Vulcanization Of Elastomers Research Articles

High Temperature Vulcanization of Elastomers

Abstract Vulcanization is a process which decreases the plastic properties of rubber while maintaining or improving the elastic properties. The term vulcanization has been applied in the past mainly to the reaction of rubber with sulfur, but now is generally used for the process which results in changes in properties, by sulfur or some other agent. There are four principal changes brought about by vulcanization: (1) rubber is changed from essentially a plastic to a non-plastic material; (2) rubber is changed from a material soluble in a number of solvents to one which is insoluble; (3) rubber is changed to a material with greatly improved physical properties; (4) these properties of vulcanized rubber are maintained over a much wider range of temperature than those of unvulcanized rubber. What is meant by high vulcanizing temperature? There is no unique answer. About 160°C can be taken conveniently as the lower limit; this temperature has been suggested as the highest suitable for some normally compounded sulfur curing rubbers. The upper limit may be 220°C, above which the polymer may begin to degrade. The range in practice extends up to about 250°C in fluid beds and salt baths. Practical vulcanization processes apply heat to the outside of the article being cured and rely on the conduction of heat to the inside. Since no drastic change can be made in the thermal conductivity of practical rubber compounds by compounding modifications, higher temperature is a common method of achieving faster vulcanization. Higher curing temperatures are used in the newer curing or molding processes such as injection molding, the liquid curing medium (LCM) process, and microwave curing.

Application of TMA for Rapid Evaluation of Low-Temperature Properties of Elastomer Vulcanizates

Abstract Static thermomechanical analysis has been investigated as a method for determining the low-temperature properties of vulcanizates. Dimensional changes of a sample in free expansion, indentation, or tension are monitored as the sample is heated at a known and reproducible rate. The first derivative of the dimensional change is simultaneously recorded. TMA/DTMA data obtained in free expansion gives the linear thermal expansion coefficient at any temperature during the experiment. The glass transition is observed as a change in slope as in dilatometric determinations. In the indentation mode, the thermogram is the result of competition between thermal expansion and indentation. For tension measurements, the thermogram records the additive sum of thermal expansion and tensional strain development. For indentation and tension, the glass transition is obtained by a standard extrapolation method. A maximum in the DTMA thermogram is also observed which represents the maximum rate of change as the sample is heated through the glass transition range. The temperature of this maximum, Tgd, is characteristic of a vulcanizate. Variation in scan rate between 2 and 20°C/min has little effect on Tgo and no effect on Tgd. At 50°C/min, thermal gradient effects predominate. For a wide range of vulcanizates in tension or indentation, Tgo or Tgd versus the Gehman rigidity modulus gives a linear relationship. Exact temperature agreement is not observed because of differences in the experimental techniques. In blends, several Tgd values are observed. Plasticizer effects can either be observed by a shift in the Tgo or by a change in the thermogram profile, the extent of indentation and temperature range over which it occurs. The extent of indentation correlates with vulcanizate hardness as expected. The indentation of a rubber sample by a flat probe has been treated mathematically in the literature, and the determination of Young's modulus by TMA/DTMA is now being investigated. In conclusion, the ease of sample preparation and the rapidity of TMA/DTMA measurements offers a quick approach to assessing the low-temperature properties of vulcanizates. At 20°C/min scan rate, runs can be completed in as little as four minutes (80°C total scan) if the sample has a single transition.

3347. Nitrosamines in food surveyed: Gough, T. A., Webb, K. S. & Coleman, R. F. (1978). Estimate of the volatile nitrosamine content of UK food. Nature, Lond.272, 161.

