Influence of nanoclays on mechanical and barrier properties of hydrogenated acrylonitrile butadiene rubber nanocomposites

In this research, two different methods have been investigated for optimising the preparation of hydrogenated acrylonitrile butadiene rubber/clay nanocomposites. Commercially available organoclay (Cloisite 20A) has been considered for the preparation of rubber nanocomposites. A detailed analysis has been made to investigate the morphological structure and mechanical behaviour at room temperature and at elevated temperature. Also the influence of organoclays on permeability has been studied. Structural analysis indicates very good dispersion for a low loading of 5 parts per hundred (phr) amount of nanoclays. Significant improvements in mechanical properties have been observed with the addition of organoclays at both room and elevated temperatures. Even with the low level of addition of nanoclays, there was a remarkable reduction in permeability. © Institute of Materials, Minerals and Mining 2011.

The ageing behaviour of hydrogenated nitrile butadiene rubber/nanoclay nanocomposites in various mediums

Hydrogenated nitrile butadiene rubber (HNBR) nanocomposites were prepared using commercially available organoclays (Cloisite 15A). The main focus of the current investigation is to study the influence of the organoclay reinforced in HNBR after subjecting it to long-term oxidative ageing and immersion studies. All the different nanoclay nanocomposites were air aged for a period of 168 h and at 150°C. The changes in the mechanical properties such as tensile strength and elongation at break have been compared with respect to the control sample. For immersion tests, three different liquid mediums were considered for this current investigation. All the samples were immersed in different mediums for a period of 168 h at 150°C. The changes in the swelling index and the mechanical properties have been reported with respect to the control sample. After reinforcing nanoclays into HNBR there was good resistance to swelling in all the three different liquid mediums in comparison to control sample. Tensile testing was performed on the immersed nanocomposites to evaluate the mechanical behaviour after immersion studies. A probable mechanism behind the improved performance has been suggested. © The Author(s) 2012.

Optimization of the processing of HNBR/organoclay nanocomposite

In the current investigation, rubber/clay nanocomposites were prepared by two different methods using hydrogenated nitrile butadiene rubber (HNBR) and the organoclay namely Cloisite 15A (C15A). A new novel approach involving swelling of C15A by ulltrasonication in HNBR solution has been carried out for improving the exfoliation and compatibilization of organoclays with HNBR matrix. With the addition of 5phr of clay, the elongation at break and tear strength improved by 16% and 24% respectively. The effect of coupling agents namely amino functional silane and tetrasulfido silane on the nanocomposites have been investigated. The elongation at break and tear strength improved by 46% and 77% respectively with the use of silanes. The improvement in the mechanical properties attributes to improved interaction between the organoclays and HNBR matrix. This interaction has been studied by X-ray diffraction and transmission electron microscope. Pre-dispersion technique clearly suggests very good improvement in the dispersion and properties due to better filler-rubber compatibility. © 2010 American Institute of Physics.

Mechanism of gas permeation in processed HNBR/nanoclay composites

The influence of the layered silicate clay platelets on the nitrogen permeation properties of hydrogenated nitrile butadiene rubber (HNBR)/nanoclay nanocomposites has been investigated. Nanocomposites of HNBR modified with different percentages of the organoclay are processed through various routes. Commercially available organoclay (CLOISITE 15A) and various silane-coupling agents are used to improve the dispersion of the nanoclay in HNBR. A total of 10 different formulations of nanocomposites are manufactured. The addition of the organoclay has resulted in a significant enhancement of the nitrogen barrier properties of the manufactured nanocomposite. The mechanism of the reduction in the permeability is explained through the changes in the morphology and its bond to the filler. These changes are confirmed through examination of the morphology using x-ray diffraction, transmission electron microscope, and dynamic mechanical thermal analysis. There has been a drastic reduction up to 55.7% in nitrogen permeability. The reduction in gas permeation in HNBR is attributed to uniformly exfoliated clay platelets. Finally, three different permeability models, namely, the Nielsen model, modified Nielsen model, and Cussler model, have also been considered to predict the permeability behavior of nanocomposites with different volume filler fractions. The experimental values of gas permeability have been compared with theoretical models. It is observed that the modified Nielsen model closely matches with the measured permeation behavior. © 2011 Wiley Periodicals, Inc.

