Influence of surface modification on thermal stability and flammability of cross-linked rubbers

The paper discusses the test results of thermal stability and flammability of cross-linked diene rubbers containing silica prepared “in situ” from alkoxysilane precursors. The effect of the surface modification of unfilled vulcanizates by means of aqueous solutions of halogens, boron and organo-phosphoric compounds on their flammability was also assessed. The thermal analysis has been performed in air with the use of derivatography. The flammability of vulcanizates has been determined by the method of oxygen index and in air. It has been found that the modification of the vulcanizates with tetraethoxysilane that makes it possible to form silica “in situ” considerably reduces the flammability of cross-linked rubbers. The surface modification of the vulcanizates with halide and organo-phosphoric compounds allows one to radically decrease their flammability. The boric flame-retardant agents are the most effective modifiers. The most beneficial results were obtained with the use of boric acid.     

Influence of carbon black on thermal properties and flammability of cross-linked elastomers

The paper presents the results of testing thermal properties and combustibility of butadiene-acrylonitrile rubber vulcanizates with different contents of bounded acrylonitrile: Perbunan NT 1845 and Perbunan NT 3945 from Bayer. The rubbers were cross-linked by means of dicumyl peroxide. Four types of carbon black with different specific surfaces were used as fillers. The test results were obtained with the use the derivatograph, DSC-204 of Netzsch, measurements of flammability by the method of oxygen index and in air. The results of measurements have shown that the thermal stability and flammability of the vulcanizates under investigation are affected by the activity of solid phase and the degree of surface development as well as the flexibility of polymeric chain and the degree of its unsaturation. A clear relationship has been found between the thermal properties and flammability of the cross-linked butadiene-acrylonitrile rubbers.     

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.     

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.     

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.     

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.     

Thermal stability and flammability of styrene–butadiene rubber (SBR) composites

The article presents the effect of attapulgite (ATT) and its synergic action with carbon or silica on the thermal properties and flammability of cross-linked styrene–butadiene rubber. It has been shown that ATT is active filler improving the thermal and mechanical properties of composites containing this aluminosilicate. The decreased flammability of vulcanizates containing ATT compared to that of unfilled vulcanizates results from good insulating properties of the ATT used. The considerable reduction in the flammability of composites containing ATT and carbon nanofiber or silica is connected, first of all, with the formation of a homogeneous boundary layer.     

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 butadiene-acrylonitrile rubbers

The paper discusses the test results of butadiene-acrylonitrile rubber, Perbunan NT 1845 and Perbunan NT 3945, flammability and properties that characterise these elastomers under fire conditions. The flammability was tested by means of oxygen index and thermovision methods. The thorough testing of flammability performed by means of a cone calorimeter made it possible to assess the behaviour of these polymers under fire conditions. The following properties of the tested copolymers were taken into account in this assessment: ignitability, heat release during combustion, smoke-forming capability and toxicity of the gaseous products of thermal decomposition and combustion. It has been found that the increase in the acrylonitrile unit content in the copolymer decreases its flammability and the relative toxic fire hazard, but clearly increases the smoke-forming capability and so the specific extinction area.The interpretation of test results of the elastomers under investigation takes into consideration their thermal stability assessed on the basis of differential thermal analysis, thermogravimetry and other complementary methods.This revised version was published online in November 2005 with corrections to the Cover Date.     

Effect of the top layer modification of polymers on their thermostability and flammability

Thermal properties, ageing resistance and flammability of peroxide vulcanizates of butadiene-acrylonitrile rubber Perbunan NT 1845 (NBR) of Bayer, modified in bulk and on a surface with synthesized hybrid functional poly(methylsiloxanes) were investigated. The derivatographic, DSC, oxygen index and FTIR methods were applied. It was stated that addition of poly(methylsiloxanes) caused distinct increase of ageing resistance and of NBR vulcanizates and decrease of their thermal decomposition rate and flammability, providing self-extinguishing samples. The mechanism of addition reactions of Si–H bond to multiple bonds of NBR has been proposed.     

