Rubber microstructure

A. S. Berensand J. H. Born, The Effect of Surface Microstructure on the Performance of Rotary Shaft Lip Type Oil Seals. Fourth Rubber and Plastics Conference, July 4-7 (1974). 

Characterization and understanding of the microstructure become important after hydrogenation and hydroformylation of the nitrile rubber since the amount and distribution of the residual double bonds influence the properties of modified rubber. The conventional analytical tools have been used to characterize the elastomers. Spectroscopy is the most useful technique for determination of the degree of hydrogenation in nitrile rubber. 

The particle size of the dispersed phase depends upon the viscosity of the elastomer-monomer solution. Preferably the molecular weight of the polybutadiene elastomer should be around 2 x 10 and should have reasonable branching to reduce cold flow. Furthermore, the microstructure of the elastomer provides an important contribution toward the low-temperature impact behavior of the final product. It should also be emphasized that the use of EPDM rubber [136] or acrylate rubber [137] may provide improved weatherability. It has been observed that with an increase in agitator speed the mean diameter of the dispersed phase (D) decreases, which subsequently levels out at high shear [138-141]. However, reagglomeration may occur in the case of bulk... 

Table 2.7 lists techniques used to characterise carbon-blacks. Analysis of CB in rubber vulcanisates requires recovery of CB by digestion of the matrix followed by filtration, or by nonoxidative pyrolysis. Dispersion of CB within rubber products is usually assessed by the Cabot dispersion test, or by means of TEM. Kruse [46] has reviewed rubber microscopy, including the determination of the microstructure of CB in rubber compounds and vulcanisates and their qualitative and quantitative determination. Analysis of free CB features measurements of (i) particulate and aggregate size (SEM, TEM, XRD, AFM, STM) (ii) total surface area according to the BET method (ISO 4652), iodine adsorption (ISO 1304) or cetyltrimethylammonium bromide (CTAB) adsorption (ASTM D 3765) and (iii) external surface area, according to the dibutylphthalate (DBP) test (ASTM D 2414). TGA is an excellent technique for the quantification of CB in rubbers. However, it is very limited in being able to distinguish the different types of... 

Polybutadiene (PB) and polyisoprene with cis-trans controlled microstructure (synthesis of "natural rubber"). 

Figure 3. Modulus contributions from chemical cross-links (Cx, filled triangles) and from chain entangling (Gx, unfilled symbols) plotted against the extension ratio during cross-linking, A0, for 1,2-polybutadiene. Key O, GN, equibiaxial extension , G.v, pure shear A, Gx, simple extension Gx°, pseudo-equilibrium rubber plateau modulus for a polybutadiene with a similar microstructure. See Ref. 10.

Figure 14.7 Schematic highlighting the microstructure of rubber-toughened PET and performance improvements when non-reactive elastomers are blended with reactive elastomers (adapted from Atofina literature entitled Lotader and Lotryl )...

The information on physical properties of radiation cross-linking of polybutadiene rubber and butadiene copolymers was obtained in a fashion similar to that for NR, namely, by stress-strain measurements. From Table 5.6, it is evident that the dose required for a full cure of these elastomers is lower than that for natural rubber. The addition of prorads allows further reduction of the cure dose with the actual value depending on the microstructure and macrostructure of the polymer and also on the type and concentration of the compounding ingredients, such as oils, processing aids, and antioxidants in the compound. For example, solution-polymerized polybutadiene rubber usually requires lower doses than emulsion-polymerized rubber because it contains smaller amount of impurities than the latter. Since the yield of scission G(S) is relatively small, particularly when oxygen is excluded, tensile... 

Obviously, typical composite propellants are highly filled polymers and, especially in the case of the rubber-based systems, are more nearly granular media than merely filled rubbers. Certain specific differences between the double-base binder and the elastomeric binder lead to some differences in behavior, but many of the resulting properties show similarities. The relationships between bulk properties and microstructure in the rubber-based systems are much better understood than those of the double-base propellants and, therefore, the following discussions focus primarily on the former category. 

