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Polymner Clay Nanocomposite

Polymner Clay Nanocomposite

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Published by Bhupendra Singh
A nanocomposite is defined as “a material having two phases, one of the phases is uniformly dispersed into the second phase on nanoscale level (10-9 m).
A nanocomposite is defined as “a material having two phases, one of the phases is uniformly dispersed into the second phase on nanoscale level (10-9 m).

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Published by: Bhupendra Singh on Nov 24, 2007
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Polymer Clay Nanocomposite

Polymer Clay Nanocomposite

Bhupendra Singh Department of Chemical Technology University of Mumbai Matunga, Mumbai – 400 019

Introduction
Nanocomposites have changed the perception towards the concept of polymer composite. They are the emerging polymer composites of the 21st century. The importance of these products is growing from industrial and research point of view. Nanocomposite show drastic improvement in the properties derived from the addition of few percent of the clays in the polymer matrix. These composites exhibit new and improved properties as compared to their micro and macro-composite counterparts. This improvement in the properties is the result of the ultra fine phase dimension of the filler. A nanocomposite is defined as “a material having two phases, one of the phases is uniformly dispersed into the second phase on nanoscale level (10-9 m)”. The dimension of the first phase is in the nanometer range of 1 to 100 nm.1 Nanocomposites typically contain 1-5 wt. % of filler loading on weight basis depending on the final properties to be achieved. 2 Nanocomposite promise to be the wave of future by having major implications in industry and technology.3

The purpose of this paper is to present an overview on polymer clay nanocomposite, their synthesis, properties, characterization and application.

By – Bhupendra Singh

Polymer Clay Nanocomposite

Raw Materials
Polymer
Polymer clay composites have been classified into three categories namely, conventional composite, intercalated nanocomposite and exfoliated nanocomposite depending on the type of dispersion. In conventional composites the filler loading is on the higher side (3060 vol. %)1 as compared to the nanocomposites (1-5 wt. %). In intercalated nanocomposites regular insertion of the polymer in between the silicate layers at the molecular level is observed while in exfoliated nanocomposites individual layers of the silicate layers are randomly dispersed into the polymer phase.3, 4

Different polymers have been used for the synthesis of the polymer clay nanocomposites in the last decade. These polymers are divided into two different classes3  Thermoplastics  Thermosets Thermoplastics The first polymer clay nanocomposite synthesis was reported by Toyota Central R & D a dozen year ago. Researchers have gone a long way since then in this arena and had developed various nanocomposites by making use of different polymer and clay combinations. Out of various thermoplastics used; polyamide-6 is the most studied and reported nanocomposite. Injection molded polyamide-6 nanocomposite showed excellent mechanical, barrier, heat distortion property and reduced flammability;5,6 without sacrificing its impact strength4.Various polyamide-6 nanocomposite products have been already commercialized. Thermoplastics such as Poly (ε-Caprolactam ),1,7,8 PET,9 PMMA,10 PP,11,12 PE,12 PS,13 PES,14 PEO,15 Polyimide16 have been used for the synthesis of polymer clay

By – Bhupendra Singh

Polymer Clay Nanocomposite

nanocomposite. Different methods are employed to synthesize these nanocomposites such as Melt intercalation process, In-Situ polymerization and Solution process. Processing of these nanocomposites can be done by conventional methods i.e. Injection and Extrusion processes. Thermosets The most commonly studied thermoset nanocomposites are Epoxy,3,17 Polyurethane9,18 and unsaturated polyesters. Epoxies are the most widely used engineering thermoset materials as it is easy to process and gives excellent engineering properties on curing.3 For thermoset nanocomposites the complete exfoliation of clay is predicted by thermodynamic principle. The free energy, ΔG for complete exfoliation of thermoset nanocomposite is the sum of the terms contributed by the polymer matrix and silicate clay. For polymer matrix ΔGp = ΔHp - TΔSp For silicate clay ΔGc = ΔHc – TΔSc The total free energy change is ΔGt = (ΔHp + ΔHc) - T (ΔSp + ΔSc) = ΔHt – TΔSt

When monomers or polymers penetrate into the silicate layers the entropy change is negative while expansion of the gallery shows positive entropy change. The total enthalpy will determine whether or not exfoliation takes place.

