Conventional Vulcanizates Research Articles

The tensile properties of strain-crystallizing vulcanizates. III. The superiority of conventional over peroxide vulcanizates in terms of network microstructure

It is proposed that, when vulcanization is performed using peroxides, crosslinking leads to a simple network, whereas in conventional vulcanization crosslinking a partially interpenetrating polymer network (PIPN) is formed. Two unfilled polyisoprene networks of similar crosslink density, produced with dicumyl peroxide and 2-bisbenzothiazole-2,2′-disulfide/sulfur formulations, were compared with respect to the effect of strain rate on their stress–strain and hysteresis curves at room and elevated temperatures. At high elongations, the stress–strain curves for peroxide vulcanizates show a steeper upturn than for conventional vulcanizates, but have lower tensile strength and elongation at break. On increasing the extension rate, stress–strain curves for peroxide vulcanizates rise less steeply, while conventional vulcanizates rise more steeply. For both vulcanizates the hysteresis ratio decreases on increasing the rate at which samples are extended and retracted. The effect on conventional vulcanizates is less than on peroxide vulcanizates. It is suggested that chains in peroxide networks disengage increasingly rapidly at higher strains, allowing increased strain-induced crystallization. Rapid strain-induced crystallization leads to low ultimate tensile strength (UTS). In more complex PIPNs, the disengagement and alignment of chains are retarded. The increased nonuniform extension of chains promotes early strain-induced crystallization at low extensions, but overall it reduces the rate of crystallization, which occurs over a wider range of strains. This improves UTS and elongation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 876–884, 2006

Effect of thermal oxidative ageing on the morphology of natural rubber networks as viewed by ESR

The change of network morphology of unfilled sulfur crosslinked natural rubber exposed to thermal oxidative ageing has been studied. Three model networks with different sulfur contents (efficient network, semi-efficient and conventional vulcanizate) have been analysed by applying spin probe ESR, equilibrium swelling measurements and mechanical measurements. By combining the density distribution deduced from the complex ESR spectra and the equilibrium swelling density, it is shown that the major network changes occur in the networks with predominantly polysulfidic bonds (conventional network) after 96 h of ageing at 373 K. The effect of ageing on the network with predominantly monosulfidic bonds is much less pronounced. Both effects (main chain scission and additional local crosslinking) have been analysed in the course of prolonged ageing up to 240 h. A correlation between network structure and its mechanical performance is established. © 2000 Society of Chemical Industry

Unusual stress-strain properties of natural rubber vulcanizates with high primary molecular weight

Natural rubber vulcanizates with high primary molecular weight were prepared by mixing raw rubber and dicumyl peroxide in benzene followed by freeze-drying. The stress-strain properties of these vulcanizates were quite different from those prepared by conventional mastication method. The important characteristics of these vulcanizates is high tensile modulus, high tensile strength, large hysteresis loss, and higher degree of strain-induced crystallization. The difference in the stress-strain behavior between these rubbers and conventional vulcanizates are discussed from the standpoint of the network structure.

Strain-Dependent Dynamic Properties of Carbon-Black Reinforced Vulcanizates. I. Individual Elastomers

Abstract The degree of carbon—black particle aggregation (transient structure) in conventional vulcanizates varies with the nature of the elastomers. This is revealed by the variation of (Gm′−G∞ƒ′), which is a measure of the transient structure. The relationship between Gm″ and (Gm′−G∞ƒ′) as well as that between strain work and normalized modulus show similarity to earlier work in which the polymer type was not varied. This suggests that carbon-black structural elements act as energy storage units and are of the same type in all these polymers. While the decrease of in-phase modulus is primarily caused by carbon-black particle units, tan δ reflects also the effect of the polymeric matrix.

Polymerization of isoprene in the presence of amines containing lithium

A study was made of the possible use of tertiary N-substituted allylamines containing lithium as di- and trifunctional initiators of anionic polymerization of isoprene. The compounds are soluble in hydrocarbons and are of the type: R n N(CH 2CH=CH 2) 3− n (R=CH 3; CH 2C 6H 5;  CH 2CH=CH 2). To evaluate the functionality of initiators, hydroxyl end groups were added to the oligoisoprene obtained via the stage of epoxidation, followed by theatment of the product with acid. The average functionality of oligoisoprene diols, which was close to two, was only obtained when using initiators prepared from diallylbenzylamine and triallylamine. Unfilled rubber was synthesized by changing oligoisoprene diol to oligoisoprenedi-isocyanate and subsequent crosslinking with triaminotriphenyl methane. A sol content in the rubber obtained much higher than that in conventional vulcanizates and a high equilibrium swelling index indicate that the initial oligoisoprene diol contains not only bi-, but also mono-functional macromolecules.