Sixteen types of children's pacifiers and baby-bottle nipples, bought in shops in Israel but produced both there and elsewhere in the world, were analyzed for their contents of N-nitrosamines, which have been shown to be potent carcinogens in animals, and of nitrosatable amines. Two methods were used: one, originating in the United States, involved dichloromethane extraction of total volatile N-nitrosamines from the nipples and pacifiers, and the other, from the Federal Republic of Germany, consisted of analysis of N-nitrosamines and their amine precursors that migrated into artificial saliva. N-Nitrosodibutylamine (NDBA), N-nitrosodiethylamine (NDEA), N-nitrosodimethylamine (NDMA), N-nitrosopiperidine (NPIP), and N-nitrosopyrrolidine (NPYR) were detected by the first method, at individual levels as high as 369 ppb. Using the second method, NDBA, NDEA, NDMA, and N-nitrosomorpholine (NMOR) were detected at concentrations up to 41 ppb, in addition to the three nitrosatable amines dibutylamine, diethylamine, and dimethylamine. Upon nitrosation in the artificial saliva, these amines produced not only the related N-nitrosamines but also relatively high levels of the corresponding N-nitramines (N-nitrodibutylamine, N-nitrodiethylamine, and N-nitrodimethylamine), probably formed by oxidation of the N-nitrosamines by peroxides used for vulcanization of elastomers. Thus, if N-nitramines are not measured in addition to N-nitrosamines after nitrosation, the second method may underestimate the quantities of nitrosatable amines present in artificial saliva extracts. Whether N-nitramines, some of which have been shown to be both mutagenic and carcinogenic, also occur in the saliva of babies exposed to these products remains to be confirmed. Of the samples tested, 50% failed to meet both the U.S. and the FRG regulations. A larger percentage, 60%, would not conform to the new standard suggested in the United States, and more than 80% failed to comply with the even stricter Dutch standard.

3351. Gut reaction to diquat: Crabtree, H. C., Lock, E.A. & Rose, M. S. (1977). Effects of diquat on the gastrointestinal tract of rats. Toxic. appl. Pharmac.41, 585.

Sixteen types of children's pacifiers and baby-bottle nipples, bought in shops in Israel but produced both there and elsewhere in the world, were analyzed for their contents of N-nitrosamines, which have been shown to be potent carcinogens in animals, and of nitrosatable amines. Two methods were used: one, originating in the United States, involved dichloromethane extraction of total volatile N-nitrosamines from the nipples and pacifiers, and the other, from the Federal Republic of Germany, consisted of analysis of N-nitrosamines and their amine precursors that migrated into artificial saliva. N-Nitrosodibutylamine (NDBA), N-nitrosodiethylamine (NDEA), N-nitrosodimethylamine (NDMA), N-nitrosopiperidine (NPIP), and N-nitrosopyrrolidine (NPYR) were detected by the first method, at individual levels as high as 369 ppb. Using the second method, NDBA, NDEA, NDMA, and N-nitrosomorpholine (NMOR) were detected at concentrations up to 41 ppb, in addition to the three nitrosatable amines dibutylamine, diethylamine, and dimethylamine. Upon nitrosation in the artificial saliva, these amines produced not only the related N-nitrosamines but also relatively high levels of the corresponding N-nitramines (N-nitrodibutylamine, N-nitrodiethylamine, and N-nitrodimethylamine), probably formed by oxidation of the N-nitrosamines by peroxides used for vulcanization of elastomers. Thus, if N-nitramines are not measured in addition to N-nitrosamines after nitrosation, the second method may underestimate the quantities of nitrosatable amines present in artificial saliva extracts. Whether N-nitramines, some of which have been shown to be both mutagenic and carcinogenic, also occur in the saliva of babies exposed to these products remains to be confirmed. Of the samples tested, 50% failed to meet both the U.S. and the FRG regulations. A larger percentage, 60%, would not conform to the new standard suggested in the United States, and more than 80% failed to comply with the even stricter Dutch standard.

Application of TMA for rapid evaluation of low-temperature properties of elastomer vulcanizates

Many elastomeric products are required to function at low temperatures and although numerous ASTM Standard procedures have been developed to evaluate low-temperature properties of vulcanizates, none is suitable for routine rapid batch-to-batch testing. Expansion, identation and tension TMA/DTMA have been used to establish low-temperature characteristics of a variety of elastomer vulcanizates (polyacrylates, neoprenes, nitriles and BR/SBR/NR blends) and it is shown that these techniques offer a rapid approach to testing for quality control. The lowest temperature at which adequate elastomeric properties can be monitored is determined by the glass transition of the elastomer; however, the rate of change of properties with temperature (e.g. increase in modulus with decreasing temperature) is significantly affected by type and amount of plasticizer (extender, softener, etc.). TMA and DTMA results are in good agreement with Gehmen rigidity modulus determinations. TMA results can be obtained in about ten minutes.

