Thermal stability and combustibility of butyl and halogenated butyl rubbers

The effects of flame retardants such as hydrated aluminium oxide, antimony trioxide and chloroparaffin on the thermal properties and flammability of sulphur vulcanizates of butyl and halogenated butyl elastomers were studied. The thermoanalytical curves of the elastomers were interpreted. Greater tendencies to thermal degradation were observed for halogenated butyl elastomers than for the original butyl rubber elastomer. This was confirmed by elastomer combustibility studies. The use of these flame retardants allowed the formation of self-extinguishing vulcanizates of the investigated elastomers.     

Mineral oxides and layered minerals in combination with itaconic acid as coagents for peroxide crosslinking of hydrogenated acrylonitrile-butadiene elastomer

The aim of this work was to study the activity of nanosized calcium and magnesium oxides and layered minerals (boehmite, hydrotalcite) as coagents in the crosslinking of hydrogenated acrylonitrile-butadiene elastomer (HNBR) with dicumyl peroxide. The surfaces of the mineral oxides and layered minerals were modified with unsaturated acid (itaconic acid) to ensure their activity during the crosslinking process. The efficiency of modification process was estimated, based on thermogravimetric analysis and zeta potential measurements of obtained coagents. In this article, we discuss the effect of coagents on the crosslinking density and mechanical properties of vulcanisates. Application of nanosized mineral oxides and layered minerals together with itaconic acid decreased the optimal vulcanisation time of rubber compounds and improved the crosslinks density as well as the tensile strength of the vulcanisates due to formation of additional ionic crosslinks in the elastomer network. It is important from technological reasons.     

Interfaces in Composites. Reinforcement of Elastomers by Carbon Black

Basic features of carbon black-aggregation of particles into structure, particle size and morphology, and surface activity-are reviewed. Carbon black reinforcement of vulcanizates is first examined in the example of tearing, and the influence of hysteresis is considered. The dynamic properties of vulcanizates containing two major types of reinforcing carbon black are compared.

While particle size gives the best correlation with tensile strength of vulcanizates, surface activity is shown to be the key to reinforcement. The role of these properties of carbon black in dissipating rupture energy is discussed.

The relation between work to tensile break and hysteresis to break in gum rubbers can be applied to black-reinforced vulcanizates by use of a strain amplification factor. The complication introduced by stress-softening is explained in terms of localized stress relaxation. Abrasion reinforcement can also be explained in terms of hysteresis.

The Flory-Rehner relationship of modulus of elasticity of swollen vulcanizates to physically-effective cross-linking applies to unswollen vulcanizates only after prestressing. Black-reinforced vulcanizates involve application of the strain amplification factor.

The concept of mobile linkages to rubber chains at the surface of black particles is related to the influence of strain magnification and strain rate magnification in the reinforcing mechanism. These linkages result in formation of “shell” rubber adjacent to carbon black particles. The slippage of rubber chains relative to carbon black aggregates allows stress-sharing by highly-stressed chains. Bound rubber results from reaction of elastomer free radicals generated during mastication with carbon black.

There is a relation between bound rubber and reinforcement which is fully developed only after vulcanization. Formation of bound rubber results from the surface activity of carbon black rather than its structure. Its contribution to reinforcement of the vulcanizate may be as important as cross-linking.     

Adsorption of curatives and activity of silica toward elastomers

To characterize an activity of silica toward elastomers usually the parameters of the filler structure and a possibility of its interactions with macromolecules of a matrix are taken into consideration [1,2,3]. As a rule, low molecular weight substances of different polarity are dissolved in a rubber mix (e.g. accelerators, activators, crosslinking substances, etc). They undergo adsorption on the surface of active fillers what exerts an effect on a structure of a network formed and influences mechanical properties of vulcanizates at the same time.     

