Review on Polymer Nanocomposites by Using Various Resins and Nanoclays and Their Applications

IJBSTR REVIEW PAPER VOL 1 [ISSUE 6] JUNE 2013

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Review on Polymer Nanocomposites by Using Various Resins and Nanoclays and Their Applications Deep Chandra Prajapati1, Praveen Gaurav Singh2, Madhuri Girdhar3 and Anupam Kumar*

ABSTRACT: This review paper focuses on recent development and current research investigated that techniques were used for enhancing the properties of nanocomposites and their potential applications. Major application of nanocomposites are in the field of aerospace, automotive, marine, infrastructure, military, food industry, food packaging, biomedical like bone replacement /repair, dental, and controlled drug delivery. In this review we are focused on the distinct type of resins and nanoclays using for enhanced the properties such as mechanical, thermal, durability, flame retardant, barrier, modulus, strength, toughness, resistance to chemical, gas impermeability, electrical instruments etc. The biodegradable nanocomposites including materials, Polymer layer silicate (PLS), Poly (L-lactide) PLA / OMLS (organo-modified layered silicate), Poly (Ɛ- caprolactone) (PCL), Nylon-6 based nanocomposites, Polyethylene (PE), Polycarbonate (PC) Poly (vinyl chloride) (PVC), Polystyrene (PS), Styrene butadiene rubber (SBR), Polyaniline (PA), Starch, Cellulose, Oil based nanocomposites.

KEYWORDS: Nanofiller, nanoparticles, carbon nanotubes CNT, Montmorillonite MMT, hectorite, and saponite, Polymethylmethacrylate (PMMA), organoclays (OCs bentonite), TPS-clay, cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB).

Introduction Nanocomposites are an advance field plastics that contain very small amount of (>10) nanometre sized clay nanoparticles; those clays particles enhanced the thermal, mechanical, flame retardant, barrier properties of base polymer (Karabulut M., 2003). When small amount of (<5 wt %) nanoparticles filler used, it can increase the modulus, strength, toughness, resistance to chemical attack, gas impermeability, resistance to thermal degradation and stability of polymeric material (Timmerman et al., 2002). The production of biodegradable nanocomposites is used for making sustainable bio- reinforced composite applied in automotive, construction materials, agriculture, packaging, medical devices (Sunday A et al., 2012). The improvement of the mechanical properties of nanocomposites such as tensile strength and elastic modulus of reinforced polymers depends on several factors ie. filler

particles size and concentration, aspect ratio, dispersion and Morphology. The addition of nanoparticles enhances the mechanical properties, thermochemical properties, and permeability (Sunday A et al., 2012).

Deep Chandra Prajapati1 Anupam Kumar* RESEARCH SCHOLAR1 AND ASSISTANT PROF* Department of Biotechnology LPU, Phagwara, Punjab (India) Email: deep.06bt@gmail.com

Improvement of nanocomposite properties are obtained with a small amount of clay mixed with polymer because the layered structure of clay provide the exceptionally good barrier properties that cannot be found in the composites filled with glass fiber (Choi et al., 2003).The combination of biodegradable PHB/HB – organocaly Nanocomposite enhances the mechanical properties (Choi et al., 2003). The nanocomposites are produced from recycled thermoplastics as the matrix and montmorillonite as the filler with the help of co rotating twin screw extruder (Karabulut. 2003). The two approaches widely used for nanoscale particles production are achieved by introducing nanoparticles into polymer matrix to create a polymer /nanoparticles composites and by another fabricating material themselves on the nanoscale .Utilization of nanoparticles in the fabricated nanocomposites include inorganic, organic and metal particles such as clays, nanotubes, magnetite, Au, Ag, hydroxyapatite, cellulose, chitin whiskers and lignin (Yang et al., 2007).

