Thermal properties and flammability of nanocomposites based on diene rubbers and naturally occurring and activated halloysite nanotubes

This article presents a procedure of the activation of halloysite and a method of the synthesis of nucleus-sheath type filler. The effects of the nanoadditives obtained on the thermal properties, flammabilities and fire hazards of peroxide and sulfur vulcanizates of NBR and SBR rubbers, are discussed. Based on the test results obtained by derivatography, oxygen index, FAA micro-calorimeter and cone calorimeter, the thermal stability, flammability, and fire hazard of the nanocomposites investigated were determined. The results obtained were interpreted from the point of view of the chemical structure of the diene elastomers investigated, their spatial network structure, and the method of halloysite modification.     

Effect of the modification of silica on thermal properties and flammability of cross-linked butadiene-acrylonitrile rubbers

The paper presents the results of testing the thermal stability and flammability of butadiene-acrylonitrile rubber vulcanizates with different contents of combined acrylonitrile: Perbunan NT 1845 and Perbunan NT 3945 from Bayer, containing unmodified and bromine- or iodine-modified silica. The test results were obtained with the use of a derivatograph, measurements of flammability by the method of oxygen index, in air and also with the use of a cone calorimeter. The effect of the modification on the zeta potential was also examined. A considerable reduction in the flammability of nitrile rubber vulcanizates filled with silica can be obtained by the modification of filler with bromine or iodine. All the vulcanizates containing modified silica are self-extinguishing. An appropriate filling of NBR 39 vulcanizates with bromine-modified silica makes it possible to obtain non-flammable polymeric materials. They neither ignite nor glow under the action of a flame source for 30 s. The findings can be a rational basis for the synthesis of modified silica that can act as active filler and effective flame-retardant agent at the same time.     

Flammability of diene rubbers

This paper presents the results of testing the flammability and fire hazard of butadiene (BR), butadiene-acrylonitrile (NBR) and butadiene- styrene (SBR) rubbers with the use of oxygen index test, ignition temperature measurement, cone calorimetry and inverse liquid chromatography. Toxicometric indices, RTFH _CO/CO2, W_LC50SM and the concentration of polycyclic aromatic hydrocarbons (PAH) have been determined. The results obtained have been interpreted from the point of view of the chemical constitution of the polymers tested.     

Influence of cryogenic modification of silica on thermal properties and flammability of cross-linked nitrile rubber

The article presents the results of testing thermal properties and combustibility of butadieneacrylonitrile rubber with 18% contents of bounded acrylonitrile, NBR 18. Two types of silica, Zeosil 175C and Ultrasil VN-3, with different specific surfaces were used as filler. Zeosil 175C and Ultrasil VN-3 were modified via cryogenic dezaggregation method. The activity of unmodified and cryogenic modified silica toward butadiene-acrylonitrile rubber were investigated. The sulphur and peroxide vulcanizates contained 20, 30, 40, and 50 phr. of the filler were studied. The article discusses also the test results of thermal stability and flammability of NBR 18 containing silica prepared "in situ" from alkoxysilane precursor. The test results were obtained with the use of derivatograph, measurements of flammability by the method of oxygen index, and in air. The effect of the silica modification on the SEM and AFM was also examined. The method of cryogenic modification enables to achieve increase of mineral fillers activity towards elastomer and reduction in the flammability of NBR 18 vulcanizates. It has been found that the modification of the vulcanizates of NBR 18 with tetraethoxysilane that makes it possible to form silica "in situ" reduces the flammability of cross-linked rubbers.     

Effect of halogenless flame retardants on the thermal properties, flammability, and fire hazard of cross-linked EVM/NBR rubber blends

This paper presents the results of investigating the thermal stability, flammability, and fire hazard of cross-linked EVM/NBR blends unfilled and filled with halogenless flame-retardant compounds such as melamine cyanurate or magnesium hydroxide. The thermal analysis of the blends was carried out in the atmosphere of air. The activation energy of the composite destruction was determined by two non-isothermal methods: Flynn–Wall–Ozawa’s and Kissinger’s methods. The flammability of the composites obtained was determined by the method of oxygen index and on the basis of their combustion in air. The fire hazard of the vulcanizates investigated was determined with the use of a cone calorimeter and on the basis of toxicometric parameters W _LC50SM. The test results have shown that the flame retardants used increase the thermal stability of the cross-linked blends and decrease their flammability, and thereby allow one to obtain self-extinguishing or non-flammable polymeric materials. The cross-linked EVM/NBR blends filled with these flame-retardant compounds are characterized by good mechanical properties and reduced fire hazard.     