By – Bhupendra Singh

Polymer Clay Nanocomposite

The complete exfoliation condition is that the heat of the intergallery polymerization released before the gel point requires larger than the van-der Walls attractive energy between the interlayer. i.e., ΔHp (t ≤ tg) ≥ ΔHc .17

Clay
Clays have been used as fillers in the conventional polymer composites at very high loading levels for economic reason. The property enhancement is moderate, which is in contrast with the property improvement in the nanocomposite; where small amount of filler loading gives higher level of property improvement.1 Clay is a generic name for a whole family of layered aluminosilicates. Clays are used in wide variety of applications like ceramic, decorating and industrial products depending upon its form and properties. Smectite are the fraction of Bentonite ores. Smectite shows its unique property of swelling in water. There are many species of smectite, of which Montmorillonite and Hectorite19are of commercial importance. The most commonly used clays in nanocomposite are organically modified Montmorillonite. Along with montmorillonite few other types of clay have been reported for the use in the nanocomposite, such as Saponite,20 Attapulgite 21 and Mica type 16, 19 silicates. Montmorillonite Approximate formula for montmorillonite is [R+0.33(Al, Mg)2Si4O10(OH)2.nH20 ] Where R+ in natural mineral can be one or more of the Na+,K+,Ca+2,cations.22 Montmorillonite have a dimension below the visible light wavelength; properly oriented and transparent, this is a critical requirement in barrier packaging. Na-montmorillonite is the major mineral constituent of Bentonites and has high swelling capacity as compared to Bentonites having Ca–montmorillonite as major mineral. Na-montmorillonite is a smectite in which Na and water molecules are the interlayer material. The largest and

By – Bhupendra Singh

Polymer Clay Nanocomposite

highest quality Na – Bentonite deposits in the world are situated in South Dakota, Wyoming and Montana. 23 Montmorillonite are the preferred materials in nanocomposite because of • • • • • • • Low levels of loading High aspect ratio ( as high as 1000 ) Good transparency Safe handling Natural abundance Economic and Good chemical resistance 1,7 Montmorillonite shows hydrophilic nature; hence it can not be homogeneously dispersed into the organic polymeric phase. The higher aspect ratio of silicate particles can be maximized by dispersing individual silicate layers into the polymer matrix.1 Therefore to incorporate montmorillonite into the polymer phase it is organically modified by a cation exchange reaction.7 This improves the compatibility of montmorillonite with the polymer. Owing to its cation exchange properties the clay gallery ions can be replaced by organic cationic species such as alkyl ammonium ions. As the gallery cation changes from inorganic to organic, the surface property changes from hydrophilic to organophilic.3

Compatibilizing Agents
Clays do not disperse well in the organic polymer matrix. The differences in the surface tension force between the clay and polymer matrix; produces an obstacle in the dispersion of clay particles in the polymer. The direct blending results in clustering tendency of the silicate layers, thus posing limitation on its use as nanoclays. Hence chemical modification is essential for the clay before using it in nanocomposite.9The inorganic cations present in the clay intergallery provide the site for the water molecules to form monolayer or multilayer structure. The layered spacing is governed by the amount of water present. This makes clay hydrophilic in nature. To mix the clay with the
By – Bhupendra Singh

Polymer Clay Nanocomposite

polymer matrix its hydrophilicity has to be decreased and organophilicity has to be improved. As smectite clays exhibit cation exchange properties, the clay gallery ions can be replaced by organic cationic species, such as alkyl ammonium ions. 3 Compatibilizing agents are typically a molecule having one hydrophilic and one organophilic functional group. Non polar nature of the alkyl chain reduces the electro static interactions between the silicate layers to facilitate the diffusion of the polymer into the galleries of layered silicate. Organically modified montmorillonite is synthesized by a cation exchange reaction between montmorillonite and alkyl ammonium ion or amino acids. The presence of this cation in the galleries provides hydrophobicity to the Na- montmorillonite. 4 Na -montmorillonite has composition of sodium ion and negatively charged montmorillonite. It forms homogeneous dispersion in water but does not disperse in the organic polymer matrix. To reduce the hydrophilicity and improve the organophilic nature of Namontmorillonite it has to be treated with compatibilizing agent.16 Various compatibilizing agents have been used for the synthesis of the polymer clay nanocomposite. Compatibilizing agents such as 11-amino acid,24 octadecylammonium salt,4 12aminolauric acid,2,19 dimethyl dehydrogenated tallow quaternary ammonium chloride,5 have been employed
26

for

the

nylon-6

clay

nanocomposite

synthesis.