The polymer nanocomposites (PNC) are the alternative of polymer (thermoplastic, thermosets and elestomers) of conventional filled polymers or polymer blends. The development of the PNC, two type’s nanoparticles used is layered silicates and carbon nanotubes. Three main constituents of the nanocomposites the matrix, the reinforcement fiber, and the so called interfacial region (E Gacitua et al.,2005).The enhancement of the thermal stability of composites from the blending of PHB with other polymer or filling PHB with nanofiller such as montmorillonite or carbon nanotubes. The metal nanoparticles may increase or suppress the thermal stability of nanocomposites. Pd and Ag

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IJBSTR REVIEW PAPER VOL 1 [ISSUE 6] JUNE 2013 nanoparticles act as the catalyst for the thermal degradation of PHB. Addition of metal nanoparticles such as metal oxides or metal chalcoginides has effect on the nanocomposites (Yeo et al., 2010). The development of the recent method is to fabricate PHB/ Polyaniline (PANE) nanocomposites. PANI is an intrinsically conductivity polymers (ICP) used as radiostabilizing agent in nanocomposites of Poly methyl methacrylate (PMMA) and PANI nanofiber (Araujo et al., 2011). Organically modified layered silicate (OMLS) clays used in nanocomposites for the improvement of physical properties such as strength gas barrier flammability and thermal and environmental stability. Montmorillonite MMT, hectorite, and saponite are clays commonly used in polymer composites (Joshi S., 2008).

The production of polymer nanocomposites with single walled carbon nanotubes enhances the mechanical properties and nanotubes alignment. Solvent evaporation method and efficient fabrication method for the multiwall carbon nanotube-polystyrene composites and SWNT polymer composites improves mechanical properties of amorphous and samicrystalline polymer (Hggenmueller et al., 2003). The fabrication of biopolymer with carbon nanotube (CNT) composites for nanocomposites improves the thermal, mechanical and electrical conductive properties. The better solubility in the PHB/chloroform solution and casted films which is mixed with PHB and Multiwall carbon nanotube MWNTs are functionalized with alkyl group (Jung et al., 2001). latex PHO (polyhydroxyoctonate) are prepared by the chemical treatment of sodium hypochloride .The natural nanocomposites material made by PHO latex as matrix and polysaccharides as fillers of cellulose whiskers and starch microcrystal (Dubief et al., 1999).The scaffold naoncomposites are formed by the salt leaching processing of poly 3 hydroxybutyrate with 10% bioglass nanoparticles.

Biomaterials play the important role for the manufacturing of the scaffold where pertinent cell attach, grow, proliferate and differentiate (Hajiali et al., 2010). Some of physical processes that determine the linear and non linear optical properties of nanocomposites, such as structures properties of composites are shown in, Maxwell Garnett geometry composites, Layered geometry composites, Bruggeman geometry composites (Boyd et al,. 1996).

Use of nanocomposites for the food industry like food and beverage packaging sector and food products are cooking oil including nanoparticles material such as micelles, liposome’s, nanoemulsion, cubosomes, nutraceutical improve the safety and quality of products (Sozer and Jozef., 2008).

ISSN 2320 – 6020 Sizes of range of nanomaterials

Another use of bionanocomposites in the field of Biomedical includes biopolymer polysaccharides, aliphatic, polyesters, proteins, polypeptides and polynueclic acids filler including clays. Nanocomposite polymers are commonly used in tissue engineering, bone replacement /repair, dental, and controlled drug delivery (Hule and Pochan., 2007). Certain polymeric nanoparticles such as micelle based used in chemotherapies of ovarian cancer. There are different types of micelle such as PLGA, polymerosmes are acid cleavable (Yallapu et al., 2010). The characterization of nanoclay nanocomposites determines the level of exflotation and dispersion. Analyzing the resin contain nanoclays and determination of different methods including X – ray diffraction, Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Environmental scanning electron microscopy (ESEM), Electron dispersive X – ray spectroscopy (EDS/EDAX), Thermogravimetric analysis (TGA), (Synder R., 2007).

Polymer layer silicate nanocomposites The layer silicate is commonly used in the formation of nanocomposites because of starting clay materials are easily available and general family of 2:1 layered or phyllosilicate (Alexander and Dubois., 2010). Their crystal structure contain a layers made by the fusion of two external silica tetrahedron atoms and central octahedral sheet of alumina or magnesium hydroxide (Ray and Okamoto., 2003). The thickness of layer is around 1 nm and lateral dimensions vary from 3 nm of micron or layers depending on the particular layer silicate. The isomorphic substitution within layer example (Al3+ replaced

by Mg2+ or Fe2+, or Mg2+ replaced by Li1+) and generate a negative charge exchange capacity inside the galleries (Lagashetty and Venkataraman., 2005). Montmorillonite (MMT), saponite, and hectorite are the most commonly used layered silicates.