The structure of a single steric network produced by heterogeneous vulcanization

The general scheme by which a single steric network forms during the heterogeneous vulcanization of elastomers, using unsaturated compounds, has been evaluated. An oriented polymer layer is assumed to form at first at the interface with the dispersed particles of the curing agent, and the adsorbed macromolecules position themselves as folded structures on the surface. The crosslinking takes place as a result of chemical reaction of the curing agent with some of the loops of the adsorbed macromolecules. A single steric network will form when the chain units of a single folded macromolecule react with various particles of the curing agent. In addition to the heterogeneous network there is also some chemical union between chains due to reactions of the dissolved peroxide present.

Thermoanalytical Methods in Vulcanizate Analysis I. Differential Scanning Calorimetry and the Heat of Vulcanization

Abstract Our objective has been to demonstrate that DSC is a convenient and rapid technique for the study of elastomer vulcanization characteristics. Although we have been concerned only with NR and NR-BR blends, the observation of exothermicity in sulfur vulcanization is quite general. Similar observations on sulfur vulcanization of IIR, SBR, EPDM, CSM, and NBR rubbers have been made in our laboratory. In non-sulfur vulcanization systems, we have found the diurethane cure of natural rubber to be exothermic and amenable to DSC study. As reported by Bruce et al., the magnesium oxide cure of chloroprenes is exothermic, but magnesium oxide-diamine vulcanization of fluoroelastomers is characterized by very low exothermicity. Future studies of the effect of various additives on soft rubber cure could make a significant contribution to our understanding of the complex cure mechanism. Successful kinetic analysis of DSC scans is perhaps the major hurdle to be overcome before the DSC technique can be meaningfully applied to such problems.

High temperature vulcanization of elastomers: 3. Network structure of efficiently vulcanized natural rubber mixes

The effect of vulcanization temperature (140–200°C) and time on the structures of pure gum natural rubber vulcanizates with two different N-cyclohexyl-2-benzothiazylsulphenamide (CBS): sulphur ratios (A, 3·5:1·5; B, 6·0:0·4 CBS/S) has been determined. Analyses of vulcanizates were carried out as reported in Part 2. Results show that both mixes are efficient in crosslinking, resulting in mainly monosulphidic crosslinks and relatively few modifications of the rubber chains. Raising the cure temperature from 140°C reduces the density of chemical crosslinks, particularly those of monosulphidic crosslinks, obtainable in the vulcanizates. This decrease in crosslink density has been shown to be irreversible with respect to cure temperature. The formation of intramolecular sulphidic groups and zinc sulphide increases with rising cure temperature, but this increase is small compared with that reported for the conventional CBS-accelerated system. The main difference between mixes A and B is that mix A yields a higher level of crosslinks and a major proportion of cyclic sulphides as main-chain modification. Negligible chain scission occurs during vulcanization at 140–200°C. These network results are interpreted mechanistically, and essential network features for obtaining good physical properties in high temperature vulcanizates are deduced.

Raman Spectral Studies of 2-Mercaptobenzothiazole Accelerator Systems

Abstract A mechanism for the formation of the rubber-bound intermediate in the vulcanization of elastomers has been proposed. The active sulfurating agent is a polysulfide. Laser Raman spectroscopy has been used to provide significant evidence for this mechanism in the presence of cis-1,4-poly(butadiene).

High temperature vulcanization of elastomers: 2. Network structures in conventional sulphenamide-sulphur natural rubber vulcanizates

A natural rubber (NR) gum mix with a conventional N-cyclohexyl-2-benzothiazylsulphenamide (CBS) accelerated sulphur system (0.5:2.5 CBS/S) was vulcanized at temperatures from 140°C to 200°C. The influence of cure temperature on (a) the chemical crosslink density, (b) the distribution of crosslink types, (c) the extent of sulphidic main-chain modifications, and (d) the zinc sulphide formation was investigated. Results show that elevated cure temperatures produce a network with a lower crosslink density, in particular a lower polysulphidic crosslink density. The formation of intramolecular sulphidic groups and zinc sulphide increases with increasing temperatures. The possibility of chain scission during vulcanization was examined by a quantitative analysis of the sol-gel data. Less than 1 site of scission per 100 crosslinked isoprene units was established in the temperature range of 140–200°C. The network results can be satisfactorily correlated with the physical properties of a tyre tread mix of NR as reported in Part 1. Mechanistic interpretations are made to account for the network results.