Some effects of monomer sequence on the viscoelastic behavior of random copolymers of butadiene and styrene

AbstractThe copolymerization of butadiene and styrene by lithium alkyls can be regulated to give either random or block copolymers. The block copolymers exhibit characteristic mechanical behavior which is attributable to their two‐phase domain structure. In random copolymers free of long sequences of styrene there exists, nevertheless, the possibility of varying the sequence distribution by changing the manner in which composition varies along the polymer chain. Since copolymers of butadiene and styrene differing sufficiently in composition are likewise incompatible and will form multi‐phase systems, it is likely that microheterogeneity can exist in certain “random” copolymers.Five copolymers of monomer ratio 70 : 30 butadiene/styrene, varying from a uniformly randomized sample, in which composition was very nearly independent of conversion, to a block polymer containing 22% block styrene chemical analysis, were prepared for the present investigation. Composition vs. conversion data indicated that all but the last polymer were free of long styrene sequences, with the composition distribution (along the chain) broadening systematically throughout the remainder of the series.The melt viscosity of the unvulcanized copolymers was distinctly affected by sequence distribution effects. Thus, the temperature coefficient of the apparent viscosity was independent of shear stress only for the uniformly randomized copolymer. In all others temperature superposition of the non‐NEWTONian flow curves was impossible, the discrepancies becoming larger the broader the composition distribution. The results can be explained qualitatively by association effects attributable to a domain structure similar to that found in block polymers. When these copolymers were cross‐linked with dicumyl peroxide at 153 °C and the dynamic properties of the networks examined, no clear evidence of a domain structure was found except in the block polymer. Only the latter exhibited more than a single loss maximum. Temperature‐frequency reduction of the dynamic measurements was successful with all but the block polymer. Whereas the parameters C1 and C2 in the WILLIAMS‐LANDEL‐FERRY equation appear to change systematically with the degree of randomness, there is evidence that this is attributable to a slight systematic drift toward higher vinyl unsaturation with increasing randomization of the monomer sequence. Relaxation spectra calculated for 25 °C were very nearly the same for all four random copolymers. When the polymers were cross‐linked by gamma radiation at room temperature, the resulting networks did show properties indicative of a domain structure in the compositionally more heterogeneous copolymers. It is proposed that compatibility of chain segments of varying composition at the temperature of cross‐linking leads to a suppression of the domain structure in the peroxide‐cured rubbers, as segments of different composition are joined together. Independent evidence from stress‐optical measurements supports this interpretation.The present investigation permits the conclusion that differences in sequence distribution of butadiene‐styrene copolymers have, at best, only very minor effects on the visco‐elastic properties of conventional vulcanizates, provided the polymers contain no long sequences of styrene units, i.e., polystyrene blocks detectable by classical methods. This is not true of the low shear melt viscosity, which senses relatively small differences in the composition and/or sequence distributions of the uncured rubbers.

Relationships between the Structures of Natural Rubber Vulcanizates and Their Thermal and Oxidative Aging

Abstract Accelerated sulfur NR vulcanizate networks are known to contain poly-, di- and monosulfidic crosslinks, sulfur-containing main chain modifications including cyclic sulfides and pendent accelerator groups, and extra-network material, primarily vulcanization residues. Both oxidative and non-oxidative aging characteristics of the vulcanizate can be improved by use of an efficient or EV curing system. These systems utilize either a high accelerator to sulfur ratio or an accelerator in conjunction with a sulfur release agent to insert predominantly mono- and disulfidic crosslinks, and produce a minimum of main chain modifications. The resulting vulcanizates have excellent aging properties, but fatigue life is poor in comparison to that of a conventional vulcanizate. With a compromise between the conventional and EV curing systems, namely use of intermediate accelerator to sulfur ratios or mixtures of sulfur and sulfur donor, vulcanizates with good fatigue properties and improved aging characteristics can be obtained. Since the most obvious difference between EV and conventional vulcanizate networks is the per cent of monosulfidic crosslinks, it has been assumed that monosulfide crosslinks are responsible for the poor fatigue resistance of EV systems. Recently, it was found that a zinc dimethyldithiocarbamate (ZDC) EV system gave an NR gum vulcanizate having fatigue resistance equal to that of a conventional sulfenamide accelerated compound. The main features of the network are a high percentage of monosulfide crosslinks and extensive main chain modification. In this paper, the aging and fatigue behavior of black filled substituted phenylenediamine protected NR ZDC accelerated systems is examined. The ZDC EV vulcanizate has imaged fatigue resistance equal to that of a conventional sulfenamide accelerated vulcanizate, but oxidative aging is very poor. By decreasing the ZDC/sulfur ratio, a vulcanizate structure equivalent in every measurable way to that of a conventional sulfenamide accelerated system is obtained. Unaged fatigue properties of the two compounds are similar. However, oxidative aging resistance of the ZDC compound is again very poor, and fatigue life of an air aged specimen is virtually zero. It is concluded that fatigue life is not necessarily a function of the crosslink type distribution. Accelerator residues and possibly main chain modifications play an important role insofar as oxidative and non-oxidative aging characteristics are concerned.