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Table: Chemical structure of 2:1 phyllosilicate

M= monovalent Cation, x =degree of substitution (Alexander and Dubois,. 2010).

isomorphous

Polymer/ layered composites are mainly classified into three types. (1) Intercalated nanocomposites, (2) flocculated nanocomposites, and (3) exfoliated nanocomposites (E Gacitua et al., 2005). (a) Intercalated nanocomposites- Polymer chains are inserted into layered structure such as clays occur in the regular fashion. (b) Flocculated nanocomposites- Sometimes silicate layered are flocculated due to hydroxylated edgeedge interaction of the silicate. (c) Exfoliated nanocomposites- Separation of the individual polymer matrix by the average distance that depending on clay.

(Ray S .Suprakas, 2006) Structure of polymer layered silicates

(Ray., 2006) Structure of phyllosilicates. Reproduced from ref. by permission of Elsevier Science Ltd., UK.

Fig .(1)Alkyl chain aggregation models.(a) Short alkyl chain, lateral monolayer;(b) intermediate chain lengths; quasi bilayers and (c) longer chain length; increased interlayer order, liquid crystalline- type (Ray and Okamoto., 2003).

Poly (L-lactide) PLA / OMLS (organo-modified layered silicate) based nanocomposites Aliphatic polyesters play an important role in the field of biodegradable material formation such as layered silicates, layered titanates, carbon nanotubes, gold silver, maghemit

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IJBSTR REVIEW PAPER VOL 1 [ISSUE 6] JUNE 2013 nanoparticles, magnetite nanoparticles, and fluorine mica. The material properties of PLA are modulus (GPa) 4.8, strength (MPa) 86, Distortion at break (1.9 %).

Bright – field (Yang et al., 2007)

TEM

images

of

nanocomposites

The formation of PLA blend done by dissolving the polymer in hot chloroform in the presence of dimethy distearyl ammonium modified MMT. In presence of clay form tactoids with several stacked monolayers. The addition of PEG to blend PLA results in improved tensile strength (28.2) and elongation (25 %) as compared to pure PLA (Sunday A et al., 2012). PLA based nanocomposites are used in wide range of application such as rheological modifier for paints, ink, and grease, drug delivery vehicle, cosmetics, adsorbent or toxic gasses, therapeutic product, and nanoclay for industrial wastewater as well as potable water treatment is referred to natural clay (Patel et al., 2005).

Polypropylene based nanocomposites There are two different method used for the preparation of polypropylene based nanocomposites. First was from pristine montmorillonite and reactive compatibilizer trimethyl ammonium bromide (C6), another from organophilic montmorillonite (OMT). Some of the polar polymer PA6, PMMA, PS has been used for successful production of nanocomposites. The OMTs produced by melt intercalation clay, Polypropylene and maleic acid modified polypropylene (MAPP) (Tang Y et al,. 2003). Different polypropylene nanoclay have been used such as Closite 20A, Closite 30A Bentenite 107. Another aspect of the nanocomposites nanoclay attracts the dye molecules through van der wall forces and possibly hydrogen bonding. Major advantages of polypropylene are its very low price and quick drying, relatively low static and resistance to staining and some of major disadvantages lace of dye ability. Mechanical and thermal nature, crystallinity and dyeability have been analyzed with the help of WAXRD, FTIR, SEM and spectrometer

ISSN 2320 – 6020 (Bahrami and Mirzaie. 2011). Polymethylmethacrylate (PMMA) was studied using blend melting techniques, mixtures of aromatic and aliphatic epoxy- nanoclay and PMMA–epoxy composites system (Park and Sahan, 2003).

PMMA/expanded graphite (EG) composites filler composites are greatest superior mechanical, thermal and barrio performance in comparison with conventional microcomposites (Zheng and Shing, 2003). Polypropylene based nanocomposites are one of the most non polar polymer and has no polar groups in its backbone. The melt intercalating methods use of compatibilizer, such as maleic anhydride grafted PP (PP-g- MA) clay (Nguyen and Baird, 2007). The mixing of clay propylene stearyl ammonium-exchanged montmorillonite, maleated polypropylene (MAPP), and the PP homopolypropylene using extraction compounds (Chen et al,.

2002). The potential of using exfoliated graphite nanoplateletes xGnP – polypropylene (PP) composites and addition of graphite sheet to a polymer matrix improve its, thermal and mechanical properties. Major applications of polymeric thermally conductive material are in light ballasts transformer housing, microchip cooling, fuses, space heater etc (Kalaitzidou et al., 2007), packaging, fibers, automotive industry, non durable goods and in building material. The degradation behaviour is PP nanocomposites compatibilizer effect on photo-degradation and its kinetics by comparison of nanocomposites with neat polymer (Panday et al., 2005).

