Synthesis and characterization of polyimide‐γ‐Fe2O3 nanocomposites

Novel polyimide‐γ‐Fe₂O₃ hybrid nanocomposite films (PI/γ‐Fe₂O₃) has been developed from the poly(amic acid) salt of oxydianiline with different weight percentages (5, 10, 15 wt %) of γ‐Fe₂O₃ using tetrahydrofuran (THF) and N,N‐dimethylacetamide (DMAc) as aprotic solvents. The prepared polyimide‐γ‐Fe₂O₃ nanocomposite films were characterized for their structure, morphology, and thermal behavior employing Fourier transform infrared spectroscopy (FTIR), scanning electron micrograph (SEM), transmission electron micrograph (TEM), X‐ray diffraction (XRD), ¹³C‐NMR, and thermal analysis (TGA/DSC) techniques. These studies showed the homogenous dispersion of γ‐Fe₂O₃ in the polyimide matrix with an increase in the thermal stability of the composite films on γ‐Fe₂O₃ loadings. Magnetization measurements (magnetic hysteresis traces) have shown very high values of coercive force indicating their possible use in memory devices and in other related applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 834–840, 2007     

Preparation of high capacity weak base poly(methyl methacrylate)–ethylene glycol dimethylacrylate copolymer anion exchange resin by modification using NOx

Macroporous poly(methyl methacrylate)–ethylene glycol dimethylacrylate (PMMA–EGDM) resin (resin 1) was prepared by suspension polymerization and gelatin was found to be the key component deciding the size of particles. To prepare aminated macroporous weak base PMMA–EGDM exchanger, resin 1 was nitrated using NO₂ gas with a minor amount of NO (termed NO_x). The modified PMMA–EGDM resin (resin 2) was reduced to NH₂ groups and the exchange capacity of the weak base anion exchange resin (resin 3) was determined. Regression analysis of NO_x consumption versus time and the exchange capacity Q versus time data suggested a second‐order kinetics for the modification reaction and these are reported. We examined the effect of duration of nitration on the exchange capacity of resin 3. It was found that it first increased with the increase in the extent of nitration, reaching a broad maximum of 4.8 meq/g of wet resin with 78% moisture for about 8 h of nitration, and decreasing for longer nitration times as a result of polymer degradation. These results were compared with commercial resin, which had an exchange capacity of 1.68 meq/wet g with 43% moisture content. To assess the salvation ability of the modified PMMA–EGDM resin, consistent with the literature, we devised three stages of removing moisture. Experiments suggest that the high capacity of the modified PMMA–EGDM resin may be attributed to this increased salvation ability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1991–1999, 2003     

Measurement of Residual Stresses in Oxide–ZrO2 Three-Layer Composites

Al₂O₃–ZrO₂ and MgO–ZrO₂ layered composites were fabricated in such a way that the outer layers of bar-shaped specimens consisted of the oxide (Al₂O₃ or MgO) and unstabilized ZrO₂, while the bulk consisted of the oxide and partially stabilized ZrO₂. During cool-down from the sintering or the annealing temperature, the outer layers expanded because of the tetragonal → monoclinic transition in ZrO₂, thereby creating compressive stresses in the outer layers and tensile stresses in the bulk. Residual stresses were determined using a strain gage technique in which a strain gage was mounted on one face while the opposing face was incrementally ground off. Measurement of the strain as a function of thickness permitted the evaluation of residual stresses using pertinent equations from simple beam theory.     