Disteryldimethlyammonium chloride,7 cetyltrimethyl ammonium bromide (CTMA),25 dimethylpropanediamine 12-aminododecanoic acid1 were used in the preparation of poly(ε-caprolactone) clay nanocomposite. Dimethyl dehydrogenated tallow quaternary ammonium chloride is reported to be used in the synthesis of SAN-MMT nanocomposite by solution polymerization method.10 Ammonium salt of dodecylamine was incorporated as compatibilizing agent for the synthesis of polyimide nanocomposite.16 n-Hexadecylammonium chromide17 and alkyl ammonium chloride3 was used in the Epoxy/clay nanocomposite as compatibilizing agent.

By – Bhupendra Singh

Polymer Clay Nanocomposite

Nanocomposite Synthesis
Nanocomposites can be synthesized by different routes. Most commonly used routes are  Melt-intercalation process  In-situ polymerization process  Solution process  Emulsion polymerization

Melt intercalation process (Compounding process)
This method involves mechanically blending organically modified clays with polymer matrix. The nanocomposite is formed by addition of swollen and pretreated layered silicate to the polymer melt. The swollen clay permits easy exfoliation of clay in the polymer matrix.27 The nanocomposite is then annealed.28 Annealing of the polymer clay nanocomposite sample at the extrusion temperature leads to coarsening of the clay (silicate) superstructure and further improvement of exfoliation. This resulted in unique rheological properties and stable morphology.29 The quality of dispersion depends on 1. Organic modifier 2. Processing and 3. Mixing conditions5 This is a promising new approach to fabricate polymer clay nanocomposite by using conventional polymer processes like extrusion and injection molding. The formation of nanocomposites by above processes is governed by the thermodynamic interaction between the polymer chains and the silicate layers; and the transport of the polymer chains from the bulk melt into the silicate layers. 4 The polymer and nanofillers are preconditioned to remove moisture. The polymer is then fed into the compounder along with nanoclay with calibrated volumetric feeders.

By – Bhupendra Singh

Polymer Clay Nanocomposite

The layered silicates are dispersed in the melt phase by shearing action. High shearing mixers or internal mixers are used for the synthesis of the nanocomposite. Twin screw compounder is ideal equipment. Screw parameters and compounding parameters are modified to achieve the optimum properties. Nylon-66 films are casted by using high shearing single screw or twin screw compounder. A schematic representation of the flow diagram for melt-intercalation process is as shown below in fig. 1

Clay Blending Thermoplastic Annealing Nanocomposite

Fig. (1) Flow chart for the synthesis of nanocomposite by melt-intercalation process The particle size of the layered silicates in the nylon 6 matrix is reduced through the melt intercalation process. Most of the silicate layers are exfoliated into nanometer layers and randomly dispersed in the nylon 6 matrixes via melt intercalation process.4 TEM results showed that the intercalated silicate layers through the melt extrusion process are exfoliated into nanoscale layers and randomly dispersed in the nylon-6 matrixes.

In situ polymerization process (In reactor polymerization)
In-situ polymerization method is very useful method for the preparation of high performance polymer nanocomposites.17 In this method nanocomposite is synthesized by introducing the monomer, into the organically modified clay and then polymerizing it insitu. Kojima Etal.30 has reported the preparation of Nylon-6 nanocomposite at normal pressure. In his experiments montmorillonite was dispersed in water, to which εcarolactam and hydrochloric acid was added. It was then stirred and filtered to get montmorillonite intercalated with ε-carolactam. This intercalated ε-carolactam is then charged into a reaction vessel along with 6-Aminocaproic acid. The mixture was heated

By – Bhupendra Singh

Polymer Clay Nanocomposite

at 2600C for 6 hours in nitrogen atmosphere under normal pressure. After reaction completion the product was cooled and subjected to milling operation to obtain pellets. Kurachi and co-workers at Toyota R&D have reported following procedure for the synthesis of nanocomposite. A 2 L Parr reactor is charged with ε-carolactam and montmorillonite that had been reacted with 12- aminolauric acid. The vessel was then purged with nitrogen for 25 minutes and sealed. The temperature is raised to 110 0C and again purged with nitrogen for 30 seconds. Temperature is then raised to 250 0C under nitrogen atmosphere. The reaction proceeds for two days with slow stirring. Pour the molten polymer into cold water, filter it and dry it for 24 hours at 0.1 mm Hg pressure.2 In most cases the synthesis involves either intercalation of a suitable monomer and then exfoliating the layered host by subsequent polymerization.4 Flow diagram for In-Situ Polymerization process is as shown fig. (2)

Monomer Swelling Clay Polymerization Nanocomposite

Fig. (2) Flow diagram for In- Situ polymerization process Swelling of clay Silicate layers swell in the monomer and exfoliate during the polymerization. Swelling occurs because of monomers entering into the gallery between the silicate layers; which increase the intergallery height. As the silicate layers move apart from each other the mutual attraction between them decreases resulting in the drop of shear rate required to disperse the silicate layers into monomers. The two important factors affecting swelling is swell time and temperature during swelling.

