Rate 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. 

Activators. Activators are chemicals that increase the rate of vulcanization by reacting first with the accelerators to form mbber soluble complexes. These complexes then react with the sulfur to achieve vulcanization. The most common activators are combinations of zinc oxide and stearic acid. Other metal oxides have been used for specific purposes, ie, lead, cadmium, etc, and other fatty acids used include lauric, oleic, and propionic acids. Soluble zinc salts of fatty acid such as zinc 2-ethyIhexanoate are also used, and these mbber-soluble activators are effective in natural mbber to produce low set, low creep compounds used in load-bearing appHcations. Weak amines and amino alcohols have also been used as activators in combination with the metal oxides. 

Rubber. The mbber industry consumes finely ground metallic selenium and Selenac (selenium diethyl dithiocarbamate, R. T. Vanderbilt). Both are used with natural mbber and styrene—butadiene mbber (SBR) to increase the rate of vulcanization and improve the aging and mechanical properties of sulfudess and low sulfur stocks. Selenac is also used as an accelerator in butyl mbber and as an activator for other types of accelerators, eg, thiazoles (see Rubber chemicals). Selenium compounds are useflil as antioxidants (qv), uv stabilizers, (qv), bonding agents, carbon black activators, and polymerization additives. Selenac improves the adhesion of polyester fibers to mbber. 

Blends of diene and backbone-saturated mbbers are frequently used in appHcations where discoloration by chemical antiozonants caimot be tolerated, yet where cost is stiH a primary consideration (eg, white sidewalls of tires). Disadvantages are that physical properties have to be compromised and the two mbbers usually differ greatly in their rates of vulcanization. Usually, at least a 25% replacement by the ozone-resistant mbber is needed for an appreciable enhancement in ozone protection (6). 

Vulcanization. Some of the chlorine atoms along the chain (1,2 units) are very labile and reactive, and provide excellent sites for cross-linking. Hence neoprene is not vulcanized by sulfur but by metal oxides, eg, magnesium and zinc oxides, although sulfur is generally included in the compound to control the rate of vulcanization. 

Table 14.2 provides comparisons of the different classes of accelerators based on their rates of vulcanization. The secondary accelerators are seldom used alone, but are generally found in combination with primary accelerators to gain faster cures. 

Accelerators are second in importance only to sulphur. Their function is to accelerate the normally slow rubber-sulphur reaction, increase the rate of vulcanization, and increase productivity. Accelerators are classified into two main classes by types, namely organic and inorganic. The inorganic accelerators such as lime, litharge and other lead compounds and magnesia were employed extensively before the introduction of organic accelerators. They are still used mainly to produce hard rubber or ebonite products. Litharge is used in rubberized fabrics, insulated wires and cables and shoe compounds as well as chemical resistant rubber products... 

The rate of vulcanization of many of the industrial rubber compounds is very rapid. This is because of demands and constraints... 

An increase of Av to a constant value was observed in the course of vulcanization of polysulphide rubbers in the presence of sodium dichromate. Rates of vulcanization were determined from the time dependence of Av, as the reciprocal time at which Av reaches the maximum constant value. It is found that the rate of vulcanization linearly increases with the oxidizer concentration37. ... 

Zinc oxide (ZnO, wurtzite structure) eliminates oxygen on heating to form nonstoichio-metric colored phases, Zni+xO with x < 70 ppm. ZnO is almost transparent and is used as white pigment, polymer stabilizer, emollient in zinc ointments, creams and lotions, as well as in the production of Zu2Si04 for TV screens. A major application is in the rubber industry to lower the temperatures and to raise the rate of vulcanization. Furthermore, it is an n-type semiconductor (band gap 3.37 eV) and shows piezoelectric properties, making zinc oxide useful for microsensor devices and micromachined actuators. Other applications include gas sensors , solar cell windows and surface acoustic devices. ZnO has also been considered for spintronic application because of theoretical predictions of room-temperature ferromagnetism . 

Rubber Chemicals. Sodium nitrite is an important raw material in the manufacture of mbber processing chemicals. Accelerators, retarders, antioxidants (qv), and antiozonants (qv) are the types of compounds made using sodium nitrite. Accelerators, eg, thiuram [137-26-8] gready increase the rate of vulcanization and lead to marked improvement in mbber quality. Retarders, on the other hand (eg, N-nitrosodiphenylamine [156-10-5]) delay the onset of vulcanization but do not inhibit the subsequent process rate. Antioxidants and antiozonants, sometimes referred to as antidegradants, serve to slow the rate of oxidation by acting as chain stoppers, transfer agents, and peroxide decomposers. A commonly used antioxidant is A/,A7-disubstituted Nphenylenediamine which can employ sodium nitrite in its manufacture (see Rubber chemicals). 

Densified polyurethane foam was used as a filler in rubber in an attempt to recycle this material. Small additions (up to 30%) did not much affect the cure rate but as the quantity was increased the rate of vulcanization slowed probably due to the effect of dilution and increasing viscosity. 

For small strains the stress-relaxation rate of vulcanized rubbers at long times is proportional to tan 8 (178). This will also be true at large strains if strain-time factorization applies. The implication of this for the results of Cotten and Boonstra (150) is that tan 8 in unswollen vulcanizates is only little affected by carbon black-polymer interactions at strain levels between 75 and 250% elongation (and at very low frequencies) and suggests that the substantial increases in tan 8 observed in filled rubbers at small strains are due primarily to the effects of secondary filler aggregation. 

Accelerators of the curing process that allow control of the time and rate of vulcanization, as well as the number and type of sulfur crosslinks which are formed. Typical accelerators include guanidines, mercaptobenzo-thiazoles and sulfenamides, etc. 

Both the rate of vulcanization after the scorch period and the final extent of vulcanization are now measured by using devices called cure meters. Many researchers have contributed to this development (Decker et al., 1963 Juve et al., 1964). Widely used cure meters are oscillating disc rheometers of the type introduced by the Monsanto Company around 1965. The development of the oscillating disc rheometer, largely through the efforts of Wise, was the beginning of modern vulcometry, which has become standard practice in the industry. Before the development of the cure meter, it was necessary to measure... 

Accelerators are products that increase both the rate of sulfur crosslinking in a rubber compound and crosslink density. Secondary accelerators, when added to primary accelerators, increase the rate of vulcanization and degree of crosslinking, with the terms primary and secondary being essentially arbitrary. A feature of such binary acceleration systems is the phenomenon of synergism. Where a combination of accelerators is synergistic, its effect is always more powerful than the added effects of the individual components. 

Rate of vulcanization Ultra-accelerators include dithiocarbamates and xanthates. Semiultra-accelerators include thiurams and amines. Fast accelerators are thiazoles and sulfonamides. A medium-rate system is diphenylguanidine. A slow accelerator is thiocarbanilide. 

Factors involved in the selection of vulcanization systems must include the type of elastomer, type and quantity of zinc oxide and fatty acid, rate of vulcanization, required resistance to fatigue, and service conditions. It is also recommended that use of nitrosamine-generating accelerators be avoided. 

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