Vulcanizate

Propellants cast into rockets are commonly case-bonded to the motors to achieve maximum volumetric loading density. The interior of the motor is thoroughly cleaned, coated using an insulating material, and then lined with a composition to which the propellant binder adheres under the environmental stresses of the system. The insulation material is generally a mbber-type composition, filled with siUca, titanium dioxide, or potassium titanate. SiUca-filled nitrate mbber and vulcanizable ethylene—propylene mbber have been used. The liner generally consists of the same base polymer as is used in the propellant. It is usually appHed in a thin layer, and may be partially or fully cured before the propellant is poured into the rocket. 

Magnesium oxide is a typical acid scavenger for chlorinated mbbers. Compounds containing zinc oxide or magnesium oxide may tend to swell upon immersion in water. These inorganic salts have some water solubiHty and osmotic pressure causes the vulcanizates to imbibe water to equalize pressure (8,9). As such, vulcanizates tend to sweU more in fresh (distilled) water than in salt water. To minimize water sweU, insoluble salts such as lead oxides can be substituted. Because of the health concerns associated with lead, there is much mbber industry interest in other acid acceptors, such as synthetic... 

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). 

Many antioxidants ia these classes are volatile to some extent at elevated temperatures and almost all antioxidants are readily extracted from their vulcanizates by the proper solvent. These disadvantages have become more pronounced as performance requirements for mbber products have been iacreased. Higher operating temperatures and the need for improved oxidation resistance under conditions of repeated extraction have accelerated the search for new techniques for polymer stabilization. Carpet backiag, seals, gaskets, and hose are some examples where high temperatures and/or solvent extraction can combine to deplete a mbber product of its antioxidant and thus lead to its oxidative deterioration faster (38,40). 

Types of Latex Compounds. For comparison with dry-mbber compounds, some examples of various latex compounds and the physical properties of their vulcanizates are given in Table 23. Recipes of natural mbber latex compounds, including one without antioxidant, and data on tensile strength and elongation of sheets made from those, both before and after accelerated aging, are also Hsted. The effects of curing ingredients, accelerator, and antioxidant are also Hsted. Table 24 also includes similar data for an SBR latex compound. A phenoHc antioxidant was used in all cases. 

Plasticity Retention Index. The oxidation behavior of natural mbber may affect both the processing characteristics and final vulcanizate performance, and the plasticity retention index (PRI) test can be used to give an indication of both. Natural antioxidants present in natural mbber give some protection and a measure of the efficacy of protection is given by PRI. PRI% = P q j Pq x 100, where Pq is the initial Wallace plasticity and P q is the... 

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). 

Table 3. Properties of Carbon Black-Filled Natural Rubber Vulcanizates With Various Cure Systems ...

Waxes are one of the two general classes of commercial antiozonants. Waxes are derived from petroleum and are of two common types, paraffin and microcrystalline (20—23). Typical carbon numbers are n = 20 50 for paraffin waxes and n = 30 70 for microcrystalline materials. If a wax is present ia a vulcanizate at a concentration exceeding its solubiUty, some of it will migrate to the mbber surface where it can form a physical barrier to prevent the penetration of ozone. Waxes, of course, are essentially unreactive towards ozone so that there is no appreciable chemical protection. Commercial waxes are... 

The ash content of furnace blacks is normally a few tenths of a percent but in some products may be as high as one percent. The chief sources of ash are the water used to quench the hot black from the reactors during manufacture and for wet pelletizing the black. The hardness of the water, and the amount used determines the ash content of the products. The ash consists principally of the salts and oxides of calcium, magnesium, and sodium and accounts for the basic pH (8—10) commonly found in furnace blacks. In some products potassium, in small amounts, is present in the ash content. Potassium salts are used in most carbon black manufacture to control stmcture and mbber vulcanizate modulus (22). The basic mineral salts and oxides have a slight accelerating effect on the vulcanization reaction in mbber. 

Mamzen Oil Co. has developed various Ziegler-Natta catalysts that can produce poly(butadiene-i //-prop5iene) (PBR) (78). PBR shows tack (self-adhesion) and green (unvulcanized) dynamic properties superior to those of BR and EPDM. Carbon black-loaded vulcanizates can be compounded to give high strength and elongation at break (79,80). PBR can also be covulcanized with SBR, BR, and EPDM. 

Two kinds of monomers are present in acryUc elastomers backbone monomers and cure-site monomers. Backbone monomers are acryUc esters that constitute the majority of the polymer chain (up to 99%), and determine the physical and chemical properties of the polymer and the performance of the vulcanizates. Cure-site monomers simultaneously present a double bond available for polymerization with acrylates and a moiety reactive with specific compounds in order to faciUtate the vulcanization process. 

As a general rule ziac oxide is not used because it is not iavolved ia the vulcanization mechanism of acryflc mbber. Ziac salts, eg, ziac stearate, have to be avoided because they may adversely affect the performance of the compound and/or the vulcanizate. 

Polyisobutylene has the chemical properties of a saturated hydrocarbon. The unsaturated end groups undergo reactions typical of a hindered olefin and are used, particularly in the case of low mol wt materials, as a route to modification eg, the introduction of amine groups to produce dispersants for lubricating oils. The in-chain unsaturation in butyl mbber is attacked by atmospheric ozone, and unless protected can lead to cracking of strained vulcanizates. Oxidative degradation, which leads to chain cleavage, is slow, and the polymers are protected by antioxidants (75). 

Polyisobutylene and isobutylene—isoprene copolymers are considered to have no chronic hazard associated with exposure under normal industrial use. Some grades can be used in chewing-gum base, and are regulated by the PDA in 21 CPR 172.615. Vulcanized products prepared from butyl mbber or halogenated butyl mbber contain small amounts of toxic materials as a result of the particular vulcanization chemistry. Although many vulcanizates are inert, eg, zinc oxide cured chlorobutyl is used extensively in pharmaceutical stoppers, specific recommendations should be sought from suppHers. 

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. 

The most widely used plasticizers are paraffinic oils. Por appHcations that specify high use temperatures, or for peroxide cures, paraffinic oils of low volatihty are definitely recommended. However, since paraffinic oils exude at low temperatures from EPDM vulcanizates, or from high ethylene EPDMs, they are often blended with naphthenic oils. On the other hand, naphthenic oils interfere with peroxide cures. Aromatic oils reduce the mechanical properties of vulcanizates, and they also interfere with peroxide cures. Therefore, they are not recommended for EPM/EPDM. 

Mechanical properties depend considerably on the stmctural characteristics of the EPM/EPDM and the type and amount of fillers in the compound. A wide range of hardnesses can be obtained with EPM/EPDM vulcanisates. The elastic properties are by far superior to those of many other synthetic mbber vulcanizates, particularly of butyl mbber, but they do not reach the level obtained with NR or SBR vulcanizates. The resistance to compression set is surprisingly good, in particular for EPDM with a high ENB content. 

The resistance to heat and aging of optimized EPM/EPDM vulcanizates is better than that of SBR and NR. Peroxide-cured EPM can, for instance, be exposed for 1000 h at 150°C without significant hardening. Particularly noteworthy is the ozone resistance of EPM/EPDM vulcanizates. Even after exposure for many months to ozone-rich air of 100 pphm, the vulcanizates will not be seriously harmed. EPM/EPDM vulcanizates have an excellent resistance to chemicals, such as dilute acids, alkaUes, alcohol, etc. This is in contrast to the resistance to aUphatic, aromatic, or chlorinated hydrocarbons. EPM/EPDM vulcanizates swell considerably in these nonpolar media. 

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