By – Bhupendra Singh

Polymer Clay Nanocomposite

Dispersion Procedure Dry silicate layers are added to the monomer under stirring condition. The stirring should be enough to create a homogeneous mixture. Temperature is increased to ease the monomer intrusion into the gallery between the silicate layers. Further stirring is continued and the mixture is then charged into the reactor. The polymerization of the mixture is carried out under agitation and blanket of nitrogen. After the completion of the reaction the nanocomposite is washed, palletized and dried. This dried nanocomposite is then used for making the final product.31 Viscosity Control Viscosity of the mixture tends to increase while mixing. To control the viscosity water can be added to the mixture without affecting the dispersibility of the clay. Also as silicate clay and polymer mixtures are thixotropic in nature hence viscosity can be controlled just by increasing the shear rate. The ε-caprolactam containing nanoclays have a tendency to develop increased viscosity while polymerizing. In-situ formed polymer clay nanocomposite outperformed melt compounding by a significant margin. The resulted nanocomposite has a “tethered” system where polymer molecules terminate at the clay surface. Tethered systems show enhanced thermal stability with improved fire retardancy property.31

Solution polymerization
Organically modified clay is suspended in suitable solvent under vigorous stirring condition. Organoclay swells in the solvent. To this mixture monomer and initiator is added. The mixture is allowed to react while vigorous stirring condition is maintained. Reaction is then terminated. The product is separated and washed several times. It is then dried under reduced pressure to remove the washing solvent. Preparation of SAN- MMT nanocomposite is reported by using this method.10 A modified method is used to prepare Rubber-Clay nanocomposite. In this method instead
By – Bhupendra Singh

Polymer Clay Nanocomposite

of monomer as used above; polymer dissolved in solvent is added to the mixture of preswollen organoclay. The last step consists of removing the solvent by evaporation under vacuum.32 Figure (3) represents the steps involved in the solution polymerization process.

Solvent Swelling Clay Solvent Evaporation

Monomer

Intercalation & Polymerization

Nanocomposite

Fig. (3) Flow diagram representing the steps involved in the solution polymerization process.

Emulsion Polymerization
A new approach to the polymer nanocomposite synthesis; based upon one step emulsion polymerization is reported by M. H. Noh Etal. Various properties such as polymer loading into the inter layer of silicates, molecular masses of intercalated polymer, gallery expansion, thermal stability, mechanical properties and dispersibility of silicate layers in polymer matrix was found to exceed to those of products made by solution polymerization method. Emulsion polymerization can play an important role in synthesis of polymer clay nanocomposite; it also eliminates the environmental problems associated with the solution polymerization process. It involves addition of surfactant along with unmodified silicate clay under stirring condition. Monomer is feed with the initiator. Emulsion polymerization proceeds under vigorous agitation condition. The reaction mixture is cooled to room temperature. The final product is obtained after filtration and washing several times with water. It is then
By – Bhupendra Singh

Polymer Clay Nanocomposite

dried under reduced pressure. Styrene-Acrylonitryl copolymer montmorillonite nanocomposite is prepared by the Emulsion Polymerization technique.10 A flow diagram for emulsion polymerization technique is as shown in the figure (4)

Initiator Surfactant Polymerization Water Monomer Clay

Nanocomposite

Fig. (4) Flow diagram for the synthesis of nanocomposite by emulsion polymerization process

Characterization
For the characterization of the polymer clay nanocomposite X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Differential Scanning Calorimeter (DSC) and NMR were used. Studies of structural and morphological characteristic were carried out. TEM images of N-6/clay nanocomposite showed that the silicate layers disperse uniformly in the polymer matrix. The microstructure in the nanocomposite was found similar to that of organoclay, but the interlayer distance was observed to become larger to 3.5 nm; which is compatible with XRD results.4 DSC studies showed the presence of clay promoted γ-crystalline form. From DSC scan curve it was observed that the Nylon-6 matrix has only one peak corresponding to the α-

