The Mechanism of Crack Formation in Rubbers under the Effect of Ozone

Abstract

The formation and growth of cracks under an effect of ozone were investigated in different types of rubbers, such as NR, PBR, BMSR, SBR and in composite materials based on these rubbers. The study was carried out by the reflection-light optical microscopy method with using the MMP-4 microscope. In the presence of microinhomogeneities in a surface structure the crack formation is shown to start from those defects. In the absence of inhomogeneities the cracks are formed uniformly over the whole surface of a specimen. It is found that even insignificant quantities of low-modulus rubber in the PBR-based composite material may result in changing the shape of a crack during its growth. An attempt is undertaken to describe the shape of formed cracks quantitatively. The calculational and experimental data are presented.

The influence of deformation on the number of cracks per surface unit, on their shape, geometrical size, cracking degree is studied for example of natural rubber specimen.     

Water-based adhesive formulations for rubber to metal bonding developed by statistical design of experiments

Waterborne adhesives for rubber to metal bonding have been available since 1990. However, published information about their formulation has been limited, as proprietary restrictions are exercised by companies. As a consequence, the way these adhesives interact with substrates has not been studied extensively. With the aim of investigating the effect the components of a waterborne adhesive have on rubber to metal bonding, fractional factorial and surface response methodologies of design of experiments were employed in this study. Twenty six formulations were prepared with a polychloroprene latex as the adhesive polymer. Viscosity, wettability and non-volatile solids content were measured with each liquid adhesive, while the mechanical strength was evaluated by applying a tensile mechanical stress over cured solid adhesive films. Adhesion properties were evaluated by using a single lap-shear test on metal to metal joints and a pull-out test on rubber to metal joints. The results showed that the components with the largest relative influence on cohesive and adhesives forces were tackifier resin, silicon dioxide and polychloroprene latex type. In order to better understand the contributions of these variables, mathematical models correlating them with the response variables were obtained. This study is valuable in explaining how, through statistical methods, a waterborne adhesive for rubber to metal bonding can be formulated with a reasonably low number of experiments.     

Rubber Particles from Tires Out of Use as Toughness Modifiers of Epoxy-Based Thermosets

Rubber particles from tires out of use (TOU) were used to modify an epoxy-based thermoset. The effect of size and particle content were evaluated. Three bending point and Charpy tests were carried out to study the mechanical behavior of the materials. A steady decrease in the critical stress intensity factor, K_Ic, with the content of TOU was observed, being attributed to the fact that the particles might also act as defects in the polymer matrix. Fractographic analysis confirmed that filled specimens showed localized shear yielding at the end of the particles along the crack propagation direction. No signs of cavitation mechanism were found on the surfaces of fracture, evidencing an extraordinary interfacial adhesion. The total energy absorbed at break increased as the size of TOU particles decreased, pointing out that particle size is crucial for the performance of these materials. Matrix yielding and plastic deformation were considered to be the main toughness mechanisms.     

Dependence of Adhesion Properties of Cross-linked Epoxidized Natural Rubber (ENR 25)-Based Pressure-Sensitive Adhesives on Benzoyl Peroxide Loading in the Presence of Gum Rosin and Petroresin Tackifiers

The effect of benzoyl peroxide loading on the adhesion properties of cross-linked epoxidized natural rubber (ENR 25)-based adhesives was studied using gum rosin and petroresin as tackifiers. Toluene and polyethylene terephthalate (PET) were used as solvent and coating substrate, respectively. The adhesion properties were determined by a Lloyd adhesion tester operating at 30 cm min^?1. Results indicate that the loop tack and peel strength of gum rosin and petroresin pass through a maximum value at 2 parts per hundred parts of rubber (phr) and 3 phr benzoyl peroxide concentration, respectively, an observation which is attributed to the optimum cross-linking of ENR 25 where optimum, cohesive and adhesive strength is obtained. The shear strength, however, increases steadily with increasing benzoyl peroxide loading due to the steady increase in the cohesive strength. At the optimum benzoyl peroxide concentration, the petroresin-based adhesive consistently exhibits higher adhesion properties compared to that of gum rosin-based adhesives. The adhesion properties of both adhesive systems increase with increasing coating thickness.     

Effect of Sol-Gel-Derived Nano-silica on the Properties of Natural Rubber-Poly Butadiene Rubber-Reclaim Rubber Ternary Blends/Silica Nanocomposites

Silica incorporation into natural rubber (NR)-polybutadiene rubber (PBR)-reclaim rubber (RR) ternary blend system was carried out by sol-gel technique at different temperatures. The effect of RR on silica reinforcement was studied for NR-PBR-RR blend systems. The physicochemical properties of sol-gel vulcanizates indicates that the reinforcing efficiency of the nanocomposites increases with increasing RR content. Sol-gel vulcanizates prepared at 50°C shows superior mechanical properties than others. The amount of silica incorporated by sol-gel technique was determined through thermogravimetry analysis, which indicates the increasing trend of thermal stability with silica content. SEM studies indicate the coherency and homogeneity in the NR-PBR-RR/SiO ₂ nanocomposites.     