Optimized process for the inclusion of carbon nanotubes in elastomers with improved thermal and mechanical properties

The effects of addition of reinforcing carbon nanotubes (CNTs) into hydrogenated nitrile-butadiene rubber (HNBR) matrix on the mechanical, dynamic viscoelastic, and permeability properties were studied in this investigation. Different techniques of incorporating nanotubes in HNBR were investigated in this research. The techniques considered were more suitable for industrial preparation of rubber composites. The nanotubes were modified with different surfactants and dispersion agents to improve the compatibility and adhesion of nanotubes on the HNBR matrix. The effects of the surface modification of the nanotubes on various properties were examined in detail. The amount of CNTs was varied from 2.5 to 10 phr in different formulations prepared to identify the optimum CNT levels. A detailed analysis was made to investigate the morphological structure and mechanical behavior at room temperature. The viscoelastic behavior of the nanotube filler elastomer was studied by dynamic mechanical thermal analysis (DMTA). Morphological analysis indicated a very good dispersion of the CNTs for a low nanotube loading of 3.5 phr. A significant improvement in the mechanical properties was observed with the addition of nanotubes. DMTA studies revealed an increase in the storage modulus and a reduction in the glass-transition temperature after the incorporation of the nanotubes. Further, the HNBR/CNT nanocomposites were subjected to permeability studies. The studies showed a significant reduction in the permeability of nitrogen gas. Copyright © 2011 Wiley Periodicals, Inc.

Enhancement of the properties of EPDM/NBR elastomers using nanoclay for seal applications

In this research, we have investigated the effects of addition of different percentages of nanoclay to the ethylene propylene diene monomer (EPDM) and nitrile butadiene rubber (NBR) on the characteristics of these rubbers as seal material. Properties such as tensile strength, modulus at different extensions, elongation at break, compressive set, hardness, and permeability and abrasion resistance are tested to assess the effect of addition of the nanoclay. Results indicate that addition of nanoclay at certain compositions could slightly reduce the strength of the rubber. However more stable modulus at different strains are provided, the hardness of the rubber is preserved and slightly enhanced, the permeability is reduced in both rubbers especially considerable decrease in EPDM is observed which is desirable in diminishing the effect of explosive decompression. At the same time the compression test shows that the nanoclay improves the performance of the rubbers under compression which is essential in seal application. The X-ray diffraction tests clarify that the dispersion of the nanoclay in the NBR samples is of high quality. In the EPDM samples, the dispersion is in need of improvement. POLYM. COMPOS., 30:1657-1667, 2009. © 2008 Society of Plastics Engineers.

Hard coatings on elastomers for reduced permeability and increased wear resistance

In this study, three different elastomers, namely hydrogenated nitrile butadiene rubber, fluoroelastomer and silicone, have been subjected to two different hard metallised coatings by ion implantation process. The three different elastomers are commonly used in various seal applications, where reduced wear and gas permeability are essential in maintaining seal performance and functionality. Samples of these rubbers have been coated with chromium coating in one set of tests. In the second set of tests, samples of elastomers have been coated with tungsten carbide coating being deposited on all the three different elastomers. Wear, gas permeability and mechanical behaviour of the coated samples were compared with each other and with the control uncoated elastomers. All the coated samples showed good reduction in gas permeability. With the use of metallised coatings, there has been improved resistance to wear in all the coated samples. Adhesion strength and effect of coating on the elastomer have been investigated by mechanical testing. Mechanical tests revealed good adhesion of metal coatings on all the rubber samples, and there was no detrimental effect on the mechanical properties after coating. © 2012 Institute of Materials, Minerals and Mining.

Polystyrene and asphaltene micelles within blends with a bitumen of an SBS block copolymer and styrene and butadiene homopolymers

Using fluorescence microscopy, DSC and DMTA we have explored blends of a bitumen with a styrene-butadiene-styrene (SBS) block copolymer, and with blends of the bitumen with SBS and one or two homopolymers - a polystyrene and a poly(cis-butadiene). The SBS polymer was progressively replaced with quantities of the homopolymers both together in the proportions found in the block copolymer and then by each homopolymer separately. At low temperatures the blends are all softer than the bitumen itself, so the polymers plasticise the bitumen-rich phase, and above 50°C the blends' stiffness (E') falls below a plateau only when a critical proportion of the block copolymer has been replaced with the two homopolymers: this supports the idea of an extensive network created by the polystyrene-rich spherical microphases that is effective even when the polystyrene microphases have melted. In one polymer blend the stiffness rose as the temperature was raised above 100°C, suggesting the development of a mesophase based upon polybutadiene plus asphaltenes, in another E' was enhanced and E" remained constant as the temperature rose above 70°C, perhaps for a similar reason; in some loss process appeared and the stiffness fell as temperature rose; but in others a good part of the SBS was replaced by either polystyrene or polybutadiene without changing the appearance of a rubbery plateau, that is, without a diminution of the mechanical properties of the soft matter.