By – Bhupendra Singh

Polymer Clay Nanocomposite

form while the nanocomposite system shows two melting peaks; high temperature peak corresponding to α-form and the lower temperature corresponding to γ-form of crystallite4. NMR studies were carried out for the observation of α and γ crystal forms and amorphous regions in Nylon-6 clay nanocomposites. Crystallization behavior of Nylon-6 nanocomposite Nylon-6 is a multicrystalline polymer having more stable α–form as compared to γ-form.4 Clays induce the γ- crystal growth in nylon 6 while the percentage crystallinity remains almost the same.2 Generally α-phase and amorphous phase is observed in nylon-6; of these α- phase is the favored one. Annealing of nylon samples at a temperature close to the glass transition temperature produces only α and amorphous phases. While, when clay particles are present in nylon-6, it adopts α and γ-crystal phases in somewhat equal amounts. Since only α form is present in commercial nylons hence it can be suggested that the presence of γ- phase must be a result of the interactions between the silicate layers and the polymer matrix. Clay increases the crystallization rate and has a strong nucleation effect on the nylon 6 matrix.4 The clay stabilizes or /and induces the γ- phase of nylon-6 in nanocomposite. The results of crystallization study after annealing for nylon-6 and nylon-6 nanocomposite showed no change in crystalline and amorphous phase for nylon-6 but at the same time the morphology was changed for the nanocomposite as it produced only γ-form of crystal and amorphous phase. The clay surface induces kinetically favored formation of γ-crystal form.2 It is well established that the presence of clay induces the formation of γ-form of crystal as compared to α form of crystal.5 Small amount of clay in nanocomposite promotes the crystallization while large clay content delays it. The isothermal crystallization is affected by diffusion and nucleation. Diffusion is related to the activation free energy for transporting polymer segment to the growing crystal surface. Nucleation term is related to the thermodynamic driving force. A

By – Bhupendra Singh

Polymer Clay Nanocomposite

small amount of clay acts as a nucleating agent while large amount hinders the transportation of polymer segment.7 Orientation The nanocomposites exhibit anisotropic properties which are attributed to the orientation of the clay layers. The preferential orientation of the clay layer in the polymer clay nanocomposite was found to be related to the injection / extrusion direction. This orientation of the clay layer plays a major role in the enhancement of the mechanical properties of the polymer clay nanocomposite.33 Orientation of montmorillonite and nylon-6 crystallites in nylon composite film is measured by X. R. D. and TEM. For the film it is seen that the pure nylon-6 film showed no preferred orientation but on the other hand presence of silicate layers contributes important role in the preferred orientation of nylon-6 crystallites. γ-form of nylon 6 crystallites tends to form planar orientation in the nylon clay nanocomposite film.6 In nylon clay nanocomposite film it was found that the silicate layers had planar orientation. The chain axes of nylon-6 crystallites (γ- form) were found parallel to the film surface but were randomly oriented within the film plane. This orientation of nylon6 crystallites in nanocomposite was assumed to be promoted by the presence of anisotropic silicate monolayer dispersed separately. The degree of orientation of an anisotropic body depends on both the magnitude of the applied shear stress and the aspect ratio of the body.34.

Properties
Properties of the nanocomposite material is governed to a greater extent by complex interactions between different phase and the interfaces between them.3

By – Bhupendra Singh

Polymer Clay Nanocomposite

Mechanical properties Surface modified silicates used in extrusion melt compounding when properly mixed with melt enhances the mechanical properties. For Nylon-6 clay nanocomposite the flexural modulus increases rapidly with increasing clay content from 0-3.5 wt %. Further increase in the clay content has little effect on the flexural modulus. Flexural strength approaches to peak at 3 wt % and decreases with further increase of the clay content. The tensile modulus increases in the range 0-15 wt % but little effect was observed for clay content higher than 15 wt %.Notch impact strength remains almost constant in the range 0-17 wt %. For low filler content the properties were found to be far superior to those of conventional counterpart composites. There is a strong interaction between the matrix and the clay layers which attributes to the nanoscale size and uniform dispersion of the clay layers in the nylon-6 matrix. 4,30 Barrier Properties The barrier properties of the polymer clay nanocomposite were enhanced by the addition of nanoclays in the polymer matrix. A conceptual figure for the path of a diffusing gas through the polymer nanocomposite is as given in the figure (5)

d

d’

