Biodeterioration of plasticized PVC/montmorillonite nanocomposites in aerobic soil environment

The aim of this study was to assess the effect of montmorillonite nanofillers, Cloisite Na⁺ and Cloisite 30B, on the biodeterioration of PVC-based nanocomposites plasticized by means of dioctyl adipate (DOA), dioctyl phthalate (DOP) and modified poly(propylene adipate) (PPA), in the aerobic environment of soil (soil burial test, time of exposure: 198 days). Tests were carried out at 25 ± 1 °C, under moisture-controlled (55 %) and aerobic conditions. The extent of the biodeterioration process was evaluated on the basis of changes in weight, tensile strength and elongation-at-break values. Finally, analysing chemical structures using FTIR and visual observation, both macroscopic and microscopic via scanning electron microscopy assisted in the evaluation process. The results of this study suggested that plasticized PVC/montmorillonite nanocomposites have an increased susceptibility for undergoing biological deterioration in comparison with plasticized PVC. In each instance, adding Cloisite 30B resulted in reducing the resistance of PVC/montmorillonite nanocomposites to the actions of microorganisms. In the case of Cloisite Na⁺ as the filler, results cannot be clearly quantified, although a negative influence prevailed, particularly a change in colour, whose change intensity was also dependent on the type of plasticizer, increasing in the following sequence: PVC/DOA/Cloisite Na⁺ > PVC/DOP/Cloisite Na⁺ > PVC/PPA/Cloisite Na⁺. However, each sample containing Cloisite Na⁺ achieved a lower rate of degradation (by normalised weight loss and FTIR) compared with nanocomposites containing Cloisite 30B. This can be attributed to the migration and accumulation of Cloisite Na⁺ on the surface of the nanocomposites particles where the former phenomenon producing a surface barrier which caused a reduction in the permeability of the material toward water and microorganisms, during the test.     

Synthesis and characterization of epoxy based nanocomposites

Epoxy‐clay nanocomposites were synthesized to examine the effects of the content and type of different clays on the structure and mechanical properties of the nanocomposites. Diglycidyl ether of bisphenol‐A (epoxy) was reinforced by 0.5–11 wt % natural (Cloisite Na⁺) and organically modified (Cloisite 30B) types of montmorillonite. SEM results showed that as the clay content increased, larger agglomerates of clay were present. Nanocomposites with Cloisite 30B exhibited better dispersion and a lower degree of agglomeration than nanocomposites with Cloisite Na⁺. X‐ray results indicated that in nanocomposites with 3 wt % Cloisite 30B, d‐spacing expanded from 18.4 Å (the initial value of the pure clay) to 38.2 Å. The glass transition temperature increased from 73°C, in the unfilled epoxy resin, to 83.5°C in the nanocomposite with 9 wt % Cloisite 30B. The tensile strength exhibited a maximum at 1 wt % modified clay loading. Addition of 0.5 wt % organically modified clay improved the impact strength of the epoxy resin by 137%; in contrast, addition of 0.5 wt % unmodified clay improved the impact strength by 72%. Tensile modulus increased with increasing clay loading in both types of nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1081–1086, 2005     

Preparation and characterization of high performance exfoliated montmorillonite/silicone rubber nanocomposites with enhanced mechanical properties

Highly exfoliated and intercalated silicone rubber (SR) nanocomposites based on natural montmorillonite (Cloisite Na⁺) and organically modified montmorillonite (Cloisite 30B and Cloisite 20A) were successfully prepared by melt‐mixing technique. Dispersion of the nanoclays in the rubber nanocomposites was subsequently investigated. As indicated by the X‐ray diffraction (XRD) analysis, intercalation, and exfoliation of the clay particles in the nanocomposites was achieved at less than 8 parts per hundred (phr) rubber by weight, irrespective of the initial interlayer spacing of the nanoclay particles. Both Cloisite Na⁺ and Cloisite 30B were spontaneously transformed into exfoliated microstructures during the vulcanisation stage. Overall, the use of the nanoclays in silicone rubber improved the Young's modulus, tensile strength, and elongation at break by more than 50% as compared with the control rubber. In addition, this work provided a fresh insight into the way intercalated and exfoliated morphologies affect mechanical properties of silicone rubber nanocomposites. It was shown that the exfoliated Cloisite Na⁺ yielded outstanding mechanical properties with low hysteresis at the same loading of the exfoliated Cloisite 30B and intercalated Cloisite 20A organoclays. As expected, the formation of crosslinks affected the mechanical properties of the rubber vulcanizate significantly. POLYM. ENG. SCI., 53:2603–2614, 2013. © 2013 Society of Plastics Engineers     