Resolution Of An Identification Problem ByCoupling Stochastic And DeterministicMethods

This paper deals with the implementation of stochastic process coupling with classical minimization methods in order to solve an identification problem. A model for an industrial process (elastomer vulcanization) is proposed and then the minimization problems and methods are presented. The effect of random perturbations on these methods is studied. Numerical results are given. The interest of the coupling of stochastic and deterministic methods is shown. INTRODUCTION We are interested in a situation issued from thermal industry: the vulcanization. Gamier [1] has shown that, while the curing of some elastomers, an exothermical reaction can occur and damage the material. In order to avoid this destruction, a sharp control is essential and a fine modelling of the physical phenomena taking place during the industrial process is important. The identification of some of the elastomer's parameters must be performed by means of physical experiments (differential scanning calorimetry,...) or numerical methods using temperature measurements can be carried out. 1 A MODEL FOR THE INDUSTRIAL PROCESS In this section, we present a model for the curing of an elastomer. In the industrial process, the natural rubber is injected under pressure in a parallelepipedic cell heated by the top and the bottom (see figure la). Heat flux is supposed equal to 0 on the other faces. This 3-D geometry involved is simplified to 1-D (see figure Ib). Transactions on Engineering Sciences vol 5, © 1994 WIT Press, www.witpress.com, ISSN 1743-3533

Sulfur Crosslinks in Polybutadiene Vulcanizates

Abstract For the first time the crosslink terminus structure of monosulfide crosslinks and the amount of that structure in an elastomer vulcanizate has been determined directly from a sample of the vulcanizate. By measuring the rate of swelling of vulcanizates, immersed in either methyl iodide or methyl bromide, the rate of crosslink cleavage was measured. Comparison of this cleavage rate with the cleavage rate of model monosulfide compounds permits a measure of the terminus structure of the monosulfide crosslinks. The fraction of each monosulfide structure was determined from the cleavage rate equation for the vulcanizate. The monosulfide crosslink terminus structure in a particular polybutadiene vulcanizate was found to be saturated, having secondary carbon atoms on both sides of the sulfur atom, i.e., it was a saturated, tetrafunctional crosslink equal to 38% of the total crosslinks.

Sulfur crosslinks in polybutadiene vulcanizates

AbstractFor the first time the crosslink terminus structure of monosulfide crosslinks and the amount of that structure in an elastomer vulcanizate has been determined directly from a sample of the vulcanizate. By measuring the rate of swelling of vulcanizates, immersed in either methyl iodide or methyl bromide, the rate of crosslink cleavage was measured. Comparison of this cleavage rate with the cleavage rate of model monosulfide compounds permits a measure of the terminus structure of the monosulfide crosslinks. The fraction of each monosulfide structure was determined from the cleavage rate equation for the vulcanizate. The monosulfide crosslink terminus structure in a particular polybutadiene vulcanizate was saturated, having secondary carbon atoms on both sides of the sulfur atom, i.e., it was a saturated, tetrafunctional crosslink. Polysulfide crosslinks in 1,4‐polybutadiene vulcanizates are readily cleaved at room temperature by a solution of phenyl lithium in benzene. The number of polysulfide crosslinks was estimated from a measure of the volume swelling of the vulcanizate before and after treatment with phenyl lithium. This reagent does not cleave the monosulfide crosslinks in polybutadiene vulcanizates.