W

L

Fig (5) Mechanism of “tortuous path”

By – Bhupendra Singh

Polymer Clay Nanocomposite

Total path of a diffusing gas d’ = d + d.L.Vf / 2W d - thickness of a film L - length of clay W- width of clay If silicate layers are dispersed parallel in the polymer matrix the torturous factor (τ) is given by τ = d’ / d τ = 1 + (L / 2W) Vf Vf- volume fraction of clay Therefore relative permeability coefficient is given by Pc / Pp = 1 / [1 + ( L / 2W ) Vf ] This equation roughly estimates the mechanism of “tortuous path” in polymer nanocomposite.16 Sorption properties of nylon 6 clay nanocomposite Nylon-6 has inferior resistance to water permeation. Hence it is of great importance to improve the resistance of Nylon-6 to water permeation since rigidity of the polymer is lowered by water absorption. Nylon-6 nanocomposites exhibit excellent resistance to water permeation because of the decrease in the diffusion coefficient as compared to Nylon-6. The diffusion coefficient decreases with increase in the length and content of the silicate layers.20 Water vapor transmission of nanocomposite film is determined by ASTM E 96.1

By – Bhupendra Singh

Polymer Clay Nanocomposite

Thermal properties The HDT increases rapidly for nylon-6 nanocomposite with an increase in the clay content from 0-5 wt. %. Nanocomposites offer effective flame retardancy without affecting the environmental problems.4 Nylon-6/clay nanocomposite prepared by intercalation compounding shows that peak value of heat releasing rate of the nanocomposite decreased by 32% and 63% when the clay content was 2% and 5% respectively. The density of the nanocomposite was found to be 65-75% of that of general composite.35 Ablative property A relative tough, inorganic char formed during the ablation of the nylon-6 nanocomposite. An order of magnitude decrease in the mass loss rate was observed as compared to the pure nylon. This property was observed for as little as 2 wt% exfoliated mica type silicates. The uniform distribution of the silicate layers at nanoscale leads to the formation of uniform char layer resulting in enhanced ablative property. The formation of char depends on specific interaction between the polymer and the clay surface.36

Mechanism of Intercalation and Exfoliation
Intercalation Regular insertion of polymer in between the silicate layers is observed in intercalated nanocomposites. The polymer to layered silicate ratio is almost fixed. They show electronic and charge transportation properties. Intercalation of 2 vol. % silicate into Nylon-6 on a nanoscale improved the tensile strength and modulus by more than twice as compared to the pristine polymer.3

By – Bhupendra Singh

Polymer Clay Nanocomposite

Exfoliation In exfoliated nanocomposite the number of polymer chains between the layered silicates (clay) is variable. These nanocomposites show superior mechanical properties. In exfoliated nanocomposite 1 nm thick layers are dispersed forming a monolithic structure at the micro scale. The ability of the silicate layers to exfoliate is affected by factors such as ion exchange capacity of the silicate, the polarity of the matrix, and the chemical nature of the interlayer cations. Matching the polarity of the organic cation with the monomer is very critical for getting good dispersion.1 As the polymer layer enters into the silicate layers, the interlayer spacing of the clay increases and the interaction between the clay layer decreases. If the miscibility of the polymer is good enough then it achieves the exfoliated homogeneous dispersion of the clay.37 Figure 6 represents the mechanism of intercalation and exfoliation. 2000Ao 10Ao Intercalation
Compatibilizer Silicate layer

Polymer chain

Exfoliation

By – Bhupendra Singh

Polymer Clay Nanocomposite

Figure (6) Diagram representing the Intercalation and Exfoliation in polymer clay nanocomposite

By – Bhupendra Singh

Polymer Clay Nanocomposite

Individual Nanocomposite
Polyamide Nylons are widely used as plastic materials for specialty purposes. They can be injection and extrusion molded. Nylons are used in automobiles, electrical goods, packaging applications; because these materials exhibit good mechanical, thermal and barrier properties.38 Semi-crystalline polymers crystallize in different phases (e.g. Monoclinic, Hexagonal) forming chain folded lamellar crystals. The stability of these phases depends on experimental conditions (e.g. temperature, pressure) and crystal size. The nanocomposites prepared by In-Situ polymerization and Melt intercalation method exhibited homogeneous distribution of the silicate layers into the polymer matrix at low clay contents. These composites show enhanced thermal stability, tensile modulus and an increased elastic behavior over a broad temperature range. No effect on Tg was observed at highest clay content.39 TEM studies for Nylon -6/clay nanocomposite showed the clays to be 1 nm thick, 100 nm wide layered filler.40 Meta-xylene adipamide (MXD6), a specialty aliphatic nylon. Intercalated