Kinetics in Non-Polar Media. Polymerization of vinyl monomers in non-polar solvents, i.e., hydrocarbon media, has been almost entirely restricted to the organolithium systems (7), since the latter yield homogeneous solutions. In addition, there has been a particularly strong interest in the polymerization of the 1,3-dienes, e.g., isoprene and butadiene, because these systems lead to high 1,4 chain structures, which yield rubbery polymers. In the case of isoprene, especially, it is possible to actually obtain a polymer with more than 90% of the eis-1,4 chain structure (7, 8, 9), closely resembling the microstructure of the natural rubber molecule. 

This new development in the microstructural architecture of polybutadiene has opened the door for the preparation of various block copolymers made from the same monomer. For example, one can use this concept to prepare various polybutadiene rubbers in which the chain segment contains various glass transition temperatures, depending on its microstructural arrangements. Similarly, manipulating the polymerization temperature using the same modifier and... 

Anionic polymerization dates back at least to the early part of this century. Indeed, sodium-initiated butadiene polymers were investigated as potential synthetic rubbers many years ago. Unfortunately, the derived, high 1,2 microstructure shows a T, of about 0°C. Electron transfer initiators also were studied by Scott in 1936. 

Natural rubber (NR) and guttapercha consist essentially of polyisoprene in cis-l, 4 and trans-1,4 isomers, respectively. Commercially produced synthetic polyisoprenes have more or less identical structure but reduced chain regularity, although some may contain certain proportions of 1,2- and 3,4-isomers. Microstructure differences not only cause the polymers to have different physical properties but also affect their response to radiation. The most apparent change in microstructure on irradiation is the decrease in unsaturation. It is further promoted by the addition of thiols and other compounds.130 On the other hand, antioxidants and sulfur were found to reduce the rate of decay of unsaturation.131 A significant loss in unsaturation was found, particularly in polyisoprenes composed primarily of 1,2- and 3,4-isomers.132,133... 

Microstructure-property correlations in dynamically vulcanized thermoplastic elastomers based on polypropylene (PP)/EPDM have shown that clay was nearly exfoliated and randomly distributed into the continuous polypropylene phase [23]. SEM photomicrographs revealed that the size of rubber particles increased with clay incorporation. Also, the clay layers act as nucleating agents, resulting in higher crystallization temperature and reduced degree of crystallinity. 

A proposed mechanism for toughening of rubber-modified epoxies based on the microstructure and fracture characteristics (310—312) involves mbber cavitation and matrix shear-yielding. A quantitative expression describes the fracture toughness values over a wide range of temperatures and rates. 

Composition and microstructure determination of polybutadiene (BR) and natural rubber (NR) can be done by infrared spectra. Three different base units are possible for linear addition polymers of 1,3 butadiene units with cis or trans internal double bands from 1,4 addition and units with side vinyl groups from 1,2 addition (see Scheme 3.1a). 

It is concluded that IR spectroscopy provides information on qualitative as well quantitative analyses of rubbery materials, apart from their microstructures (that is, whether cis or trans, syndiotactic, atactic or isotactic). Different types of rubber blends (compatibilised or self-crosslinked) can be identified by the infrared spectroscopy. Synthesis, and degradation of polymers can also be followed by IR spectra. Mechanism of interaction between rubbers and fillers, can also be studied by IR-spectra. Different types of chemical reactions like the milling behaviour of rubbers, mechanism of adhesion and degradation can also be studied with the help of IR spectroscopy. The technique plays a great role in the product analysis under reverse engineering. 

Infrared spectroscopy is one of the most important tools used to characterise the chemical structure, composition and microstructure of different polymers [8-10]. In earlier chapters, the principles and applications of infrared (IR) spectroscopy in the characterisation of rubbers have been discussed. This chapter describes how IR spectroscopy can be used to characterise different types of chemically modified elastomers. 

The simplest diene rubber for hydrogenation is BR. The structure of the hydrogenated BR (HBR) depends on the different microstructures present in BR. Hydrogenation of BR with high 1,4 structure converts this elastomeric polymer into a tough semicrystalline... 

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