Mechanism of Peroxide Vulcanization of Elastomers

Abstract As is now well known, the use of an organic peroxide as a crosslinking agent for an elastomer was first reported by Ostromislensky in 1915. In this work benzoyl peroxide was used to cure natural rubber; similar acyl peroxides together with more recently discovered, less active, and more convenient dialkyl peroxides have since this time been used to crosslink a very large number of polymers. With the common unsaturated polymers the vulcanizates produced have mechanical properties rather inferior to those obtained with accelerated sulfur cures. They do, however, have the good aging and low compression set properties which are, in general, associated with sulfurless cures. The commercial use of peroxides in unsaturated elastomers is nevertheless small, being employed only where the presence of sulfur would be deleterious. In spite of its technological disadvantages peroxide crosslinking has been extensively studied since it forms a chemically simple means of introducing crosslinks into a wide variety of rubbers and leads to vulcanizates of simple structure with physically and chemically stable, carbon-to-carbon crosslinks. Interest in the industrial use of peroxides as curing agents has increased recently with the introduction of a number of fully saturated rubbers for which the usual accelerated sulfur systems are unsuitable. Such saturated rubbers are, in general, more resistant to aging, are more thermally stable, and will probably be used to increasingly greater extents as operational conditions become more and more severe. The study of curing systems available for use with such rubbers is therefore of considerable importance and organic peroxides, forming one such system, are worthy of detailed examination. Much work has been done on the technological evaluation of peroxide vulcanizates and much of this is summarized in a recent book edited by Alliger and Sjothun which is recommended as a source of references for a more detailed study of this aspect of the subject. The basic mechanism of the peroxide crosslinking of a wide variety of rubbers has, however, been neglected until relatively recently. For this reason, and for reasons of length, it is proposed to limit the present review to this latter aspect of the subject.

Vulcanization of Elastomers. 47. Vulcanization of Natural Rubber and Polybutadiene with Benzoyl Peroxide

Abstract The present article reports experiments intended to elucidate the kinetics of benzoyl peroxide decompositions in natural rubber and polybutadiene, and of consequent reactions. Both in natural rubber and in polybutadiene and at all temperatures, peroxide decomposition is first order with respect to concentration as well as time. The decomposition rate is substantially higher in natural rubber than in polybutadiene, and independent of the constitution of the polymer chains of the polybutadiene (tacticity, vinyl side groups, and the like). A somewhat higher activation energy of peroxide decomposition was derived for polybutadiene than for natural rubber. Formation of benzoic acid and crosslinking both follow a first order time law; the rates for peroxide decomposition, formation of benzoic acid, and crosslinking are the same in natural rubber and polybutadiene. It seems probable that peroxide decomposition in polybutadiene is purely homolytic. Interaction between peroxide and natural rubber is assumed, resulting in an increase in the rate of decomposition. The benzoic acid yield is considerably higher in natural rubber than in polybutadiene, and diminishes in the latter with the increase in vinyl side groups. In natural rubber this yield is a function of temperature, but in polybutadiene it shows practically no temperature dependence. Benzoyloxy radicals are incorporated into the elastomers as benzoate groups, as confirmed by infrared spectroscopic determinations with cis-1,4 polybutadiene. An interpretation of the formal kinetics of the vulcanization of 1,5-polyenes is proposed, which, together with the experimental results, may be used as a basis for consideration of the reaction mechanism.

Vulcanization of Elastomers. 44. Vulcanization of Polybutadiene with Cumyl Peroxide. I.

Abstract Cumyl peroxide vucanization of cis-1,4 polybutadiene with 2“3 per cent 1,2 addition was compared with that of natural rubber. The essential findings are: 1) In both rubbers, cumyl peroxide decomposed at exactly the same rate. 2) As shown earlier for natural rubber, the crosslinking reaction was over in polybutadiene when cumyl peroxide decomposition was complete. 3) Final crosslink density in polybutadiene decreased with increasing vulcanization temperatures. 4) Crosslinking yield in polybutadiene can be estimated simply by comparison with the crosslinking yield in natural rubber.

Vulcanization of Elastomers. 40. Vulcanization of Natural Rubber and Synthetic Rubber with Sulfur in Presence of Sulfenamides. III

Abstract Vulcanization of natural rubber with sulfur was studied in presence of six sulfenamides, to determine the effect of the chemical constitution of the sulfenamide on sulfur decrease and on crosslinking. The results can be condensed as follows: (1) The kinetics of sulfur disappearance is in every respect qualitatively independent of the chemical constitution of the sulfenamide. (2) For the sulfenamides investigated, the smallest and largest rate constants for sulfur decrease differed only by a factor of two. (3) Greater differences are encountered in the induction times for sulfur decrease and for crosslinking. The latter are notably longer than those for sulfur disappearance. (4) The same activation energy, 23 kcal/mole, is derived from the temperature dependence of the induction times for all the sulfenamides. (5) The dissociation of sulfenamides in solution and their reaction with mercaptobenzothiazole were investigated further. The results provide the basis for a proposed reaction mechanism, which is presented in detail and can account for a number of the features typical of sulfenamide-accelerated vulcanization. (6) The drop in sulfur concentration goes at practically the same rate, if one introduces, instead of N, N-dicyclohexyl-2-benzothiazolesulfenamide, the corresponding ammonium mercaptide in equimolar concentration.

