnO
and in the visible region on the ruthenium dye sensitized cells. The results showed
relatively high efficiencies for such systems and demonstrated the potential of ZnO
Hajji et al [74] using a five step procedure. Different types of materials were prepared by
changing the particle size (50 to 80 nm in diameter) and the weight fraction of silica (in
the range of 5-30 wt. %). Study of their swelling in chloroform showed that
tridimensional structure were likely to be formed, especially at high silica wt. fraction and
small particle size. As far as the thermo-mechanical properties are concerned, the main
formation, as expected the glassy modulus increased with the wt.fraction of silica, in
quite good agreement with the predictions of theoretical models. Finally the yield stress
simple shaped nano particles of silica have been elaborated by Reynaud et al [75].
Three different ways an industrial route, a solvent technique with use of acetone and
mechanical alloying, and evolution of the dynamical mechanical thermal properties are
discussed with regard to the filler content. Eventually the comparison is drawn from 10
synthesized from ODA modified MMT and poly(amic acid). Organoclay/BDTA –ODA
two-fold increase in modulus and a half fold increase in maximum stress in case of 7:93
/BTDA-ODA nanocomposites is even slightly higher than the pure BTDA-ODA which is
clay. A Clay–rich nanocomposite not only exhibits mechanical properties but also
The Cone-Calorimeter is one of the most effective bench-scale method for studying the
properties such as heat release rate (HRR), and carbon monoxide yield, among others.
Heat release rate, in particular peak HRR has been found to be the most important
parameter to evaluate the safety. Gilman et al [66] have characterized the flammability
using the cone calorimeter. The calorimeter data shows that both the peaks and
e 2%
Delaminated
Nylon –66 6 378 304 27 2 96 0.02
silicate –
nanocomposit
e5%
delaminated
Process history and use of temperature determine the relative fraction of the crystalline
polymer phases in the semicrystalline polymer composites, and thus have significant
influence on the stability of the crystalline region at the elevated temeperature. Vaia et
al [56] studied the influence of nanodisperesed MNT layer and process history on the
crystal structure of the nylon-6 between the room temperature and it’s melting. XRD and
TEM have been taken in account to note the behavior. The temperature dependence of
total crystallinity and relative fraction of α - and γ -phases imply that the γ -phase is
preferentially in the proximity of the silicate layers whereas the α - phase exists away
from the polymer silicate interface region.Liu et al [48] studied the nonisothermal
crystallization behavior of polyamide –6/ clay nanocomposite (PA6CN) with the help of
differential scanning calorimeter (DSC) and X-ray diffraction (XRD). DSC results
showed that the nanometric silicate layer in the PA CN acted as an effective nucleating
agent. The addition of the silicate layers influenced the mechanism of nucleation and
the growth of Polyamide. It has been found that the addition of the silicate layers
with increasing cooling rate. Authors have also proposed a Non-isothermal kinetic
model.
syndiotyactic PS nanocomposites has been investigated by the DSC and FTIR. The
results show that the presence of the clay plays important role in facilitating the
formation of the thermodynamically favorable β form crystal when the s-PS is melt or
cold-crystallized.
Numbers of the nanoscale system experiments have been done for the studies of
hetrogenities, which varies on the length scale as short as a function of nanometer. Zax
et al [82] applied their efforts on the use of the nuclear magnetic resonance
polarization experiments with spin-echo experiments was also done; it has been
suggested that the PS in the center of nanopores is more mobile than the bulk at
comparable temperatures, while the chain segments which interact with the surface are
Polymer surfaces play an important role in their application such as adhesion, protective
coating, friction and wear, microelectronics and thin film technology. However up till
now the term surface has not been well defined because a surface defined by one
technique can be the bulk as revealed by another technique. Chan et al [83] used the
surface of the poly(N-vinyl-2 pyrrolidone) thin films containing nanoparticles. The study
XPS suggested that the concentration of the silica particles increases as the sampling
presence of these sub-surface nano particles. Polymer dispersed liquid crystals (PDLC)
are important in development of electronic appliances. Bunning et al [84] have used the
small-angle X ray scattering and high resolution scanning electron microscopy for
detecting the nano and mesoscale morphology of the polymer dispersed liquid crystal
It is well known that the dispersion of clay affects mechanical and thermal
solvent. Hanley et al [85] has used SANS to investigate the dispersion in toluene of
colloidal suspension under external electric field strength change abruptly via structural
change in the particle aggregation in either chain or column like structures. Kim et al
[51] studied the strongly hydrophobic PS was intercalated into the hydrophilic silicate
layers via emulsion polymerization which has been previously sued to produce
/acrylonitrile copolymer and Na+- MMT are filled with sodium cations , the hydrophilic
optical, electrical, and gas barrier properties, and decrease the flammability. This
happens due to the large contact area between polymer and clay on a nanoscale as
has been known for 50 years and one of the pioneering works was from Toyota as
reported by Cho and Paul [87]. To be compatible with polymer matrices, sodium
smectite clays need to be modified by using quaternary ammonium salts with at least 12
carbon atoms in aqueous dispersions. In these dispersions, the clay particles or layers
must be separated one from another and not be stacked in order to facilitate the
introduction of the organic compounds. As a result, the clay exchangeable cations are
replaced by the organic cations of the quaternary ammonium salt that are adsorbed on
the negative sites of the clay surfaces. The obtained clay is known as organoclay [7–
Figure 3 presents the X-ray diffraction patterns for the PA 6,6 systems with 2 wt.% of
unmodified (MMT) and modified clay (OMMT). The interlayer distance was determined
by the diffraction peak in the X-ray method using the Bragg equation. It can be
observed for the modified clay (OMMT) three peaks corresponding to an interlayer
spacing d001 of 29.2, 19.2, and 12.5 A° . The two first peaks indicate that the
intercalation of the salt between the layers of clay has occurred. According to the
literature [91, 92] another peak corresponds to interlayer spacing’s of 12.5A° (d001 for
residual Na-MMT remaining in the material. . The results indicated that the quaternary
ammonium salt was intercalated between two basal planes of OMMT leading to an
diffraction peak around 14.71 A° , which is close to the distance of 12.5 °A of the
unmodified clay indicating that the increase of the basal spacing practically did not
occur. On the other hand, the sample of the nanocomposites of PA6,6 with the modified
clay (OMMT) presented the displacement of the XRD peak toward a lower angle values,
which represents an increase to 19.20 °A in the basal spacing. It can be thus noticed
that with the organoclay presence, the peak related to the PA66/unmodified clay
interlayer spacing disappeared and a new broad diffraction peak appeared. This peak
may be due to the intercalation/partially exfoliation of the polymer chains between the
layers of organoclay. These results were be confirmed by TEM. Figure 4 shows the
TEM images of the PA66 system. In Figure 3(a), it can be seen clearly agglomerates of
clay and in Figure 3(b) exists intercalated clay layers but it can be seen too several
exfoliated clay layers present in the PA6,6 matrix. Therefore, the obtained PA66/OMMT
systems are partially exfoliated nanocomposites according to the XRD pattern (Figure
Figure 2.3: XRD patterns of montmorillonite clay modified with Praepagen salt
(OMMT),A66/MMT, and PA66/OMMT nanocomposites. [101]
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