Thermal properties and combustibility of cross-linked XNBR/CSM blends

The article describes the measurement results of the thermal properties of cross-linked blends of carboxylated butadiene-acrylonitrile rubber (XNBR, Krynac X.7.50) and chlorosulfonated polyethylene (CSM, Hypalon 48) under inert gas (DSC, TG) and in air (derivatography). The blends were cross linked at a temperature of 150 °C by means of MgO in the presence of stearic acid. The thermal curves were interpreted from the point of view of phase transitions and chemical reactions of high-molecular components. It has been found that the polymers under investigation show a good compatibility resulting from the presence of both inter-polymeric covalent bonds and inter-polymeric ionic bridges containing magnesium ions that fulfill the role of chemical compatibilizer. The study has shown that XNBR/CSM blends belong to a group of polymeric materials that are self-extinguished in air. Their flammability, determined by OI and the combustion time in air, clearly depends on the cross-linking degree associated with the quantity of MgO incorporated into the blend of elastomers.     

Effect of mineral fillers on thermal properties and flammability ofcis-1,4-polyisoprene vulcanizates

The effect of mineral fillers such as Ultrasil VN-3, Ze?O?Sil P-45, Aerosil 200, Frantex 8, Kaolin and precipitated calcium carbonate on the thermal properties sulphur vulcanizates ofcis-1,4-polyisoprene were studied by means of thermal analysis. It was found that the addition of a mineral filler did not change the nature of the thermal processes in isoprene vulcanizates essentially, but it distinctly affected the positions of the peaks recorded in the DTA curves. The mineral fillers affected the temperatures and rates of degradation and destruction of polyisoprene cross-linked with sulphur. The presence of a mineral filler brought about a decrease in the flammability ofcis-1,4-polyisoprene sulphur vulcanizates.     

Synergistic effect of 4,4′‐bis(maleimido) diphenylmethane and zinc oxide on the vulcanization behavior and thermo‐mechanical properties of chlorinated isobutylene–isoprene rubber

It is well known that the vulcanization of chlorinated isobutylene–isoprene rubber (CIIR) with ZnO alone is very slow and the resulting vulcanizate shows low crosslinking density as well as poor mechanical and thermal properties. For these problems to be addressed, 4,4′‐bis(maleimido) diphenylmethane (BMDM) has been applied along with ZnO to cure CIIR. The curing behavior was investigated using oscillating disk rheometer and differential scanning calorimetry analysis. The crosslinking densities, mechanical, dynamic mechanical, and thermal properties of the vulcanizates were also evaluated as a function of BMDM content. From the rheometer and differential scanning calorimetry analysis, it has been confirmed that the rate of curing, as well as the extent of curing between CIIR and ZnO, has remarkably increased in the presence of BMDM. The Diels–Alder reaction between the in situ formed conjugated diene butyl from CIIR/ZnO with the maleic moieties of BMDM has been identified as a primary reason for the higher rate and state of cure. The crosslinking densities of the vulcanizate CIIR/ZnO have significantly increased with increase in the content of BMDM. As a result, the compression set of the vulcanizate was remarkably decreased at elevated temperature. Moreover, the vulcanizates contain BMDM that has exhibited high thermal degradation temperature and good retention of the mechanical properties even after 7 days of thermal ageing. Copyright © 2016 John Wiley & Sons, Ltd.     

The thermal properties and the flammability of pigmented elastomeric materials

This paper presents thermal properties of organic pigments such as zinc phthalocyanine and chloroaluminum phthalocyanine that were synthesized according to the literature data. These pigments were characterized by means of elementary analysis and measurements of particle size. They were then incorporated into butadiene-styrene rubber and butadiene-acrylonitrile rubber. The elastomeric mixtures were cross-linked by two methods: using organic peroxide or sulfur. The effect of phthalocyanines on the thermal properties, flammability, and fire hazard of the pigmented polymeric materials obtained as well as on their mechanical properties and cross-linking degree was studied. It has been shown that the phthalocyanine pigments not only impart appropriate esthetic values to the final goods but also increase their thermal stability and considerably reduce the flammability and fire hazard of elastomers and even make possible materials that are self-extinguishing under air atmosphere. These pigments also have a beneficial influence on the degree of cross-linking of the elastomers investigated and their mechanical properties.     

Thermal properties and combustibility of cross-linked XNBR/CSM blends

The article describes the measurements results of the thermal properties of cross-linked blends of butadiene?Cacrylonitrile rubber (XNBR, Krynac X.7.50) and chlorosulfonated polyethylene containing different quantity of combined chlorine (CSM24??Hypalon 48, CSM29??Hypalon 20, CSM35??Hypalon 40, and CSM43??Hypalon 30) under inert gas (DSC) and in air (derivatography). The blends were non-conventionally cross linked at a temperature of 150?°C by means of MgO in the presence of stearic acid. The thermal curves obtained were interpreted from the point of view of phase transitions and chemical reactions of the macromolecular components used. It has been found that the elastomers investigated show a good compatibility brought about by the formation of both interpolymeric covalent bonds and interpolymeric and intrapolymeric ionic bridges, which play the role of a chemical compatibilizer. The results of the examinations performed show that the non-conventional cross-linked XNBR/CSM blends prove very good mechanical properties and are self-extinguished in air. Their flammability defined with the value of OI and combustion time in air clearly depends on the type of CSM.     