Ruthenium complexes of the 1,4-bis(diphenylphosphino)-1,3-butadiene-bridged diphosphine 1,2,3,4-Me-4-NUPHOS: Solvent-dependent interconversion of four- and six-electron donor coordination and transfer hydrogenation activity

In chloroform, [RuCl2(nbd)(py)(2)] (1) (nbd = norbornadiene; py = pyridine) reacts with 1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene (1,2,3,4-Me-4-NUPHOS) to give the dimer [Ru2Cl3(eta(4)-1,2,3,4-Me-4-NUPHOS)(2)]Cl (2a), whereas, in THF [RuCl2(1,2,3,4-Me-4-NUPHOS)(PY)(2)] (3) is isolated as the sole product of reaction. Compound 2 exists as a 4:1 mixture of two noninterconverting isomers, the major with C, symmetry and the minor with either C, or C-2 symmetry. A single-crystal X-ray analysis of [Ru2Cl3 (eta(4)-1,2,3,4-Me-4-NUPHOS)(2)] [SbF6] (2b), the hexafluoroantimonate salt of 2a, revealed that the diphosphine coordinates in an unusual manner, as a eta(4)-six-electron donor, bonded through both P atoms and one of the double bonds of the butadiene tether. Compounds 2a and 3 react with 1,2-ethylenediamine (en) in THF to afford [RuCl2(1,2,3,4-Me-4-NUPHOS)(en)] (4), which rapidly dissociates a chloride ligand in chloroform to give [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)] [Cl] (5a). Complexes 4 and 5a cleanly and quantitatively interconvert in a solvent-dependent equilibrium, and in THF 5a readily adds chloride to displace the eta(2)-interaction and re-form 4. A single-crystal X-ray structure determination of [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)][ClO4] (5b) confirmed that the diphosphine coordinates in an eta(4)-manner as a facial six-electron donor with the eta(2)-coordinated double bond occupying the site trans to chloride. The eta(4)-bonding mode can be readily identified by the unusually high-field chemical shift associated with the phosphorus atom adjacent to the eta(2)-coordinated double bond. Complexes 2a, 2b, 4, and 5a form catalysts that are active for transfer hydrogenation of a range of ketones. In all cases, catalysts formed from precursors 2a and 2b are markedly more active than those formed from 4 and 5a.

The Dissociative Recombination of Protonated Acrylonitrile, CH2CHCNH+, with Implications for Nitrile Chemistry in Dark Molecular Clouds and the Upper Atmosphere of Titan

Measurements on the dissociative recombination (DR) of protonated acrylonitrile, CH2CHCNH+, have been performed at the heavy ion storage ring CRYRING located in the Manne Siegbahn Laboratory in Stockholm, Sweden. It has been found that at~2meV relative kinetic energy about 50% of the DR events involve only ruptures of X–H bonds (where X=C or N)while the rest leads to the production of a pair of fragments each containing two heavy atoms (alongside H and/or H2). The absolute DR cross section has been investigated for relative kinetic energies ranging from ~1 meV to 1 eV. The thermal rate coefficient has been determined to follow the expression k(T) = 1.78 × 10-6 (T/300)-0.80 cm3 s-1 for electron temperatures ranging from ~10 to 1000 K. Gas-phase models of the nitrile chemistry in the dark molecular cloud TMC-1 have been run and results are compared with observations. Also, implications of the present results for the nitrile chemistry of Titan’s upper atmosphere are discussed.

Adsorption of Ni(SO4) on Malaysian rubber-wood ash

The possible use of wood ash as an adsorbent of nickel sulphate from dilute solutions and the effect of operating parameters were investigated in this study. The rate constants of adsorption were determined at different concentrations and temperatures. The applicability of the first-order reversible equation and an empirical kinetic model were tested to understand the kinetics of nickel sulphate removal at different concentrations. Pore diffusion was found as the rate-controlling step. The Langmuir and Freundlich isotherms were applied to find out the adsorption parameters. The activation energy of adsorption was -11.54 kJ mol-1. The value of the enthalpy change was ?H=-10.35 kcal mol-1.

Femtosecond lasers for mass spectrometry: Proposed application to catalytic hydrogenation of butadiene

Mass spectra from the interaction of intense, femtosecond laser pulses with 1,3-butadiene, 1-butene, and n-butane have been obtained. The proportion of the fragment ions produced as a function of intensity, pulse length, and wavelength was investigated. Potential mass spectrometry applications, for example in the analysis of catalytic reaction products, are discussed.