Improving heat ageing and thermal properties of silicone rubber using montmorillonite clay

Heat ageing and thermal stability of a silicone rubber (SR) filled with montmorillonite clay (MMT) was investigated. Three types of rubber nanocomposites were prepared with highly exfoliated Cloisite 30B (SR/C30B), intercalated/exfoliated Cloisite Na⁺ (SR/Na⁺MMT), and highly intercalated Cloisite 20A (SR/C20A). This study showed that the SR/C30B nanocomposite exhibited excellent heat resistance in comparison to the other two nanocomposites and neat SR as revealed by higher retention strength. The thermal stability of the rubber in air was strongly dependent on the clay morphology and increased in the following order: highly intercalated/exfoliated SR/Na⁺MMT < highly intercalated SR/C20A < highly exfoliated SR/C30B. The thermogravimetric analyses of the SR/C30B nanocomposite showed a substantial increase in the final residue in comparison with the neat SR. This indicated a major improvement in the thermal stability of the rubber containing the exfoliated clay, which was also supported by the higher activation energy of decomposition measured for the nanocomposite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41061.     

Effect of hydrogen bonding on the rheology of polycarbonate/organoclay nanocomposites

The linear dynamic viscoelastic properties and non-linear transient rheology of polycarbonate (PC)/clay nanocomposites were investigated at temperatures ranging from 240 to 280 °C. For the study, nanocomposites of PC and natural montmorillonite (Cloisite Na⁺) or chemically modified clay (Cloisite 30B) were prepared by melt blending in a twin-screw extruder. Cloisite 30B is a natural montmorillonite modified with methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium chloride (MT2EtOH). In both PC/Cloisite Na⁺ and PC/Cloisite 30B nanocomposites the concentration of clay was varied from 2.3 to 4.3 wt%. In situ Fourier transform infrared (FTIR) spectroscopy results show that at temperatures ranging from 30 to 280 °C the carbonyl groups in PC and the hydroxyl groups in MT2EtOH of Cloisite 30B in PC/Cloisite 30B nanocomposites formed hydrogen bonds, while no evidence of hydrogen bonding was observed in the PC/Cloisite Na⁺ nanocomposites. There are no discernible sharp reflections in the X-ray diffraction (XRD) patterns of PC/Cloisite 30B nanocomposites, after Cloisite 30B having the d₀₀₁ spacing of 1.85 nm was mixed with PC, whereas the d₀₀₁ spacing changes little (1.17 nm) before and after the mixing of Cloisite Na⁺ to PC. Transmission electron microcopy (TEM) images show that organoclay platelets are well dispersed in PC/Cloisite 30B nanocomposites, while the untreated clay platelets are poorly dispersed in PC/Cloisite Na⁺ nanocomposites. The observed differences in XRD patterns and TEM images between the two nanocomposite systems are explained by in situ FTIR spectroscopy. The results of rheological measurements (linear dynamic viscoelasticity, non-linear transient shear flow, and steady-state shear flow) support the conclusions drawn from the results of XRD, TEM, and FTIR spectroscopy.     