Economic and environmental application of nanocomposites in the field of automobiles, steel or aluminium of light- duty vehicle body panel (Lloyd and Lava., 2003).

Poly (Ɛ- caprolactone) (PCL) based nanocomposites Poly (Ɛ- caprolactone) (PCL) is another types of aliphatic polyester. PCL Based nanocomposites are commonly synthesized through ring opening polymerization of Ɛcaprolactone under mild condition. These are polymers prepared by the different composition of PCL with organomodified montmorillonite by melt blending (Yang et al., 2007) .PCL based nanocomposites for rigidity, heat resistance of inorganic materials may become the most important (Avella et al., 2006). In the latest study of sufficiently exfoliated PCL based nanocomposites, made of PCL and organoclays (OCs) with polar and nonpolar modifiers are done by the melt mixing and heat treatment methods (Chung et al., 2007). Another type of PCL can be improved in ductility and stiffness by the addition of montmorillonite clay and electrospun fibers to PCL (Causin et al., 2009). It can be fabricated using two techniques: in the melt blending the polymer matrix (PCL) mixed with CNTs using a DSMs microextruder and in the coprecipitation method PCL is solubilised in an organic solvent like tetrahydrofurane (THF). The PCL based nanocomposites have highest conductivity and highest dielectric constant (Molenberg et al., 2010). The main limitation of PCL based nanocomposites is low melting temperature (650 C), which can be overcome by blending with

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other polymer/ nanocomposites mixed with synthetic BAP and OMS (Pandey et al,. 2005).

(Ray and Okamoto, 2003) Multiwall carbon nanotubes (MWNTs)/nylon (PA6) nanocomposites has been improves the dispersion and strengthen the interaction between the nanotubes (Lui et al., 2004). The Multiwall carbon nanotube is used because of single wall carbon nanotubes (Lai et al., 2004). Polyamide Nylon 12 is family of polyamide, comparison of the nylon (PA 12) with longer aliphatic chain and lower melting point and strength than nylon 6 and nylon 66 (Phang et al,. 2005). The nylon 6 clay nanocomposites reduced the flammability and form rentation after burn compared with pure nylon 6, polyamide-clay nanocomposites with improved thermal stability and flammability (Zhang et al,. 2005).

Polyethylene (PE) based nanocomposites The polyethylene based nanocomposites is synthesized by in situ polymerization, solution blending and melt intercalation.

Comparing of the PP and intercalated PE–OMMT by using of twin extruder. These are composites more is pure PE polymers (Pandey et al,. 2005). Especially nanoclay has been increases in modulus, strength, barrio properties, and flammability resistance but PE is hydrophobic in nature because PE/clay is not easily prepared (Lei et al.2007).

SEM micrographs of 15% PCL + 3% MWNT SEM micrographs of 13,5% PCL + 3% MWNT

Polycarbonate (PC) based nanocomposites

Nylon-6 based nanocomposites Nylon is made by anionic ring opening polymerization of caprolactam and it is used in filaments of toothbrushes, ropes raincoats and automobiles industry for self-lubricating gears and bearing. During production of composites the presence of clay transforms the α-phase of nylon-6 into the γ-phase of nylon (Pandey et al., 2005). The α-phase crystal is thermodynamically more stable with anti parallel chain linked by the hydrogen bonds to adjacent chain where the γ-phase crystal consists of parallel chain (Phang et al., 2006). The effect of the particles size on nylone-6 nanocomposites is more as the addition of smaller particles gives better reinforcement (Yun Fu et al., 2008). Mostly nylon-6 matrix is used in the in situ intercalative polymerization (Alexander and Dubois. 2000). Successful reinforcement of Nylon- 6 nanocomposites with CNT within the matrix of Nylon-6 is found to increase the mechanical properties. Nylon -6 show good affinity for the silicate surface because of hydrogen bonding achieved by high level of exfoliation (Paul and Robeson,. 2008).

Major properties of the bisphenol-A based polyester (PC) because of greater transparency, toughness, thermal and dimensional stability. PC based nanocomposites is major application for the making of compact disc, riot shield, vandal proof glazing, baby feeding bottles, electric component, helmets etc (Pandey at al., 2005).