Vulcanization of Elastomers. 39. Vulcanization of Natural and Synthetic Rubbers by Sulfur and Sulfenamides. II

Abstract The dependence of the kinetics of vulcanization of natural rubber by sulfur in presence of N-cyclohexyl-benzothiazolylsulfenamide (CHBS) on temperature and for varied molar ratios of accelerator and sulfur was more exactly investigated. 1. Although the vulcanization of natural rubber accelerated with N-cyclohexyl-benzothiazolylsulfenamide with conventional experimental conditions is characterized by very long induction times, nevertheless—as also for other accelerated vulcanization reactions—sulfur decrease follows a time law with nt<1 and the activation energy, as in other cases, is calculated to be 29 kcal/mole. 2. The value nt=0.6 is found for the exponent of the time law, independent of temperature and concentration of reactants. 3. The concentration dependence of the rate of sulfur decrease under conditions of constant sulfur content and increasing sulfenamide concentration is found to be consistent with catalysis by an intermediate compound. 4. The actual accelerator may be essentially cyclohexylammonium-benzothiazoylmercaptide. 5. The temperature and concentration dependence of the induction periods for sulfur decrease and crosslinking were investigated. The course of crosslinking with reaction time, which is characterized by strong reversion, is discussed.

Vulcanization of Elastomers. 36. Vulcanization of Natural Rubber and Synthetic Rubbers with Sulfur in Absence of Accelerators. II

Abstract In continuation of earlier work with natural rubber, the kinetics of sulfur decrease were studied in certain synthetic rubbers for different temperatures and sulfur concentrations. At the same time the formation of polysulfide bound sulfur was studied, using as example the reaction of sulfur with natural rubber and synthetic rubbers. It was found that: 1) When the decrease in sulfur concentration is portrayed by curves which are convex to the time axis (Perbunan), the 0.6th order time-law is fulfilled, (as in the case of natural rubber independent of temperature and concentration. 2) In contrast, the concentration dependence of the rate at which sulfur decreases, both in Perbunan and cis 1,4-polybutadiene, denotes a first-order reaction in agreement with experience with natural rubber. 3) The activation energy of sulfur decrease has the same magnitude for all the elastomers investigated (34 to 36 kcal/mole). 4) The disagreement between the time law and the concentration dependence of the rate of sulfur disappearance encountered in all the experiments with 1,5-polyenes, is interpreted as indicating autocatalysis, which likewise explains the shape of the curves for sulfur disappearance. 5) Sulfur reacts considerably faster in natural rubber and Perbunan than in cis 1,4-polybutadiene; consequently a homolytic dissociation of the S8-ring cannot be rate-determining. 6) Polysulfide sulfur shows, in each case, a maximum with reaction time, and in completely reacted vulcanizates it tends toward a limiting value. An equation was found, which provides a good description of change with time of polysulfide concentration (natural rubber and cis 1,4-polybutadiene). 7) An explanation is given for the appearance of the polysulfide maximum; and how the reaction of sulfur with 1,5-polyenes can be represented, making use of all available results, is discussed.

Vulcanization of Elastomers. 46. The Kinetics of Crosslinking

Abstract The present article represents a first contribution to the investigation of the crosslinking kinetics of 1,5-polyenes, with sulfur as the vulcanizing agent. It is principally concerned with working out the pertinent methodology, and hence is a report on our experience with the “Agfa Vulcameter” (also called the Bayer Vulcameter). Using as an example the zinc benzothiazolyl mercaptide (ZnMBT)/zine stearate accelerated vulcanization of natural rubber with sulfur, which in any case runs with practically no reversion at moderate temperatures, and thus permits an experimental determination of the crosslinking end-values, we were able to show that crosslinking can be described quantitatively and qualitatively with the help of an Agfa Vulcameter. It was proved that the same reaction order and the same rates are obtained, as when the static modulus is used as the criterion for crosslinking. The scientific and practical importance of the results are pointed out.