Steel cords brass-coated

Tire Cord. Melamine resins are also used to improve the adhesion of mbber to reinforcing cord in tires. Textile cord is normally coated with a latex dip solution composed of a vinylpyridine—styrene—butadiene latex mbber containing resorcinol—formaldehyde resin.. The dip coat is cured prior to use. The dip coat improves the adhesion of the textile cord to mbber. Further improvement in adhesion is provided by adding resorcinol and hexa(methoxymethyl) melamine [3089-11 -0] (HMMM) to the mbber compound which is in contact with the textile cord. The HMMM resin and resorcinol cross-link during mbber vulcanization and cure to form an interpenetrating polymer within the mbber matrix which strengthens or reinforces the mbber and increases adhesion to the textile cord. Brass-coated steel cord is also widely used in tires for reinforcement. Steel belts and bead wire are common apphcations. Again, HMMM resins and resorcinol [108-46-3] are used in the mbber compound which is in contact with the steel cord to reinforce the mbber and increase the adhesion of the mbber to the steel cord. This use of melamine resins is described in the patent Hterature (49). 

Insoluble Sulfur. In natural mbber compounds, insoluble sulfur is used for adhesion to brass-coated wire, a necessary component in steel-belted radial tires. The adhesion of mbber to the brass-plated steel cord during vulcanization improves with high sulfur levels ( 3.5%). Ordinary rhombic sulfur blooms at this dose level. Crystals of sulfur on the surface to be bonded destroy building tack and lead to premature failure of the tire. Rubber mixtures containing insoluble sulfur must be kept cool (<100°C) or the amorphous polymeric form converts to rhombic crystals. 

Adhesives in the Tire Industry. Cobalt salts are used to improve the adhesion of mbber to steel. The steel cord must be coated with a layer of brass. During the vulcanization of the mbber, sulfur species react with the copper and zinc in the brass and the process of copper sulfide formation helps to bond the steel to the mbber. This adhesion may be further improved by the incorporation of cobalt soaps into the mbber prior to vulcanization (53,54) (see Tire cords). 

Recently, van Ooij et al. have reviewed adhesion of steel tire cord to rubber (van Ooij et al., 2009). The authors reviewed the literature extensively and provided an updated model for adhesion to brass-plated tire cord, which incorporated observations made by many techniques. They discussed the effects of different compounding ingredients and the possible alternatives to the current brass coatings. They note that the use of cobalt compounds improves the adhesion between rubber and brass-coated cords, but new adhesion promoters have been developed as replacements for Co, or for combined use with Co. They also discussed the use of phenolic-resin adhesion promoters. They describe the various techniques that have been developed to study the rubber-brass interface and its aging mechanism. 

The thin coating of brass on the steel cord is the primary adhesive used in steel-to-rubber bonding. The quality of this bonding system built up during vulcanization of, for example, a radial tire will influence the performance of the steel ply or steel belt in the tire and, ultimately, the durability of the product. Though the mechanism of bond formation in rubber-steel cord adhesion is very complex, a brief review of the current understanding of wire to rubber adhesion is presented. 

The adhesive layer between the rubber and cord is generally considered to be formed by the interaction between the copper and the vulcanization system. As a result of this, optimization of the vulcanization system with respect to adhesion is critical. Also, a change in the composition of the brass coating on the steel wires, or a change in the thickness, can require a change in the vulcanization system in order to maintain the optimum level of adhesion. 

The bond is not unduly sensitive to influences such as humidity, low mix viscosity and low vulcanizing pressures. The main drawbacks are connected with the plating process, which requires considerable investment and expertise. Brass plating has now been largely superseded by the use of proprietaiy bonding agents, except in the tyre industry, where bonding to brass-coated steel cords is still undertaken. ... 

The brass-steel couple is a very unfavourable one from a corrosion standpoint. The presence of the brass coating accelerates steel corrosion when water and salt reach the cords through punctures. However, improved cord constructions and tyre designs have largely eliminated this problem. Water and salt can no longer propagate along the entire circumference of the tyre, as the rubber fills the capillaries of the cords because of the more open cord constructions that have been developed in recent years. 