Effect of the spatial network structure and cross-link density of diene rubbers on their thermal stability and fire hazard

The paper presents the results of investigating the effect of the density and spatial network structure of diene rubbers (NBR and SBR) on their thermal properties and fire hazard. The rubbers were either conventionally cross-linked by means of sulfur and organic peroxide or nonconventionally with the use of iodoform (CH₃I). Based on thermo-kinetic analysis, the destruction activation energy of the elastomers investigated and their vulcanizates was determined under air and inert gas. The analysis of particular stages of their thermal decomposition was also presented. During the combustion of the elastomeric materials obtained, it has been found that their fire hazard depends not only on the elastomer chemical structure but also on the method of its cross-linking.     

Thermal properties of diene elastomers

The paper presents the results of investigating the effect of the macromolecule chemical structure and the spatial network structure of butadiene (BR), butadiene-styrene (SBR) and butadiene-acrylonitrile (NBR) rubbers on their thermal properties. The rubbers were cross-linked by the conventional method by means of dicumyl peroxide or sulfur as well as by the non-conventional way using iodoform (CH₃I). The rubber and their vulcanizates were assessed by the derivatographic method (under air) and by means of differential scanning calorimetry (DSC) under inert gas. The thermal cross-linking degree of the polydienes and the efficiency of the cross-linking processes, dependent on both the chemical structure of elastomer macromolecules and their spatial network structure were determined. The cross-linking of elastomers with iodoform changes the thermal properties of polymers, significantly increasing their glass transition temperature during both sample heating and cooling, which results from the increase in mutual interaction of macromolecules connected with their modification with iodine compounds.     

Reinforcement of compatibilized NR/NBR blends by fly ash particles and precipitated silica

Effects of precipitated silica (PSi) and silica from fly ash (FA) particles (FASi) on the cure and mechanical properties before and after thermal and oil aging of natural rubber (NR) and acrylonitrile–butadiene rubber (NBR) blends with and without chloroprene rubber (CR) or epoxidized NR (ENR) as a compatibilizer have been reported in this paper. The experimental results suggested that the scorch and cure times decreased with the addition of silica and the compound viscosity increased on increasing the silica content. The mechanical properties for PSi filled NR/NBR vulcanizates were greater than those for FASi filled NR/NBR vulcanizates in all cases. The PSi could be used for reinforcing the NR/NBR vulcanizates while the silica from FA was regarded as a semi‐reinforcing and/or extending filler. The incorporation of CR or ENR enhanced the mechanical properties of the NR/NBR vulcanizates, the ENR being more effective and compatible with the blend. The mechanical properties of the NR/NBR vulcanizates were improved by post‐curing effect from thermal aging but deteriorated by the oil aging. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and properties of graded styrene‐butadiene rubber vulcanizates

Styrene‐butadiene rubber (SBR) vulcanizates with graded network‐chain densities in the thickness direction were prepared by layering and heat pressing the compounding sheets. The effect of the gradient of network‐chain density on the mechanical properties of the graded rubber vulcanizates was investigated in comparison with those of SBR vulcanizates that were prepared from the homogeneous compounding sheets. The matrix with a high network‐chain density exclusively affected the mechanical properties of the graded rubber vulcanizates when the gradient was given in the thickness direction. © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 358–364, 2002; DOI 10.1002/polb.10096     

Colouring Agents for SBR Vulcanizates and Their Effects on Ageing and UV Radiation Resistance

Summary: Metal free and some metal-perylene polymers as well as some metal phthalocyanine polymers were incorporated into styrene butadiene rubber (SBR) compounds as colouring agents. The ageing and UV resistance of the vulcanizates obtained were studied in terms of their mechanical properties. The results obtained revealed that cobalt perylene and cobalt phthalocyanine polymers showed superior performance in SBR vulcanizates against thermal ageing and UV radiation. The optimum concentration of cobalt phthalocyanine polymer was found to be 1 phr (parts per hundred parts of rubber).     

Considering factors on determination of microstructures of SBR vulcanizates using pyrolytic analysis

Properties of styrene-butadiene rubbers (SBRs) are depending on their microstructures (contents of 1,4-unit, 1,2-unit, and styrene), but it is hard to determine the microstructures of SBR vulcanizates. Pyrolytic method such as pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) has been used for microstructures of cured rubbers without pretreatment. Microstructure of SBRs can be estimated using the major pyrolysis products (butadiene, 4-vinylcyclohexene (VCH), and styrene). In this study, considering factors for determination of microstructures of SBR vulcanizates using Py-GC/MS were investigated. The principal considering factors were found to be change of the major pyrolysis products due to radicals formed in carbon backbone and sulfur by dissociation of sulfide crosslinks in SBR vulcanizates. Relative abundances of the major pyrolysis products of raw and cured SBRs were different due to rearrangements of the radicals. Influencing factors on pyrolysis behaviors of SBR vulcanizates were found to be 1,2-unit block, alternating sequence of 1,4- and 1,2-units, styrene-1,4-unit and styrene-1,2-unit sequences, and location of the radicals. Especially, the 1,2-unit block influenced on change of the VCH/butadiene ratio, while the styrene-1,2-unit sequence affected change of the styrene/(butadiene + VCH) one.     