Chitosan/clay nanocomposite film preparation and characterization

Nanocomposites of chitosan and nanoclays (MMT‐Na⁺ and Cloisite 30B) were prepared by solvent casting. The structural properties, thermal behaviors, and mechanical properties were characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy, differential scanning calorimetry, thermogravimetry analyses, and an Instron universal testing machine. XRD and TEM results indicated that an exfoliated structure was formed with addition of small amounts of MMT‐Na⁺ to the chitosan matrix. Intercalation along with some exfoliation occurred with up to 5 wt % MMT‐Na⁺. Micro‐scale composite (tactoids) formed when Cloisite 30B was added to the chitosan matrix. Surface roughness increased with addition of a small amount of clay. Tensile strength of a chitosan film was enhanced and elongation‐at‐break decreased with addition of clay into the chitosan matrix. Melt behavior and thermal stability did not change significantly with addition of clays. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1684–1691, 2006     

Preparation and investigation of anticorrosion properties of the water-based epoxy-clay nanocoating modified by Na+-MMT and Cloisite 30B

In this study the effect of using nanoclay particles in two different matrices on anticorrosive performance improvement of a novel water-based epoxy coating was investigated. For this purpose, Na⁺-montmorillonite (Na⁺-MMT) and organo-montmorillonite (Cloisite 30B) were introduced into water-based hardener (RIPI-W.B.H.) and epoxy resin matrices, separately. Nanoclays were added to polymeric matrices using direct mixing under an ultrasonic homogenizer. The coatings were analyzed to ensure the intercalation and distribution of layered silicates by means of X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses. The structure of products is studied by infrared (IR) spectrometer. The corrosion protection performances of the coatings were investigated using salt spray test and electrochemical impedance spectroscopy (EIS) in 3.5% sodium chloride solution. The results showed that using Cloisite 30B in water-based hardener had the best performance and its application in anticorrosion water-based zinc rich epoxy coating approved of it.     

Influence of nanoclay on adhesion of EPDM vulcanizate

The influence of unmodified clay, Cloisite Na⁺ on adhesion between prevulcanized EPDM rubber and unvulcanized EPDM rubber containing nanoclay was investigated using 180° peel test. The rubber showed improvement in peel strength with increasing clay concentration up to 4 phr, beyond which it decreased. A maximum of 51% improvement in peel strength was obtained for 4 phr Cloisite Na⁺. This was attributed to enhanced tensile strength, monomer friction coefficient, marginal improvement of polarity and micro-roughness of the clay filled rubber. At higher clay loading (8 phr), the peel strength reduced due to formation of boundary layer of Zn-stearate, accelerators and clay on the outermost surface, diffusion of the fewer rubber chains, agglomeration of the clay particles and increased modulus of the rubber.     

Nanoclay distribution and its influence on the mechanical properties of rubber blends

The distribution of modified and unmodified nanoclays inside the rubber phases of immiscible rubber–rubber blends composed of nonpolar–polar natural rubber (NR)/epoxidized natural rubber (ENR) and nonpolar–nonpolar NR/polybutadiene rubber (BR) was investigated for the first time. The distribution of clays at various loadings in the blends was calculated from the viscoelastic properties of the blends. For example, in the 50 : 50 NR/ENR blend, 42% Cloisite 30B migrated to the NR phase, and 58% went to the ENR phase. However, in the same blend, only 7% Cloisite Na⁺ was found in the NR phase, and 93% was found in the ENR phase. Again, in the 50 : 50 NR/BR blends, the NR phase contained 85% Cloisite 30B, whereas 55% Cloisite Na⁺ migrated to the NR phase. All these observations were explained with the help of viscosity, X‐ray diffraction, and morphology analyses. The effect of the distribution of the clay on the mechanical properties was also discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Cure kinetic study of organoclay‐unsaturated polyester resin nanocomposites by using advanced isoconversional approach