Mechanical properties of carbon black filled hydrogenated acrylonitrile butadiene rubber for packer compounds

Hydrogenated acrylonitrile butadiene rubber (HNBR) was chosen to develop peroxide cured and carbon black N220 (CB) reinforced high modulus vulcanizates with possible applications in packers for oil exploration. HNBR vulcanizates are investigated by Rubber Processing Analyzer RPA 2000 and stress-strain tests conducted both in elongation and compression mode. All the mechanicals properties were tested both at room temperature (RT) and 150 °C in order to reflect application of packers. The results show that the modulus of CB filled HNBR vulcanizates increases with the increase of CB loadings in shear, tensile and compression mode. The physical interactions resulting from CB reinforcements show a stronger temperature-dependence than chemical crosslinks formed by curing agent. So the addition of reinforcing carbon black will have limited benefit for producing packer compounds with high enough modulus at high temperature, but more amount of curing agent will contribute to a stable high enough modulus. It is testified the filler-filler interaction is more temperature dependent than filler-rubber interaction and more chemical crosslinks increase the filler-rubber bonding and slightly decrease the filler-filler interaction, which is confirmed by the reinforcement factors. Compression tests show a strong dependence on the geometry of the samples and the compressive Payne Effect is examined by the multiple compression cycles. It gets stronger as the CB loading is increased.     

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.     

Adhesion of carbon black to elastomers

Measurements are described of the strength of adhesion of lightly-crosslinked elastomer sheets, either with clean contacting surfaces or with one or both surfaces coated with layers of carbon black particles. The strength of self-adhesion showed large differences that correlated with the glass temperature, thus indicating that a major factor in self-adhesion is viscous energy dissipation. A lesser but still marked effect of the elastic modulus was observed, the more highly crosslinked sheets showing lower self-adhesion. When layers of carbon black particles were interposed, the measured strength of adhesion was increased in all cases, becoming about twice as high for elastomers with low self-adhesion, and showing a somewhat smaller increase for elastomers with high self-adhesion. After correcting for incomplete coverage of the surface, the actual strength of adhesion to carbon black is inferred to be about four times higher. Similar levels of bonding to carbon black were found for several hydrocarbon elastomers, although the increase in adhesion was most evident for those with low levels of self-adhesion - polybutadiene and natural rubber in the present study. Thus, no specific effect of elastomer surface chemistry was found. Instead, adhesion to carbon black appeared to be governed by simple wetting considerations.     

Effect of carbon nanofibers on mechanical and electrical behaviors of acrylonitrile‐butadiene rubber composites

Recently, carbon nanofibers have become an innovative reinforcing filler that has drawn increased attention from researchers. In this work, the reinforcement of acrylonitrile butadiene rubber (NBR) with carbon nanofibers (CNFs) was studied to determine the potential of carbon nanofibers as reinforcing filler in rubber technology. Furthermore, the performance of NBR compounds filled with carbon nanofibers was compared with the composites containing carbon black characterized by spherical particle type. Filler dispersion in elastomer matrix plays an essential role in polymer reinforcement, so we also analyzed the influence of dispersing agents on the performance of NBR composites. We applied several types of dispersing agents: anionic, cationic, nonionic, and ionic liquids. The fillers were characterized by dibutylphtalate absorption analysis, aggregate size, and rheological properties of filler suspensions. The vulcanization kinetics of rubber compounds, crosslink density, mechanical properties, hysteresis, and conductive properties of vulcanizates were also investigated. Moreover, scanning electron microscopy images were used to determine the filler dispersion in the elastomer matrix. The incorporation of the carbon nanofibers has a superior influence on the tensile strength of NBR compared with the samples containing carbon black. It was observed that addition of studied dispersing agents affected the performance of NBR/CNF and NBR/carbon black materials. Especially, the application of nonylphenyl poly(ethylene glycol) ether and 1‐butyl‐3‐methylimidazolium tetrafluoroborate contributed to enhanced mechanical properties and electrical conductivity of NBR/CNF composites.     

Synthesis of silica in elastomer's matrix

We tried to synthesise silica's fillers in polar and nonpolar elastomers. Di-, tri- and tetraalkoxysilanes were used as a precursor of silica. Such functionality allowed us to obtain a filler with different ratio of crosslinking. We could expect some interactions between elastomer and silanes, which contained additional functional groups. We investigated vulcanizates by using the following methods: crosslink density in toluene and 10% solution of ethylenediamine in toluene, mechanical properties, IR microscopy, DMA. It appeared that alkoxysilanes influenced advantageously on elastomers and properties.     