Thermal stability,flammability and fire hazard of butadiene-acrylonitrile rubber nanocomposites

This article presents the effect of the method of NBR cross linking on the thermal properties, flammability and fire hazard of its nanocomposites containing modified montmorillonite (NanoBent or Nanofil), using test results obtained by means of a derivatograph, oxygen index and cone calorimetry. It has been found that the thermal stability and flammability of the nanocomposites investigated depend on both the rubber network structure and the type of montmorillonite. The nanoadditives used reduce the flammability of cross-linked nitrile rubber and considerably limit its fire hazard.     

TG-MS analysis of nitrile butadiene rubber blends (NBR/PVC)

Blends of nitrile butadiene rubber (NBR) with polyvinyl chloride (PVC) are widely used in products such as hoses and seals. As part of a project that uses NBR/PVC blends for manufacturing forest fire hoses, blends of NBR/PVC with various inorganic fillers, such as Mg(OH)₂, china clay (organic modified kaolin) and nano clay (organic modified bentonite) were studied by TG-MS. No significant changes were observed to the type of the polymers’ decomposition products, compared to that of NBR/PVC blend without additives. The most remarkable change was the absence of HCl from decomposition products in the presence of the Mg(OH)₂ additive.     

Effect of nature and extent of crosslinking on swelling and mechanical behavior of styrene–butadiene rubber membranes

The influence of crosslink type and crosslink density on the swelling and mechanical behavior of styrene–butadiene rubber (SBR) membranes were studied in four aliphatic hydrocarbons. To vary the crosslink type and crosslink density, SBR was vulcanized by four different vulcanizing systems viz conventional, efficient, peroxide and a mixture of sulfur and peroxide. SBR vulcanizates having mono or disulfidic crosslinks (efficient system) exhibited the highest solvent uptake whereas those with C–C bonds (peroxide system) showed the lowest. SBR crosslinked by the mixed system showed superior mechanical properties in the unswollen, swollen and deswollen conditions. Arrhenius and thermodynamic parameters were evaluated from the diffusion data. Finally, a comparison between theoretical and experimental diffusion results was carried out.     

Effect of halloysite nanotube on microstructure,rheological and mechanical properties of dynamically vulcanized PA6/NBR thermoplastic vulcanizates

Dynamically vulcanized thermoplastic vulcanizate (TPV) nanocomposites based on polyamide-6 (PA6) and acrylonitrile butadiene rubber (NBR) reinforced by halloysite nanotubes (HNT) were prepared via a direct melt mixing process. The effects of HNT on the physical, mechanical, and rheological properties of nanocomposites were investigated. The prepared PA6/NBR/HNT nanocomposites were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning colorimeter (DSC), dynamic mechanical thermal analysis (DMTA), and rheological measurements. The morphology study of prepared nanocomposites shows that the introduction of HNT into the PA6 phase causes a decrease in the size of NBR droplets. The mechanical measurements revealed that Young’s modulus of TPV nanocomposites increased with the HNT loading up to 54%. DMTA results show that the introduction of 10 wt% of HNT into the PA6/NBR TPV leads to a 30% increase in storage modulus. The rheological measurements revealed that the storage modulus of nanocomposites has an increase of more than 200% in the presence of 7 wt% of HNT loading. Analytical stiffness modeling of Young’s modulus of the TPV nanocomposites was investigated using Hui–Shia and Wu models. Both models have some deviations from experimental results and been modified to predict Young’s modulus of the nanocomposites containing HNT with more precisions. The viscosity behavior of TPV nanocomposites was studied using a Carruea–Yasuda model and showed that the yield stress of nanocomposites increases with higher HNT loadings, indicating the formation of a nanotube network along with NBR phase network.     