nanocomposites of MXD6 with modified phyllosilicate silicate (smectite clay) layer showed expansion in the intergallery spacing by at least 5Aº. Poly (ε-caprolactone) Poly (ε- caprolactone) is biodegradable aliphatic polyesters and their use in degradable packaging, medical devices and controlled drug release systems is under investigations. For poly (ε-caprolactone) - silicate nanocomposite the permeability was reduced by an order of magnitude at only 4.8 % loading by volume. Full delamination of the nanocomposite leads to the formation of high aspect ratio (100-1000) impermeable layer having very good barrier property.1

By – Bhupendra Singh

Polymer Clay Nanocomposite

Polymethylmethacrylate (PMMA) PMMA is polymerized in presence of sodium lauryl sulfate with potassium persulfate in the presence of Na- Montmorillonite at 70oC for 12 h. It is then coagulated by adding aluminum sulfate solution. The product is then filtered and dried to form the nanocomposite. The average interlayer distance of the composite was found to be higher than the pristine polymer. TGA thermogram of the weight loss as a function of temperature showed the shift in the thermal decomposition temperature towards the higher temperature range as compared to the pure PMMA. The tensile modulus of the composite was found to be increased with the increase in the clay content. The improvement in the tensile modulus is due to the higher resistance exerted by the clay layer against the plastic deformation and the effect of the oriented backbone bonds of polymer chain in the gallery. In DSC studies the nanocomposite does not show any clear transition as compared to the pure PMMA, which shows endotherm at approximately at 102oC, corresponding to the Tg of the PMMA.41 Polyimide Polyimides are used in microelectronics as it has good heat resistance, chemical stability and superior electric properties. For its use in advanced electronics it is desirable to reduce coefficient of thermal expansion, moisture absorption and dielectric constant. Layers of organically modified montmorillonite are dispersed homogeneously into the polymer matrix. These layers align themselves parallel to the surface. A film of polyimide nanocomposite containing 2 wt. % of montmorillonite is found to be as transparent as polyimide itself. This phenomenon occurs because of molecular level dispersion and the size of montmorillonite (< 200 nm ) being lesser then the wavelength of visible light. As

By – Bhupendra Singh

Polymer Clay Nanocomposite

the content of montmorillonite increases in the polyimide nanocomposite the thermal expansion coefficient decreases notably. This will play an important role in matching the thermal expansion coefficient of nanocomposite to that of silicon substrates in electronic applications.16 PET nanocomposite PET is a polymer having low cost and high performance, finds variety of applications in packaging films, bottle and engineering plastic applications to fiber application. In PET nanocomposite the exfoliated silicate layers acts as nucleation promoter. With a clay content of 5%, the modulus of nanocomposite was improved as much as 3 times that of pristine PET. The average particle size distribution ranges from 10-100 nm. The heat of fusion decreases with the content of clay; and the HDT increase with the content of clay. The melting point of the PET nanocomposite decreased slightly with the content of clay. At the degradation temperature of the nanocomposite, the nanoscale particle showed strong interaction with the polymer matrix; thus explaining the enhancement in the degradation temperature.9 PP/clay nanocomposite PP containing organophilic layered silicate nanocomposite was prepared by melt extrusion process at 210º C. PP-g-MA used as a compatibilizer, led to strong exfoliation of silicate layers within the polymer matrix. Annealing of the sample at the processing temperature led to coarsening of the silicate superstructure and improvement in the exfoliation. Stable morphology with network like superstructure was obtained by this process.29 In another process montmorillonite dispersed in water and ethylene glycol was treated with hexadecyl trimethyl ammonium bromide. The dried dispersion was mixed with PP melt using an extruder, from which the glycol was evaporated.27 A house of cards structure in PP/clay nanocomposite under elongational flow was observed in TEM analysis.42