Low-Frequency Losses in Rubbers Cross-Linked in the Presence of Diluent

Abstract Measurements of the complex shear compliance have been made from 0.1 to 7 cycles/sec and from − 5° to 45° C on several samples of natural rubber cross-linked by dicumyl peroxide in the presence of a diluent oil (volume fraction of rubber, v2=0.63 and 0.76) which was subsequently extracted. The properties of the extracted vulcanizates were compared with those having the oil still present and with those of conventional undiluted vulcanizates. Measurements of the diffusion coefficient of radioactively tagged n-hexadecane in trace amounts through the polymer structure were also made both before and after extraction of the oil. The diffusion coefficient was higher in the presence of the oil by an amount consistent with the Fujita theory for concentration dependence of diffusion rate based on free volume considerations. The low-frequency mechanical losses (reduced to 25° C by the method of reduced variables), as measured by the loss tangent, were shifted to higher frequencies by the presence of oil to a much larger degree than would be expected from the difference in local mobility gauged by the diffusion coefficient. The equilibrium modulus, derived by extrapolation to zero frequency, was diminished by the presence of oil to a greater extent than the factor of v21/3 expected from the simple theory of rubberlike elasticity. The low-frequency losses in the extracted vulcanizates were smaller than those in conventional vulcanizates with comparable degrees of cross-linking; the differences are attributed to differences in network topology.

Low‐frequency losses in rubbers cross‐linked in the presence of diluent

AbstractMeasurements of the complex shear compliance have been made from 0.1 to 7 cycles/sec. and from −5° to 45°C. on several samples of natural rubber cross‐linked by dicumyl peroxide in the presence of a diluent oil (volume fraction of rubber, v2, = 0.63 and 0.76) which was subsequently extracted. The properties of the extracted vulcanizates were compared with those having the oil still present and with those of conventional undiluted vulcanizates. Measurements of the diffusion coefficient of radioactively tagged n‐hexadecane in trace amounts through the polymer structure were also made both before and after extraction of the oil. The diffusion coefficient was higher in the presence of the oil by an amount consistent with the Fujita theory for concentration dependence of diffusion rate based on free volume considerations. The low‐frequency mechanical losses (reduced to 25°C. by the method of reduced variables), as measured by the loss tangent, were shifted to higher frequencies by the presence of oil to a much larger degree than would be expected from the difference in local mobility gauged by the diffusion coefficient. The equilibrium modulus, derived by extrapolation to zero frequency, was diminished by the presence of oil to a greater extent than the factor of v2⅓ expected from the simple theory of rubberlike elasticity. The low‐frequency losses in the extracted vulcanizates were smaller than those in conventional vulcanizates with comparable degrees of cross‐linking; the differences are attributed to differences in network topology.

Microstructural Variations in Commercial Carbon Blacks

Abstract Conventional and diffracted beam electron microscopy can be used to resolve the ultimate crystallite units in standard and heat treated carbon blacks. They are very sensitive in the detection of small differences in crystallite size and orientation. Combined with x-ray diffraction methods and conventional vulcanizate testing, high resolution electron microscopy appears to be a useful and practical means to study carbon black surface activity. All commercial blacks appear to conform in part to the Heckman and Harling concentric crystallite model. Surface activity appears to be related to the extent of this alignment; the less the tangential orientation of the graphite layer planes to the surface, the greater the surface activity. Heating carbon blacks in an inert atmosphere for varying times and temperatures (850 to 1400° C) causes a gradual depression of surface activity with increasing treatment severity, defined by increases in the size and concentric orientation of surface crystallites. At no time was the effect of carbon black on vulcanizate properties changed significantly by heat treatment without disrupting the initial orientation of surface crystallites. Carbon blacks differ in the rate of change of crystallite orientation in response to heat treatment. The initial degree of crystallinity, porosity, and surface volatile content all appear to affect the rate of crystallite orientation and growth. Increases in average crystallite height, Lc, are a good measure of effects of heat treatment in excellent agreement with changes in surface crystallite size and orientation observed with the electron microscope. Commercial ISAF carbon blacks of varied structure have relatively minor differences in surface crystallite orientation, indicating small differences in surface activity. The higher modulus and treadwear associated with the use of high structure blacks appear to be predominantly a result of the chain structure itself. Further evidence was obtained showing that black structure and surface activity are independent properties each of which can have a significant influence on vulcanizate properties such as modulus, treadwear, and hysteresis.