Vulcanizate cross-link

Vulcanizate Cross-links Chemical bonds formed between polymeric chains in rubber as a result of vulcanization. 

Accelerators. During sulfur vulcanization of rubber, accelerators serve to control time to onset of vulcanization, rate of vulcanization, and number and type of sulfur cross-links that form. These factors in turn play a significant role in determining the performance properties of the vulcanizate. 

There are three generally recognized classifications for sulfur vulcanization conventional, efficient (EV) cures, and semiefficient (semi-EV) cures. These differ primarily ki the type of sulfur cross-links that form, which ki turn significantly influences the vulcanizate properties (Eig. 8) (21). The term efficient refers to the number of sulfur atoms per cross-link an efficiency factor (E) has been proposed (20). 

In general, however, the vulcanizates suffer from poor low temperature crystallization performance compared to a conventional sulfur cure, and also have inferior tensile and tear properties. Urethane cross-linking systems (37), eg, Novor 950 (see Table 3) are also extremely heat resistant, but exhibit inferior tensile and dynamic properties compared to conventional sulfur-cured vulcanizates. One added virtue is that they can be used in conjunction with sulfur systems to produce an exceUent compromise according to the ratios used (38). 

Curing. Carboxyl cure sites are incorporated in the ethylene—acryhc terpolymer to permit cross-linking with primary diamines (1,7). Guanidines are added to accelerate the cure. Peroxides may also be used as curing agents in the terpolymer, but generally give inferior properties to vulcanizates based on diamine systems (8). Dipolymers are cured only with peroxides. 

Better cross-linking with the latter also improves post Tg viscoelastic responses of the rubber vulcanizates. Similar effect has also been observed with polychloroprene as investigated by Sahoo and Bhowmick [41]. Figure 4.8 represents the comparative tensile stress-strain behavior of polychloroprene rubber (CR) vulcanizates, highlighting superiority of the nanosized ZnO over conventional rubber grade ZnO [41]. 

In an alternate synthesis, the formation of thermoplastic vulcanizate (TPV) is accomplished with two polymers, wherein one polymer is grafted with a carboxylic acid anhydride, which then is reacted with an aminosilane, which reacts with the acid anhydride and then cross-links with moismre. The vulcanizates exhibit good mechanical properties and lower melt-flow index than the starting polymers. 

The ability of the E-plastomers to participate in the peroxide-mediated chain-extension processes can be augmented in blends with EPDM, where the mixture is homogeneously cross-linked with free radicals [5]. The use of these blends of EPDM and E-plastomers leads to improved processing and physical properties of the combination, compared to the EPDM alone, though the resulting vulcanizates are somewhat harder than the EPDM vulcanizates alone due to the presence of the semicrystalline plastomers in the vulcanized mixture. 

Sulfur cross-links have limited stability at elevated temperatures and can rearrange to form new cross-links. These results in poor permanent set and creep for vulcanizates when exposed for long periods of time at high temperatures. Resin cure systems provide C-C cross-links and heat stability. Alkyl phenol-formaldehyde derivatives are usually employed for tire bladder application. Typical vulcanization system is shown in Table 14.24. The properties are summarized in Tables 14.25 and 14.26. 

This conclusion is supported by the experimental result " given by the pulsed-NMR measurement that the spin-spin relaxation time T2 is considerably shorter for the gel than that for the matrix mbber vulcanizate, which of course, indicates that the modulus is considerably higher for the gel than for the matrix mbber. More quantitatively, Maebayashi et al. measured the acoustic velocity of carbon gel by acoustic analysis and concluded that the compression modulus of the gel is about twice that of matrix mbber. Thus, at present, we can conclude that the SH layer, of course without cross-linking, is about two times harder than matrix cross-linked mbber in the filled system. 

Addition of scrap rubber in the form of either ground waste vulcanizates or reclaim in rubber compounds gives economic as well as processing advantages. In addition to lowering the cost of rubber compounds, the use of cross-linked rubber particles has beneficial effects such as faster extrusion rate, reduced die swell, and better molding characteristics. 

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