Swelling behavior and mechanical properties of endlinked poly (dimethylsiloxane) networks and randomly crosslinked polyisoprene networks

Measurements of the equilibrium degree of swelling and of the equilibrium modulus were performed on poly(dimethylsiloxane) networks (PDMS) and on polyisoprene vulcanizates. The results support the concept that topological interactions between network chains, e.g. entanglements or the like, have a large influence on the rubber elastic behavior, at least within a certain range of network densities.PDMS networks having network chains of different lengths and varying functionlities of the crosslinks were prepared in bulk by endlinking fractionated ,-divinyl PDMS via multifunctional hydrogen-siloxanes (f=3 to 22). Natural rubber (NR) and synthetic liquid polyisoprene (IR) were cured in bulk with various amounts of dicumyl peroxide to give randomly crosslinked samples.The experimentally determined moduli and degrees of swelling were compared with theoretical predictions based on the phantom network theory and affine network theory, taking into account only chemical crosslinks. The observed discrepancies can be traced back to a contribution of topological interactions (trapped entanglements) to the total effective network density. The modulus and swelling data are consistent, thus ruling out non-equilibrium effects.     

Thermal characterization of the effect of fillers and ionic liquids on the vulcanization and properties of acrylonitrile–butadiene elastomer

Different thermal analysis techniques were used to study the effect of fillers and ionic liquids (ILs) on the vulcanization process, thermal and dynamic mechanical properties of acrylonitrile–butadiene elastomer (NBR). The products of the studies were composites of NBR filled with hydrotalcite, nanosized silica or carbon black. ILs such as 1-butyl-1-methylpyrrolidinium (BMpyrrolBF₄), 1-butyl-4-methylpyridinium (BMpyrBF₄) or 1-butyl-1-methylpiperidinium (BMpipBF₄) tetrafluoroborates were applied to improve the dispersion degree of the curatives and filler particles in the elastomer and to increase the efficiency of vulcanization. The differential scanning calorimetry results indicated that ILs reduced the vulcanization temperature of NBR compounds and increased the homogeneity of cross-link distribution in the elastomer network. NBRs filled with carbon black or silica exhibited similar thermal stabilities, whereas hydrotalcite reduced the temperature of thermal decomposition. The lowest mechanical loss factors were determined for vulcanizates filled with nanosized silica.

     

Measurements of freezing‐point depression to evaluate rubber network structure. Crosslinking of natural rubber with dicumyl peroxide

An experimental approach based on the freezing‐point depression of a solvent in a swollen gel has been developed to characterize the structure of rubber networks. This property depends on the conditions required for the formation of crystalline nuclei, which are limited by the elastomer network restrictions. Information about the functionality, spatial distribution, and number of crosslinks can be obtained by the use of this easy and ready experimental method. Application of the tube model of rubber elasticity in the uniaxial stress–strain experiments of natural rubber samples vulcanized with dicumyl peroxide yields the characteristic parameters of the rubber networks, which are in concordance with the network structures predicted by the freezing point method. Finally influence of vulcanization conditions in network structure and its relationship with the mechanical properties was evaluated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 544–556, 2007     

Sulphur and peroxide vulcanisation of rubber compounds — overview

Vulcanisation is a process of transforming a plastic rubber compound into a highly elastic product by forming a three-dimensional cross-linked network structure in the rubber matrix. Many systems have been developed to vulcanise rubber compounds, among which sulphur and peroxide curing systems remain the most desirable. The application of sulphur systems leads to the forming of sulphidic cross-links between elastomer chains, while carbon–carbon bonds are formed in peroxidecuring. Both vulcanisation systems provide certain benefits to the cross-linked rubber articles, but also some disadvantages. The present work seeks to provide an overview on both vulcanisation systems; their composition, possibilities of their application, reaction mechanisms, structure of the cross-links formed and the main feature of the final cross-linked materials — vulcanisates.     

Natural rubber biocomposites containing corn,barley and wheat straw

The development of high-performance materials made from available and cheap natural resources is increasing worldwide. A new solution – composites of natural rubber, containing barley, corn and wheat straw as biofillers, was reported and researched. The latest developments and trend's exams of the elastomers filled with cereal straw represent a scientific and technological innovation. The use of straw as a filler for elastomer composites bradens the range of functional properties and reduces the costs of production. The biocomposites are more ecofriendly and give the opportunity to increase the possibility of straw management which is a problematic agricultural waste. The rubber mixtures containing lignocellulosic materials demonstrate a favorable characteristic kinetics of crosslinking. The addition of filler, in an appropriate amount, modified natural rubber vulcanizates, improving mechanical and barrier properties of composites and the ability to damp under the influence of compression stress. Dynamic mechanical analysis showed change in the G′ values of the vulcanizates upon addition of straw. That indicates the presence of strongly developed network of fillers into polymer matrix which ensure of reinforcing character. The negative impact of natural fillers on resistance to thermo-oxidative aging was not observed.     

