Irradiation vulcanization

The use of high energy radiation for vulcanization is therefore mainly of academic interest. Different unvulcanized rubbers behave differently in irradiation vulcanization . The irradiation of unvulcanized rubbers gives similar results to irradiating vulcanized rubbers when a splitting reaction takes. 

Over the last few decades, the use of radiation sources for industrial applications has been widespread. The areas of radiation applications are as follows (i) Wires and cables (ii) heat shrinkable tubes and films (iii) polymeric foam (iv) coating on wooden panels (v) coating on thin film-video/audio tapes (vi) printing and lithography (vii) degradation of polymers (viii) irradiation of diamonds (ix) vulcanization of mbber and rubber latex (x) grain irradiation. 

EB irradiation (like the other ionizing radiation techniques) can bring about the vulcanization of saturated chemically inert polymers which cannot be achieved in the conventional thermochemical curing methods [44]. 

The prevulcanization of natural rubber in latex form has also been a subject of much investigation. The cross-linking mechanism is not yet fully understood, but the water apparently plays a major role in it. Irradiation results in the cross-linking of the rubber molecules and in coarsening of the latex particles. A process of cross-linking of natural rubber latex has been developed to the point that it can be used for an industrial-scale application. The irradiation is performed in aqueous media by electron beam without a prorad (sensitizer) at a dose of 200 kGy (20 Mrad) or in the presence of n-butyl acrylate at considerably lower doses, typically 15 kGy. The cross-linked film exhibits physical properties comparable to those obtained from sulfur cured (vulcanized) film. As an alternative, the addition of a variety of chloroal-kanes makes it possible to achieve a maximum tensile strength with radiation doses of less than 5 Mrad (50 kGy). ... 

A process of cross-linking of natural rubber latex has been developed to where it should be soon ready for an industrial-scale process.149 The irradiation is performed in aqueous media by electron beam without a prorad ( sensitizer ) at a dose of 200 kGy (20 Mrad) or, in the presence of n-butyl acrylate at considerably lower doses, typically 15 kGy. The cross-linked film exhibits physical properties comparable to those obtained from sulfur-cured (vulcanized) film. 

In the case of rubber this cross linking is called vulcanization. Experiments conducted in 1946 at the Clinton Pile (D6) demonstrated a slight curing action of pile irradiation on natural rubber. Charlesby has shown that the degree of cross linking is directly proportional to radiation dose. Approximately 50 X 106 r. produces one cross link/90 isoprene units. 

The new absorptions in the spectra of crosslinked rubber are assigned on the basis of 13C solution NMR chemical shifts for a variety of model compounds, such as pentenes and mono-, di- and tri-sulfidic compounds, by using the 13C chemical shift substituent effect. From the calculated values for particular structural units, the experimental spectra of a sulfur vulcanized natural rubber 194,195,106), natural rubber cured by accelerated sulfur vulcanization 197 y-irradiation crosslinked natural rubber198 and peroxide crosslinked natural rubber and cis-polybutadiene 193 1991 are assigned. 

Early work in this field was conducted prior to the availability of powerful radiation sources. In 1929, E. B. Newton "vulcanized" rubber sheets with cathode-rays (16). Several studies were carried out during and immediately after world war II in order to determine the damage caused by radiation to insulators and other plastic materials intended for use in radiation fields (17, 18, 19). M. Dole reported research carried out by Rose on the effect of reactor radiation on thin films of polyethylene irradiated either in air or under vacuum (20). However, worldwide interest in the radiation chemistry of polymers arose after Arthur Charlesby showed in 1952 that polyethylene was converted by irradiation into a non-soluble and non-melting cross-linked material (21). It should be emphasized, that in 1952, the only cross-linking process practiced in industry was the "vulcanization" of rubber. The fact that polyethylene, a paraffinic (and therefore by definition a chemically "inert") polymer could react under simple irradiation and become converted into a new material with improved properties looked like a "miracle" to many outsiders and even to experts in the art. More miracles were therefore expected from radiation sources which were hastily acquired by industry in the 1950 s. 

Many filled systems are exposed to irradiation during processing or use. Such processes include radiation crosslinking and vulcanization, development of antistatic properties, production of y-radiation shields, and sterilization. The effect of fillers in these applications is studied. 

Radiation vulcanization of carbon fiber reinforced styrene-butadiene rubber causes a substantial increase in crosslink density (Figure 11.4) and tensile strength (Figure 11.5). This magnitude of change is possible only when the interaction between the filler and the matrix is improved. When irradiated in the presence of air, carbon fibers gain functionality which substantially increases their adhesion resulting in a spectacular improvement in properties. SEM studies show that as the dose of radiation increases, the adhesion of the... 

The adhesive properties, coupled with the fact that monomer I was shown to be a vulcanizing agent for rubber (15), indicated that the polymer might make a suitable tire-cord adhesive. The data in Table III demonstrate the adhesive properties of the polymer, which may be data and R. Kindle for the adhesion data. Irradiation work was done by D. I. Relyea at the Uniroyal Reseach Center in Wayne, N. J. 

The degradative radiation-recycling of PTFE led to a successful pilot-scale plant producing 12 tons/year recycled powder at Sumitomo, Japan [9], For similar polymerdegrading industrial developments several other candidates are very promising. Among other synthetic polymer products, discarded automobile tires represent a major environmental concern, in an amount close to 10 Mtons/a. A promising method is mentioned in the literature [9] in which the vulcanized rubber product is crushed at low temperature, irradiated at a dose rate of 100 kGy, and milled repeatedly, if necessary. The reclaimed de-crosslinked material can be added to an extent 10 - 15% to various new rubber blends. 

Polymers are the materials most often treated by radiation. Therefore in the recent past the IAEA has organized Cooordinated Research Projects (CRPs) in closely related areas, namely the stability and stabilization of polymers under irradiation, the radiation vulcanization of natural rubber latex, the modification of polymers for biomedical applications such as the radiation synthesis of membranes, hydrogels and adsorbents. 

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