The influence of nano silica particles on gamma-irradiation ageing of elastomers based on chlorosulphonated polyethylene and acrylonitrile butadiene rubber

The goal of this work was to study gamma irradiation ageing of rubber blends based on acrylonitrile butadiene rubber (NBR) and chlorosulphonated polyethylene rubber (CSM) reinforced by silica nano particles. The NBR/CSM compounds (50: 50, w/w) filled with different content of filler (0–100 phr) were crosslinked by sulfur. The vulcanization characteristics were assessed using the rheometer with an oscillating disk. The vulcanizates were prepared in a hydraulic press. The obtained materials were exposed to the different irradiation doses (100, 200, 300 and 400 kGy). The mechanical properties (hardness, modulus at 100% elongation, tensile strength and elongation at break) and swelling numbers were assessed before and after gamma irradiation ageing.     

Separation of benzene—n-heptane mixtures by pervaporation with elastomeric membranes. I. Performance of membranes

The different parameters affecting the separation characteristics by pervaporation of a benzene—n-heptane mixture on poly(butadiene—acrylonitrile) (NBR) and poly(butadiene —styrene) (SBR) membranes were investigated. A selectivity for benzene of between 2 and 8 may be obtained with pervaporation rates from 600 to 20 μm-l/hr-m² . In the ranges investigated, level of curing agent, agitation and downstream pressure factors have a negligible effect compared with membrane composition, temperature and feed composition.     

Shape memory properties of dynamically vulcanized poly(lactic acid)/nitrile butadiene rubber (PLA/NBR) thermoplastic vulcanizates: The effect of ACN content in NBR

Morphology structure and interfacial interaction are crucial factors for shape memory thermoplastic vulcanizates. In this study, shape memory thermoplastic vulcanizates based on poly(lactic acid) (PLA) and nitrile butadiene rubber (NBR) were prepared through dynamic vulcanization. The influence of acrylonitrile (ACN) content on the morphology, compatibility, shape memory property, and mechanical property was investigated. A co‐continuous structure was observed. The interfacial compatibilization between PLA and NBR phases occurred, resulting in a significantly improved interface adhesion and interfacial interaction, which was confirmed by Fourier transform infrared spectroscopy. With such a novel structure, the PLA/NBR TPVs owned an excellent shape memory property and further improved with increasing ACN content of NBR, which could be explained that the cross‐linked continuous NBR phase provided a stronger recovery driving force. In the meantime, tensile strength and elongation at break of TPVs increased with increase in ACN content. It is concluded that the preparation of dynamically vulcanized thermoplastic vulcanizate with co‐continuous structure and strong interfacial adhesion is beneficial to obtain outstanding shape memory effect.     

Microstructure and properties of styrene‐butadiene rubber based nanocomposites prepared from an aminosilane modified synthetic lamellar nanofiller

In this work, a novel nanocomposite series based on styrene‐butadiene rubber (SBR latex) and alpha‐zirconium phosphate(α‐ZrP) lamellar nanofillers is successfully prepared. The α‐ZrP lamellar filler is modified at the cation exchange capacity by γ‐aminopropyltrimethoxysilane and the filler surface modification is first discussed. A significant improvement of the mechanical properties is obtained by using the surface modified nanofillers. However, no modification of the gas barrier properties is observed. The impact of addition of bis(triethoxysilylpropyl)tetrasulfide (TESPT) as coupling agent in the system is discussed on the nanofiller dispersion state and on the filler–matrix interfacial bonding. Simultaneous use of modified nanofillers and TESPT coupling agent is found out with extraordinary reinforcing effects on both mechanical and gas barrier properties and the key factors at the origin of the improvement of these properties are identified. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1051–1059     

Characterization of electron-beam-modified surface coated clay fillers and their influence on physical properties of rubbers

A novel process of surface modification of clay filler has been developed by coating this with an acrylate monomer, trimethylol propane triacrylate (TMPTA) or a silane coupling agent, triethoxy vinyl silane (TEVS) followed by electron beam irradiation. Characterization of these surface modified fillers has been carried out by Fourier-transform infrared analysis (FTIR), electron spectroscopy for chemical analysis (ESCA), wettability by dynamic wicking method measuring the rise of a liquid through a filler-packed capillary tube and water flotation test, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). Presence of the acrylate and the silane coupling agent on the modified fillers has been confirmed from FTIR, ESCA, and EDX studies, which has also been supported by TGA studies. The contact angle measurement by dynamic wicking method suggests improvement in hydrophobicity of the treated fillers, which is supported by water flotation test especially in the case of silanized clay. However, XRD studies demonstrate that the entire modification process does not affect the bulk properties of the fillers. Finally, both unmodified and modified clay fillers have been incorporated in styrene butadiene rubber (SBR) and nitrile rubber (NBR). Rheometric and mechanical properties reveal that there is a definite improvement using these modified fillers specially in the case of silanized clay compared to the control sample, probably due to successful enhancement in interaction between the treated clay and the base polymer.