NMR imaging of elastomeric polymers

We have used NMR imaging to determine the dispersion in crosslinking density in complex elastomers both along the chains as well as spatially. Our work has established that the ordinary industrial accelerator systems generate a broad distribution of crosslink densities in rubber articles due to the poor mixing of the solid accelerator/sulfur recipe in the raw rubber. This high inhomogeneity in elastomeric network has an adverse effect on the properties of the elastomer system. In particular, the variation in crosslink density leads to substantial differences in the coefficients of thermal expansion and high internal stresses in the rubber article.     

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.     

A theory of green strength in polyisoprene

It is shown that, at ?25°C, natural rubber (NR) crystallizes more readily than synthetic polyisoprene (IR), the long induction period for nucleation in IR in particular being dependent on the carbon black loading. Both elastomers form bound rubber with carbon black but not with nonreinforcing fillers such as CaCO₃ and glass powder. At room temperature, in the presence of carbon black, NR has good green strength but not IR, while neither rubber has good green strength with nonreinforcing fillers. However, at 0°C CaCO₃ filled NR too has good green strength. A theory is proposed to account for the good green strenth characteristics found with certain compounds. In the model rubber molecules, already bound to the carbon black surface, are linked together, at low strains, via stress-induced crystal lamellae, giving a three-dimensional network in the compound. Such crystal lamellae are known to grow at right angles to the direction of strain from row nuclei formed at low strains. The coherence provided by the network permits the formation, at higher strains, of stress-induced crystals in which polymer chains are now aligned in the direction of strain. This leads to an upturn in the stress–strain curve. In the absence of either bound rubber or of crystal lamellae, a long range network structure cannot form and extension of the sample continues at constant stress.     

Raman investigation of thermoplastic vulcanizates based on hydrogenated natural rubber/polypropylene blends

Raman spectroscopy including mapping technique appears as a powerful technique for the characterization of polymer blends like thermoplastic elastomers (TPEs) and thermoplastic vulcanizates (TPVs). The Raman spectra of polymers blends such as natural rubber/polypropylene (NR/PP) and 65% hydrogenated natural rubber/polypropylene (65%HNR/PP) were identified and the phase distribution was determined. The study was driven for the same type of blends in TPEs state and TPVs state obtained after to 2 different processes, either peroxide cure or sulfur cure. The morphology of TPEs and TPVs obtained by Raman spectroscopy were compared and confirmed using scanning electronic microscopy.Raman mapping shows that the phase morphology of NR/PP, 65%HNR/PP, were characterized as continuous rubber phase morphology of the thermoplastic elastomers (TPEs) and a fine dispersion of cross-linked rubber phase in a continuous matrix of the thermoplastic vulcanizates (TPVs). Raman spectroscopy is demonstrated to be a reference to determine the content ratio of each component in the TPVs. Moreover, Raman mapping could be used to calculate the phase size of cross-linked rubber phase dispersed in the thermoplastic vulcanizates (TPVs).     

Stress relaxation of natural rubber during irradiation

The site of chain scission and crosslinking in vulcanized natural rubber irradiated with 4 MeV electrons has been determined by analysis of stress relaxation data. Sulfur and peroxide vulcanizates of different crosslink densities were prepared and the crosslink densities determined from stress-strain measurements. Stress relaxation was measured during irradiation using modified commercial relaxometers. The specimens were maintained in an atmosphere of nitrogen to minimize oxidative side effects. Scission is deduced to take place in the vicinity of crosslinks, since the rate of continuous stress relaxation is independent of crosslink density. Scission may be associated both with crosslinks initially present and with those subsequently introduced by irradiation. Crosslinking by radiation is largely a random process. However, there is a crosslinking reaction dependent to a slight extent on crosslink density as well as a small contribution from random scission reactions. G values for the random reactions are given.     

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.