Curing behavior of an unsaturated polyester (UP) resin containing 3 wt % Cloisite 10A (UP/10A) and 3 wt % Cloisite 30B (UP/30B) catalyzed with methyl ethyl ketone peroxide (MEKP) as initiator and promoted by cobalt naphthenate as accelerator was investigated by dynamic differential scanning calorimetry (DSC) at heating rates of 2, 2.5, 3, and 3.5°C min⁻¹. X‐ray diffraction and transmission electron microscopy were utilized to evaluate the morphology of UP/10A and UP/30B nanocomposites. Kinetic parameters of cure reactions were evaluated using the advanced isoconversional method. The addition of nanoclay resulted in a decrease in the activation energy of the redox reaction compared to that of the neat UP resin. The pre‐exponential factor of the redox reaction for UP/10A and UP/30B was less than that of the neat UP. Results showed an increase in the concentration of styrene between Cloisite 10A platelets leading to a decrease in the intralayer styrene content. The high concentration of styrene between nanoclay layers may lead to the formation of polystyrene chains grafted on the alkyds chains. This homo‐polymerization was also observed in the variation of activation energy of UP/10A specimen versus the degree of conversion for 0.42 ≤ α ≤ 0.6 which is very close to the activation energy of free radical homo‐polymerization of styrene. POLYM. COMPOS., 34:1824–1831, 2013. © 2013 Society of Plastics Engineers     

Transparent and thermally stable improved poly (vinyl alcohol)/Cloisite Na/ZnO hybrid nanocomposite films: Fabrication,morphology and surface properties

A series of poly(vinyl alcohol)/Cloisite Na⁺-Tyrosine/Zinc oxide (PVA/Cloisite Na⁺-Tyr/ZnO) bionanocomposites were prepared by dispersing ZnO nanoparticles in solution containing mixture of the PVA and modified Cloisite Na⁺. Structure of nanocomposite coatings was investigated by X-ray diffraction and Fourier-transform infrared spectroscopy. The thermal stability and optical properties of bionanocomposite were characterized by thermogravimetric analysis and UV–vis spectroscopy, respectively. The introduction of ZnO nanoparticles into PVA/Cloisite Na⁺-Tyr mixed solutions significantly increased the thermal stability of the obtained films. The results revealed that the high UV-shielding efficiency of the composites: for a film containing 6.0 wt% of ZnO nanocrystals, over 92% of UV light at wavelengths of 368 nm was absorbed while the optical transparency in the visible region was slightly below that of a PVA/Cloisite Na⁺-Tyr film.     

Melt-compounded salt-containing poly(ethylene oxide)/clay nanocomposites for polymer electrolyte membranes

The present study demonstrates the use of a simple and versatile melt-compounding route to prepare NaClO₄-containing poly(ethylene oxide) PEO/clay nanocomposites combining excellent mechanical properties with a competitive level of the ionic conductivity. The nanostructure and the resulting thermal, mechanical and conductive properties of the salt-containing PEO/clay nanocomposites were found to be highly sensitive to the clay type, i.e. aspect ratio of the clay, to the presence of an organic modifier in the intergallery spacing, and to the salt concentration. The highest increase of the shear storage modulus is obtained in the presence of single silicate layers, thus an exfoliated nanostructure, having a high aspect ratio. These structures are only obtained with an (polar) organically modified clay (Cloisite 30B), regardless of the presence of salt. The use of non-organically modified clays (Cloisite Na⁺ and Laponite) resulted in intercalated nanocomposites, with only a minor improvement in stiffness. A strong interaction between the Na⁺ from NaClO₄ and the Cloisite 30B silicate layers might be responsible for an increased PEO crystallinity and resultant additional increase in stiffness. A mechanism is proposed whereby the Na⁺ ions are drawn away from the PEO phase, to be complexed by the silicate layers, or even ion-exchanged with modifier cations. The addition of clay did not greatly affect the ion conductivity below the melt temperature of PEO. At higher temperatures, the nanocomposites displayed only slightly lower conductivities compared to the PEO/NaClO₄ complex, due to the presence of the clay platelets.     

Synthesis of montmorillonite-modified acrylic impact modifiers and toughening of poly(vinyl chloride)