Effect of carbon black on properties of rubber nanocomposites

Polymer based nanocomposites were prepared using brominated poly(isobutylene‐co‐paramethylstyrene) (BIMS) rubber and octadecyl amine modified montmorillonite nanoclay. The effect of nature and loading of carbon black on these nanocomposites and the control BIMS was investigated thoroughly using X‐ray diffraction technique (XRD), Fourier transform infrared spectroscopy (FTIR), and mechanical properties. The addition of 4 parts of the modified nanoclay to 20 phr N550 carbon black filled samples increased the tensile strength by 53%. Out of the three different grades of carbon black (N330, N550, and N660), N550 showed the best effect of nanoclay. Optimum results were obtained with the 20 phr filler loading. For comparison, china clay and silica at the same loading were used. Fifty‐six and 46% improvements in tensile strength were achieved with 4 parts of nanoclay added to the silica and the china clay filled samples, respectively. N330 carbon black (20 parts) filled styrene butadiene rubber (SBR) based nanocomposite registered 20% higher tensile strength with 4 parts of the modified nanoclay. In all the above carbon black filled nanocomposites, the modulus was improved in the range of 30 to 125%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 443–451, 2005     

Adhesive tack and green strength of EPDM rubber

Measurement of tack of EPDM (ethylene-propylenediene terpolymer) rubber with natural rubber (NR) of four different molecular weights, styrene-butadiene rubber (SBR), butadiene rubber (BR), bromobutyl rubber (BIIR), and polychloroprene rubber (CR) was done over a range of rates of testing, contact times, and temperatures of contact. The effect of different additives, namely carbon black, phenol-formaldehyde resin, coumarone-indene resin, and methyl methacrylate is also reported. Green strength of all the rubbers was measured. Tack strength increases with increase in contact time for all the rubbers. Adhesive tack between EPDM and low-molecular-weight NR is much higher than that between EPDM and NR of high molecular weight. Tack strength of EPDM with BIIR is the highest among the tack values obtained for synthetic rubbers. The adhesive tack between EPDM and natural/ synthetic rubber passes through a maximum when plotted against temperature of contact. It increases with testing rate. All these phenomena could be explained in terms of interdiffusion of rubber chains under different conditions and solubility parameter of two contacting rubbers. It was observed that tack strength varies with (contact time)^1/2 and (rate)^1/2 in accordance with the reptation theory. Phenol-formaldehyde resin (PF) or coumarone-indene (CI) resin in EPDM improves the tack strength quite significantly. The resin in the NR phase does not have a marked effect. The presence of carbon black decreases adhesive tack strength between EPDM and NR. The surface of EPDM, however, becomes smoother with the addition of the additives. Peel tests and commercial tack tests give similar results in the tack strength between EPDM/NR and EPDM/SBR.     

Ethylene propylene diene terpolymer/ethylene vinyl acetate/layered silicate ternary nanocomposite by solution method

A new ternary nanocomposite has been developed using ethylene propylene diene terpolymer (EPDM), ethylene vinyl acetate (EVA‐45) copolymer, and organically modified layered silicate (16 Me‐MMT) from sodium montmorillonite (Na⁺‐MMT). Wide angle X‐ray diffraction and transmission electron microscopic analysis confirmed the intercalation of the polymer chains in between the organosilicate layers and the nanoscale distribution of 16 Me‐MMT in polymer matrix, respectively. The measurement of mechanical properties for 2–8 wt% of 16 Me‐MMT loadings showed a significant increase in tensile strength, elongation at break, and modulus at different elongations. Such an improvement in mechanical properties has been correlated based on the fracture behavior of nanocomposite by SEM analysis. Thermal stability of EPDM/EVA/layered silicate ternary nanocomposites also showed substantial improvements compared with the neat EPDM/EVA blend, confirming thereby the formation of a high performance nanocomposite. POLYM. ENG. SCI., 46:437–843, 2006. © 2006 Society of Plastics Engineers     

Ethylene–octene copolymer (engage)–clay nanocomposites: Preparation and characterization