Poly (vinyl chloride) (PVC) based nanocomposites It is widely used in the formation of pipes, house siding, window profiles, wire cable insulation and flooring because of PVC is high chemical and abrasion resistance. Thermal dehydrochlorination of the PVC contains internal allylic chloride and tertiary chain (Pandey at al., 2005). Hectorite and bentonite clay is use for the making of poly (vinyl chloride).

In the recent work on PVC – LDH (layered double hydroxide) composites is better properties than PVC because of hydroxide can be absorbed the HCL. PVC-montmorillonite nanocomposites are made by melt blending, solution blending, and polymerization for the use pristine sodium clay and organically modified clay (Awad et al., 2009).

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IJBSTR REVIEW PAPER VOL 1 [ISSUE 6] JUNE 2013 Polystyrene based nanocomposites It can be prepared by different method, such as in situ polymerization, bulk polymerization, melt blending and solution blending, by the mixing of clay because of strong plastic. Clay used in situ polymerization VB-16 (virgin polymer) and nanocomposites (Pandey et al,. 2005).

Styrene butadiene rubber based nanocomposites SRB is a hybrid Nanocomposite containing compounds carbon black and organo modified nanoclay (NC). Carbon black is mostly used in rubber industry. It is important reinforcement filler for improving tear strength, modulus (Praveen at al,.

2008).

Polyaniline based nanocomposites (PANI) PANI-inorganic nanocomposites, it is wide range of properties such as electrical mechanical structural properties because of mixing with organic components in low level. The physical mixture of Na-MMT and PANI is more thermally stable (Pandey et al,. 2005). PANI is an intrinsically conductive polymer (IPC), like metal type characteristics, and good biocompatibility. PANI represents four type’s oxidation state, leucoemeraldine, emeraldine, nigraniline and pernigraniline.

PHB/PANI nanofiber composites are formed by the aniline polymerization reaction in the presence of emulsion of PHB in water/chloroform/SDS (Araujo et al., 2011).

ISSN 2320 – 6020 acetate propionate (CAP), and cellulose acetate butyrate (CAB) are thermoplastic. Some of modified nanoclay with mixing CA/organocaly nanocomposites, trimethyl citrate (TEC) combined with Cloisite 30B organoclays, and maleic anhydride-grafted cellulose acetate butyrate (CAB-g-MA) (Yang et al,. 2007). The production of nanocomposites, cellulosic plastic with 80% wt% pure cellulose acetate and 20% wt % trimethyl citrate plasticizer was used as polymer matrix (Sunday et al,. 2012). Another type of reinforce materials cellulose nanocrystal, it is very low cost, high availability, renewability, nanoscale dimensions, high surface area, easy to modification, and good mechanical response to strees (Lucia and Cao., 2007) Oil based nanocomposites The production of oil based nanocomposites from natural oil such as, soya oil that has been used in the production of resins.

Vegetable oil have contain long fatty acid chain, causes by desirable flexibility and toughness, to otherwise brittle resin system such as epoxy, urethane and polyester resins (Pandey et al., 2005). Plant oil/silica nanocomposites are produced from the acid-catalyzed curing of epoxidized plant oils with 3glycidoxypropyltrimetoxysilane (Yang et al,. 2007). In the oil based composites soy-based epoxy resin was mixed with montmorillonite clay in different concentration then resulting tensile strength increased (Sunday et al., 2012).

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Starch based nanocomposites Starch based nanocomposites is a low cost and readily available in market and become to growing interest as promising option toward enhancing the mechanical and barrier properties (Yang et al,. 2007). Starch based nanocomposites is formed by mixing between polymers in the matrix of thermoplastic. The first nanocomposites were thermoplastic starch and kaolin clay interaction (Pandey et al,. 2005). In the resent studies TPS-clay with nanocomposites formed by natural smectite clays, montmorillonite and hectorite. Advance studies on the both biodegradable polymer such as, PLA/ starch based nanocomposites, one was cheap and another is good mechanical properties (Yu Long et al,. 2006).

Cellulose based nanocomposites The most important advantages of nanofiber reinforcement has been obtained high strength, random-oriented, biobased, easily degradable and recycled (Yang et al,. 2007). It has been used in the polymer reinforcement. The fibers of cellulose of nanocomposites are called cellulose whiskers. For the improvement of the cellulose based nanocomposites use of clay such as, cellulose acetate, TEC, plasticiser and OMS clay (Pandey et al,. 2005). Raw cellulose is not useful because poor solubility and thermoplastic character so use for some modified cellulose, such as cellulose acetate (CA), cellulose

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