Pyrolysis of scrap tire rubbers: Relationships of process variables with pyrolysis time

The functional relationships of industrially interesting variables such as pyrolysis temperature, heating rate, and sample size with pyrolysis time were explored to provide basic information on designing energy efficient processes. Pyrolysis kinetics of scrap tire rubbers tested in this study were investigated to formulate the functional relationships of pyrolysis temperature and heating rate. The pyrolysis time decreases exponentially with increasing pyrolysis temperature and heating rate, indicating high activation energies of pyrolysis reaction of the scrap tire rubbers tested in this study. The effect of heat transfer on the pyrolysis kinetics was evaluated by seeking the functional relationship between the sample size and pyrolysis time.The pyrolysis time increases linearly with increasing sample diameter. The slope of the straight line is proportional to the specific heat of the sample.     

Review of the Adhesively Bonded Interface in a Solid Rocket Motor

One of the most challenging requirements in a solid rocket motor (SRM) is the integrity of the charge structure which is a multilayer adhesive joint involving the propellant, liner, and insulation. The propellant/liner/insulation interface is considered to be the weakest part of the whole structure. This interface has some of the usual features of an adhesively bonded interface, as well as its own special characteristics: the co-cured process, ingredient migration between interfaces, and complicated damage mechanisms. We give a technical and critical review of the past 50 years of existing research on many aspects of the propellant/liner/insulation interface in terms of the adhesive properties and adhesive mechanisms, ingredients migration, damage determination, and fracture analysis. To present a comprehensive outline of this interface we also clarify some remaining problems which should be addressed in the future. With significant improvements in the theoretical and experimental studies of the propellant/liner/insulation interface, the problem of integrity failure of the charge structure in SRM will be well resolved.     

Stress singularity in a rectangular bond specimen of a solid rocket motor: Effects and elimination

The propellant/liner interface is the weakest and most concerning part of the grain structure in a solid rocket motor. Rectangular bond specimen tests have gradually become one of the standard methods to measure the bonding abilities of propellant/liner/insulation joints. We performed a three-dimensional numerical study to give full knowledge of this new test, paying close attention to the stress singularity at the crack tip. The asymptotic stress field was presented to show the singularity at the crack tip on the steel/insulation interface. Subsequently the stress singularity was investigated numerically. Numerical results show that the stress singularity has a considerable effect on the stress distribution of the nearby propellant. Also we proposed some methods to eliminate these effects, such as inserting a cohesive zone model into the steel/insulation interface or increasing the thickness of insulation layer. Moreover, Mises stress and maximum principle stress have completely opposite distributions on the propellant/liner interface; thus the accurate failure criterion can be confirmed by the damage initialization observed in experiments.     

Shear Property of Kaolin-filled Standard Malaysian Rubber (SMR L) Pressure-sensitive Adhesive

The effect of kaolin loading on the viscosity and shear strength of natural-rubber-based pressure-sensitive adhesive was studied using coumarone-indene resin, toluene, and polyethylene terephthalate as tackifier, solvent, and substrate, respectively. Kaolin loading ranged from 10 to 60 parts per hundred parts of rubber (phr) whereas the tackifier content was fixed at 40 phr. The viscosity and shear strength—from lap shear test—were determined by a Brookfield viscometer and Lloyd adhesion tester, respectively. Results show that viscosity increases with increasing kaolin loading. However, shear strength increases up to 20 phr kaolin loading, after which it decreases with further filler loading. This observation is attributed to the culmination of cohesive strength at the optimum loading of kaolin filler. For a fixed kaolin loading, the shear strength increases with coating thickness and testing rate.     

Influence of nanoclay on adhesion of EPDM vulcanizate

The influence of unmodified clay, Cloisite Na⁺ on adhesion between prevulcanized EPDM rubber and unvulcanized EPDM rubber containing nanoclay was investigated using 180° peel test. The rubber showed improvement in peel strength with increasing clay concentration up to 4 phr, beyond which it decreased. A maximum of 51% improvement in peel strength was obtained for 4 phr Cloisite Na⁺. This was attributed to enhanced tensile strength, monomer friction coefficient, marginal improvement of polarity and micro-roughness of the clay filled rubber. At higher clay loading (8 phr), the peel strength reduced due to formation of boundary layer of Zn-stearate, accelerators and clay on the outermost surface, diffusion of the fewer rubber chains, agglomeration of the clay particles and increased modulus of the rubber.