In this work, preparation and properties of nanoclay modified by organic amine (octadecyl amine, a primary amine) and Engage (ethylene–octene copolymer)–clay nanocomposites are reported. The clay and rubber nanocomposites have been characterized with the help of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The X‐ray results suggest that the intergallery spacing of pristine clay increases with the incorporation of the amine. The XRD peak observed in the range of 3–10° for the modified clay also disappears in the rubber nanocomposites at low loading. TEM photographs show exfoliation of the clays in the range of 10–30 nm in Engage. In the FTIR spectra of the nanocomposite, there are common peaks for the virgin rubber as well as those for the clay. Excellent improvement in mechanical properties, like tensile strength, elongation at break, and modulus, is observed on incorporation of the nanoclay in Engage. The storage modulus increases, tan δ peak decreases, and the glass transition temperature is shifted to higher temperature. The results could be explained with the help of morphology, dispersion of the nanofiller, and its interaction with the rubber. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 603–610, 2006     

Acrylic rubber‐fluorocarbon rubber miscible blends: Effect of curatives and fillers on cure,mechanical, aging,and swelling properties

The cure characteristics and mechanical properties of gum and filled acrylic rubber (ACM), fluorocarbon rubber (FKM), and their blends of varying compositions were studied both under unaged and aged conditions. The rheometric study showed that optimum cure properties were obtained using a mixed curing system of blocked diamine, hexamethylenediamine carbamate (Diak #1), and ammonium benzoate. From varying the curing agents, the optimum levels of Diak #1 and ammonium benzoate were found to be 1.5 and 2.5 phr, respectively. The addition of different fillers and their loading influenced the cure properties, with increased torque and reduced scorch safety. The gum and filled 50:50 (w/w) ACM‐FKM showed overall performance in strength properties. Postcuring improved the strength of all the systems, especially the systems with a higher proportion of FKM. None of the properties changed significantly during aging of the blends. FKM and the blends containing a higher proportion of FKM were affected least by aging. Swelling of the blends was reduced by the addition of fillers. Dynamic mechanical thermal analysis showed a single tan δ peak corresponding to a single phase transition for both cured and filled blends. The storage modulus of the blend increased from the gum blend to the filled blend, indicating the presence of polymer‐filler interaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1442–1452, 2003     

High-Toughness Ce-TZP/Al2O3 Ceramics with Improved Hardness and Strength

Simulataneous additions of SrO and Al₂O₃ to ZrO₂ (12 mol% CeO₂) lead to the in situ formation of strontium aluminate (SrO · 6Al₂O₃) platelets (∼0.5 μm in width and 5 to 10 μm in length) within the Ce-TZP matrix. These platelet-containing Ce-TZP ceramics have the strength (500 to 700 MPa) and hardness (13 to 14 GPa) of Ce-TZP/Al₂O₃ while maintaining the high toughness (14 to 15 MPa ± m^1/2) of Ce-TZP. Optimum room-temperature properties are obtained at SrO/Al₂O₃ molar ratios between 0.025 and 0.1 for ZrO₂ (12 mol% CeO₂) with starting Al₂O₃ contents ranging between 15 and 60 vol%. The role of various toughening mechanisms is discussed for these composite ceramics.     

Cubic-to-Tetragonal Displacive Transformation in Gd2O3–Bi2O3 Ceramics

Gd₂O₃-doped Bi₂O₃ polycrystalline ceramics containing between 2 and 7 mol% Gd₂O₃ were fabricated by pressureless sintering powder compacts. The as-sintered samples were tetragonal at room temperature. Hightemperature X-ray diffraction (XRD) traces showed that the samples were cubic at elevated temperatures and transformed into the tetragonal polymorph during cooling. On the basis of conductivity measurements as a function of temperature and differential scanning calorimetry (DSC), the cubic → tetragonal as well as tetragonal → cubic → teansition temperatures were determined as a function of Gd₂O₃ concentration. The cubic → tetragonal transformation appears to be a displacive transformation. It was observed that additions of ZrO₂ as a dopant, which is known to suppress cation interdiffusion in rare-earth oxide–Bi₂O₃ systems, did not suppress the transition, consistent with it being a displacive transition. Annealing of samples at temperatures 660°C for several hundred hours led to decomposition into a mixture of monoclinic and rhombohedral phases. This shows that the tetragonal polymorph is a metastable phase.