Rubber tyre cord adhesion W J VAN OOlJ Adhesion to brass-coated steel Rubber-based adhesives J M MARTfN MARTInEZ General introduction Rubber-based adhesives compounding J M MARTIN MARTfNEZ Formulations, etc. 

Tyre cord adhesion W J VAN OOIJ Adhesion to brass-coated steel... 

Both of these curatives are added in the lower temperature, final mixing stage. HMTA must be isolated from the other rubber curatives during storage and batch preparation since its basicity can cause premature decomposition of the rubber cure accelerators and can accelerate the conversion of insoluble sulfur into the soluble form. The structure of HMTA and the reaction with resorcinol are illustrated in Scheme 4.1. Classical chemical studies indicate that as much as 75% of nitrogen remains chemically bonded to the rubber though some ammonia is released during the cure of the resin and the rubber, which can have detrimental effects on rubber composites reinforced with brass coated steel cords. 

A low cobalt and boron-containing additive was also described by Bobrov [37], although their materials were not specified. It was shown that the effect of a resorcinol derivative (aminolysis of the brass coating), could be negated by the cobalt-boron additive, resulting in a high-modulus belt compound with a high corrosion resistance of the steel cord. 

Overall this new process is very attractive and has several environmental advantages, if it could replace brass on steel tyre cords. Tests with silane-treated tyre cords are in progress. The authors proposed use of a new tyre cord without brass coating but with a zinc coating instead, as tyre cords without brass coating are difficult to manufacture (the brass lubricates the die in the final wire drawing process). The final zinc-plated cord is then passed through a silane bath and dried. Quite remarkable in this system is that the silane-based film does not impair the adhesion of brass to sulphur-cured compound. If the adhesion of a brass plated cord is mediocre, the silane process actually improves its performance, as shown in Table 6.1 [58]. 

The other major development that needs to be recapped here is that of silane systems for bonding a wide range of metals to a wide range of compound types and formulations. This process may become a panacea for bonding in many industries, but much more work will have to be done before the process can replace the brass-coating process for bonding rubber steel to tyre cords. 

Steel cord has been the main reinforcing material for tyres, hoses and conveyor belts for many decades, indeed the first steel reinforced tyres appeared over ninety years ago. However, it was not until the emergence of radial tyres that steel cord became a common form of reinforcement and understandably the adhesion between brass-coated steel cord and rubber compound became a significant factor governing the performance and durability of car and truck tyres. Therefore, it is necessary to achieve a high level of adhesion and sustain this level throughout the service history of the tyre. 

Figure 7.1 Diagram of brass-coated steel cord surface (Reproduced with permission from W. J. Van Ooij, Rubber Chemistry and Technology, 1984, 57, 421, Figure 10. 1984, Rubber Division, American Chemical Society, Inc.)...

The influence of polymers and additives on the service life of non-tread tyre components is discussed on the basis of results obtained from studies of inner liner, belt and sidewall compounds. The effects of the bromine content of bromobutyl rubbers on the performance of inner hners, and of sulphenamide accelerators on the adhesion of NR belt compounds to brass coated steel cords were investigated. The mechanical properties and ageing and ozone resistance of black sidewall compounds consisting of NR blends with neodymium catalysed polybutadiene protected with different antioxidants and antiozonants were also evaluated. 5 refs. 

Zinc oxide is essential in rubber technology because it is the most commonly used activator for sulfur cure systems. Just about every rubber compound that uses sulfur as the vulcanizing agent will most likely contain a small amount of zinc oxide to activate the cure. Also zinc is alloyed with copper to form brass. Special brass-plated steel tire cord is a primary reinforcing material for producing steel-belted radial tires. The brass coating of the steel tire cord enables very good rubber-to-metal adhesion. Therefore, zinc metal and zinc oxide are very important to the rubber industry. 

Cobalt is important to the rubber industry to promote rubber-to-metal adhesion. The use of cobalt salts, such as cobalt stearate or cobalt naphthenate as compounding additives, will promote better adhesion between cured rubber and brass-coated steel tire cord. 

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