A series of Na-montmorillonite (Na⁺-MMT) modified acrylic impact modifiers (mAIM) were prepared by seeded emulsion polymerization. These mAIM modifiers were characterized by XRD. A 0.24?nm of increased interlayer distance of Na⁺-MMT was an indication of polymer chains intercalation within interlayer spacing. The notched Izod impact tests proved that the impact strength of the PVC/AIM composites prepared by melt blending was 43?J/m, markedly higher than the impact strength of pure PVC. Furthermore, with increasing content of AIM, the composites exhibited changes from brittle fracture to ductile fracture, with the impact strength increasing from 200 to about 1,000?J/m. The impact strength of PVC/mAIM also showed the same trend, although there were drops in some values. The impact strength of PVC/mAIM composites decreased with the increases in Na⁺-MMT content, but the yield strength and modulus of the composites increased with higher Na⁺-MMT content. The result also showed that the tensile strength of mAIM with 2 wt?% Na⁺-MMT is lower than that of mAIM with 0.8 and 1 wt?% contents, but still sufficiently large in comparison to the tensile strength of mAIM with 0 wt?% Na⁺-MMT. The dynamic mechanical analysis (DMA) result showed that the glass transition temperature (T _g) of mAIM did not show obvious changes and the elasticity of mAIM was reduced with the additional Na⁺-MMT content.     

Rigid PVC/(layered silicate) nanocomposites produced through a novel melt‐blending approach

On the basis of the fusion behavior of poly(vinyl chloride) (PVC), the influence of compounding route on the properties of PVC/(layered silicate) nanocomposites was studied. Four different compounding addition sequences were examined during the melt compounding of PVC with montmorillonite (MMT) clay, including (a) a direct dry mixing of PVC and nanoclay, (b) an addition of nanoclay at compaction, (c) an addition of nanoclay at the onset of fusion, and (d) an addition of nanoclay at equilibrium torque. Both unmodified sodium montmorillonite (Na⁺‐MMT) and organically modified montmorillonite (Org.‐MMT) clays were used, and the effect of the addition sequence of the clay during compounding on its dispersion in the matrix was evaluated by X‐ray diffraction and transmission electron miscroscopy. The surface color change, dynamic mechanical analysis, and flexural and tensile properties of PVC/clay nanocomposites were also studied. The experimental results indicated that both the extent of property improvement and the dispersion of nanoparticles in PVC/(layered silicate) nanocomposites are strongly influenced by the degree of gelation achieved in PVC compounds during processing. The addition of nanoclay to PVC must be accomplished at the onset of fusion, when PVC particles are reduced in size, in order to produce nanocomposites with better nanodispersion and enhanced mechanical properties. Overall, rigid PVC nanocomposites with unmodified clay (Na⁺‐MMT) were more thermally stable and exhibited better mechanical properties than their counterparts with organically modified clay (Org.‐MMT). J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Morphology and Thermal Stability of Novolac Phenolic Resin/Clay Nanocomposites Prepared via Solution High‐Shear Mixing

Phenolic resin/clay composites were prepared by high‐shear mixing of clay suspended in CH₃OH solutions of Novolac resin and curing agent. Pure clay Cloisite Na⁺ and pillared clays Cloisite 10A, 30B, and Na⁺Cloisite that was pillared by 3‐hexadecyl‐1‐methylimidazolium bromide were studied. After CH₃OH evaporation, Novolac was cured at low temperatures. XRD showed that clay gallery d‐spacings decreased upon solvent evaporation and partial curing. Slight d‐spacing increases were sometimes observed from a partially cured stage to a further cured composite. Na⁺Cloisite gave the highest nanodispersion, Cloisites 10A and 30B the lowest. TGA revealed that Na⁺ clay or organoclay incorporation in partially cured and cured composites did not improve the thermal stability of Novolac.

     

Dispersion of chiral amino acid organomodified Cloisite Na in poly(vinyl alcohol) matrix for designing of novel bionanocomposite films

In this study the inorganic nanolayers of Cloisite Na⁺ was modified with ammonium salt of l-valine amino acid (Val) and then it was dispersed in poly(vinyl alcohol) (PVA) matrix. The PVA/Cloisite Na⁺/Val bionanocomposites (BNC)s were prepared by solution intercalation technique using ultrasonic irradiation. The reaction between this novel organically modified Cloisite Na⁺ and PVA occurred by the hydrogen bonding and hydrophobic interactions. The basal spacing of the Cloisite Na⁺/Val was studied by X-ray diffraction. The thermal stability and optical clarity of PVA and PVA/Cloisite Na⁺/Val are also studied by thermogravimetric analysis (TGA) and UV–visible transmission spectra, respectively. TGA results show that using Cloisite Na⁺/Val in the PVA matrix improved the thermal stability property of the resulting BNC films. The morphological image of synthesized materials was studied by scanning electron microscopy, and transmission electron microscopy. The nanocomposite structure study specified a coexistence of exfoliated and intercalated Cloisite Na⁺/Val layers in the PVA matrix.     