Effect of accelerated thermal ageing on the thermal behaviour of the recently made parchments

To reveal the fire injuring of parchment, the changes in the thermal behaviour of some goat parchments, obtained from skins originating from different animals, as a result of thermal aging were determined by thermal analysis methods (DSC; simultaneous TG/DTG, DSC; micro hot table (MHT)). Thermal aging of parchments was revealed to bring about the decrease in shrinkage temperature, absolute value of enthalpy of denaturation in water and some changes in non-isothermal parameters characteristic for dehydration process in static air atmosphere. The results obtained by DSC analysis performed in N₂ and O₂ flows as well as those obtained by simultaneous TG/DTG, DSC analyses have shown that both softening (melting) process parameters and parameters of thermo-oxidative processes have not been changed by thermal ageing. The results obtained by thermal analysis methods were correlated with those obtained by microscopic investigation of parchment samples immersed in water and scanning electron microscopy (SEM). The application of these microscopic techniques has revealed the morphology changes in the investigated parchments as a result of thermal degradation.     

Thermal properties of swollen butadiene-acrylonitrile rubber vulcanizates

The present paper discusses the results of assessing thermal properties of nitrile rubber, Perbunan NT 3945 and its peroxide vulcanizates, before and after their swelling in solvents such as benzene, toluene and dimethylformamide. The measurements were carried out by means of differential scanning calorimetry (DSC) and thermogravimetry (TG) under nitrogen. It has been found that a slight rise in the glass transition temperature due to the elastomer cross-linking is clearly revealed under the influence of its vulcanizates swelling in solvents whose solubility parameters considerably differ from the solubility parameters of the polymer. The thermal curves of swollen samples reveal processes resulting from polymer-solvent interactions and thermodesolvation processes, which accompany the initial stage of solvent evaporation.The authors would like to express their thanks to the Bayer company for providing free of charge samples of Perbunan NT 1845 and Perbunan 3945 which were used in this study.     

Thermal Properties of Cis-1,4-Poly(butadiene)

Thermal properties of cis-1,4-poly(butadiene), Europrene cis, were investigated by means of thermal analysis and complementary methods. Thermal analysis of polymer was carried out both in air and inert atmosphere with a derivatgraph, DSC and internal TG-FTIR coupling system as well as internal TG, DTA-MS coupling system. It was found that investigations in air atmosphere the method of the sample preparation ofcis-1,4-poly(butadiene) influences the results of thermal analysis, which is connected with the rate oxygen diffusion into the reaction zone. Taking into consideration both the method of the sample preparing and atmosphere of thermal studies, the values of activation energy of destruction of cis-1,4-poly(butadiene) were determined. Using TG-FTIR and TG-MS methods, some products of thermal destruction of elastomer were determined.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal stability and combustibility of rubbers and sealing plates

The present paper describes the test results concerning the thermal properties and flammability of the selected sealing plates and rubbers that may become components of plates. The thermal analysis methods (DTA, DSC, TG, and DTG) and flammability methods (OI, rate of burning in air, and ignition temperature) were used in this study. The thermal analysis of plates was also performed under isothermal conditions. It was stated that investigated sealing plates belong to the group of flame-retardant materials and type of rubber included in plate influences its thermal stability and combustibility.     

Thermal properties of fibres from a new polymer of the polyimideamide group

The paper presents the thermal properties of fibres made of a modified polyimideamide. The effects of as-spun draw ratio and deformation during the fibre drawing stage on the structure, thermal properties, moisture absorption and tenacity of the obtained fibres have been determined. Based on the findings obtained by the DTA and DSC methods, it has been found that the modification of the polymer under investigation causes its glass transition temperature to decrease through the increase of molecular mobility. At the same time, the heat-resistant fibres with the amorphous oriented structure are characterized by a tenacity of 16 cN/tex, good absorption properties and increased porosity. The thermal stability indices of the examined fibres have been determined on the basis of thermogravimetric curves obtained both under air and inert gas. This revised version was published online in July 2006 with corrections to the Cover Date.