By – Bhupendra Singh

Polymer Clay Nanocomposite

PP-g-MA Nanocomposite PP-g-MA/Layered silicate nanocomposite was prepared by melt intercalation process using PP modified with maleic anhydride by solid- phase grafting process. Montmorillonite was modified with octadecylammonium ion. This nanocomposite showed higher tensile strength and modulus as compared to PP and PP-g-MA. Dramatic improvement in the tensile property was observed up to the silicate content of 3% and remained constant over 5%. The nanocomposite showed the faster crystallization than PP-g-Ma.43 PES nanocomposite Low molecular weight reactive fume silica was successfully dispersed to nanoscale in PES matrix with small amount of low molecular weight epoxy. Viscosity and processing temperature were reduced significantly. Improvement in the barrier property and heat deflection temperature was observed over pristine PES.14 PS nanocomposite A shear induced ordered structure was observed in an exfoliated PS/clay nanocomposite. A series of sharp XRD peaks was reported for the extruded PS/clay nanocomposite as compared to the broad peaks of PS. The ordered structure resulted from the planer orientation and local ordered microstructure of the 1º particles of silicate layers, induced by shear flow.13 ABS nanocomposite The mixture of acrylonitrile and butadiene- styrene was subjected to polymerization in the presence of fluoromica as clay. The fluoromica was ion exchanged with benzalkonium ion and 4- vinylpyridinium ion. The mixture was then suspension polymerized in aqueous poly (vinyl alcohol) to form a precursor. This precursor was then

By – Bhupendra Singh

Polymer Clay Nanocomposite

blended with ABS copolymer and butadiene rubber in a twin screw extruder to form the nanocomposite.44 PEO PEO-block-PS copolymer was prepared by melt-intercalation technique. Samples having higher PEO volume fraction were more likely to produce intercalation.28 Epoxy/clay nanocomposite The organic modified clay is easily intercalated by the epoxy precursor during the mixing process. Addition of suitable catalyst and coupling agent into the cured system significantly reduces the maximum reaction temperature thus leads to favorable reaction in the formation of Epoxy nanocomposite.17

Applications
Nanocomposites have been rapidly commercialized for different applications. Nylon-6 and PP nanocomposites are used for packaging and injection molded articles. Semi-crystalline nylon nanocomposites have been used for barrier, containers and fuel tank system applications. Layered silicate promotes rapid crystallization; hence better clarity is obtained as compared to pristine nylons; which makes them ideal for film applications. Nanocomposites can be run at higher line speeds as a result of improved strength. MXD6 nanocomposite is finding its use as a barrier resin in packaging applications. It is very useful in applications requiring good barrier properties in high humid conditions. Nylon clay nanocomposite having excellent mechanical and heat resistance property find its use in automobile parts. Nylon nanocomposite film having good barrier property finds use in wrapping films for food industry.45 Polyamide nanocomposite prepared by melt intercalation process can be used in all molded parts which can be produced using polyamide compounds. It find use in the motor compartment of a vehicle for casing and for connectors.46 Polymer clay

By – Bhupendra Singh

Polymer Clay Nanocomposite

nanocomposites are widely used in electronics, transportation, construction and consumer products as they exhibit combination of properties like stiffness and toughness which are not present in individual polymers.4 Polyimides find use in microelectronics because of it superior electric properties.16 Alicyclic copolymer mixed with disteryl dimethylammonium chloride treated montmorillonite was found to be useful for automobile parts, electrical parts and packaging applications.47 Polyamide sheets containing 4 % montmorillonite showed reduced curling and were useful for packaging drug tablets.48 Multilayer fuel tanks with excellent gasoline barrier properties and fire resistance were manufactured by HDPE/ clay nanocomposite.49 A subclass of nanocomposite by using graphite as nanofiller may be used as conducting polymer.50

Conclusion
Nanocomposites can be synthesized for both thermoplastic as well as for thermoset. Conventional processes such as injection and extrusion molding are employed to get the final product. The drastic enhancement in the nanocomposite properties is attributed to the ultra fine phase dimensions of the filler and homogeneous dispersion in the polymer matrix. To get homogeneous dispersion the compatibility of the clay with polymer matrix has to be improved. The type of clay and chemical treatment governs the dispersion of the clay. Compatibilizing agent plays an important role in the dispersion. Low levels of loading, high aspect ratio, cation exchange capability and natural abundance makes the Montmorillonite the most effective clay for use in the nanocomposite. Various compositions of polymer and clay nanocomposite have been developed by different processes. Manipulation in the compositions will result in getting optimum properties. The enhanced mechanical properties, barrier properties will increase its use in the automotive and packaging industry.

By – Bhupendra Singh

Polymer Clay Nanocomposite

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By – Bhupendra Singh

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By – Bhupendra Singh

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By – Bhupendra Singh

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