Can We Make Better Polyurethane Composite Foams with Oil Sands Mature Fine Tailing?

This study explains how to make rigid polyurethane/mature fine tailings (PU/MFT) foam composites with good mechanical and thermal properties by in situ polymerization. Compared to PU/Cloisite Na⁺ and PU/Cloisite 30B composites, the novel PU/MFT composites have similar tensile properties, but better thermal properties. Adding 2 parts per hundred parts (pphp of polyol by weight) of MFT particles decreases the thermal conductivity of polyurethane foam by 10%, while adding Cloisite Na⁺ or Cloisite 30B decreases it by only 6% and 5%, respectively, resulting in considerable energy savings in large‐scale insulation applications. PU/MFT foams also sustain about the same compressive strength and modulus even when loaded up to 20 pphp MFT. These results are important for oil sands industries trying to decrease the environmental footprint of their operations and for polyurethane‐producing companies attempting to improve properties of their products and contribute to environmental cleanup.

     

Synthesis and characterization of elastomeric polyurethane and PU/clay nanocomposites based on an aliphatic diisocyanate

This investigation reports preparation of polyurethane and polyurethane/clay nanocomposites based on polyethylene glycol, isophorone diisocyanate (IPDI), an aliphatic diisocyanate and 1,4‐ Butanediol as chain extender by solution polymerization. In this case PU/clay nanocomposites were prepared via ex‐situ method using 1, 3, and 5 wt % of Cloisite 30B. Thermogravimetric analysis showed that the maximum decomposition temperature (T_max) of the PU/clay nanocomposite is much higher than the pristine PU. The tensile properties improved upon increasing the organoclay (Cloisite 30B) content upto 3 wt %, and then decreased to some extent upon further increasing the nanoparticle loading to 5 wt %. Optical properties of the nanocomposites were studied by UV‐vis spectrophotometer. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) were used to study the morphology of the nanocomposites. It was observed that with the incorporation of 3 wt % nanoclay the crystallinity in PU nanocomposite increases, then diminishes with further loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3328–3334, 2013     

Preparation and Properties of Biodegradable Thermoplastic Starch/Clay Hybrids

Biodegradable thermoplastic starch (TPS)/clay hybrids were prepared by melt intercalation. Three organically modified montmorillonite (MMT) with different ammonium cations and one unmodified Na⁺ MMT (Cloisite Na⁺) were used. Cloisite Na⁺ showed the best dispersion in the TPS matrix. It was observed that the TPS/Cloisite Na⁺ hybrid showed an intercalation of TPS in the silicate layer due to the matching of the surface polarity and interactions of the Cloisite Na⁺ and the TPS, which gives higher tensile strength and better barrier properties to water vapor as compared to the other TPS/organoclay hybrids as well as the pristine TPS. It was found that the dynamic mechanical properties of the TPS/clay hybrids were also affected by the polar interactions.     

Investigation of the corrosion protection behavior of natural montmorillonite clay/bitumen nanocomposite coatings

The influence of clay particles on the corrosion properties of bituminous coating was studied. Different percentages of natural montmorillonite clay (Cloisite Na⁺) were added to emulsified bitumen in water to make 2 wt.%, 3 wt.% and 4 wt.% of clay/bitumen nanocomposite coatings. The coatings were applied on steel 37. Optical microscopy and transmission electron microscopy (TEM) were employed to study the structure of nanocomposite. To investigate the anti-corrosion properties of the coated panels, electrochemical impedance spectroscopy (EIS) was used. The findings indicated that the addition of clay nanolayers improved corrosion resistance of the coatings. Moreover, increasing clay loading up to 4 wt.%, increased the corrosion resistance.