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    Presentation1 Degradation Mechanism of Rubber

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    sangleminh36
    Rubber compounds can be degraded through several mechanisms including oxidation, ozone, light, heat, and metal ions. Oxidation generally results in hardening or softening of rubber and is initiated by free radicals forming through bond cleavage. Ozone degradation primarily affects the surface and causes discoloration and cracking. Antioxidants inhibit oxidation through several modes including metal deactivation, free radical termination, and peroxide decomposition. The rate of oxidation increases in the presence of metal ions and ultraviolet light.

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    Presentation1 Degradation Mechanism of Rubber

    Uploaded by

    sangleminh36
    210 views33 pages
    Rubber compounds can be degraded through several mechanisms including oxidation, ozone, light, heat, and metal ions. Oxidation generally results in hardening or softening of rubber and is initiated by free radicals forming through bond cleavage. Ozone degradation primarily affects the surface and causes discoloration and cracking. Antioxidants inhibit oxidation through several modes including metal deactivation, free radical termination, and peroxide decomposition. The rate of oxidation increases in the presence of metal ions and ultraviolet light.

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    Rubber compounds can be degraded through several mechanisms including oxidation, ozone, light, heat, and metal ions. Oxidation generally results in hardening or softening of rubber and is initiated by free radicals forming through bond cleavage. Ozone degradation primarily affects the surface and causes discoloration and cracking. Antioxidants inhibit oxidation through several modes including metal deactivation, free radical termination, and peroxide decomposition. The rate of oxidation increases in the presence of metal ions and ultraviolet light.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    210 views33 pages

    Presentation1 Degradation Mechanism of Rubber

    Uploaded by

    sangleminh36
    Rubber compounds can be degraded through several mechanisms including oxidation, ozone, light, heat, and metal ions. Oxidation generally results in hardening or softening of rubber and is initiated by free radicals forming through bond cleavage. Ozone degradation primarily affects the surface and causes discoloration and cracking. Antioxidants inhibit oxidation through several modes including metal deactivation, free radical termination, and peroxide decomposition. The rate of oxidation increases in the presence of metal ions and ultraviolet light.

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    The key takeaways are that rubber compounds can be degraded by reactions with oxygen, ozone, light, metal ions and heat. Degradation by oxygen and ozone proceeds via different chemical mechanisms and results in different effects on the physical properties of rubber.

    Rubber compounds can be degraded by reactions with oxygen, ozone, light, metal ions and heat.

    Oxygen degradation results in hardening or softening of rubber properties, while ozone degradation results in discoloration and eventual cracking of rubber samples. Ozone degradation is primarily a surface phenomenon.

    DEGRADATION MECANISM

    Rubber compounds can be degraded by

    reactions with oxygen, ozone, light, metal ions and heat Degradation by oxygen and ozone proceeds via different chemical mechanism and results in different effects on physical properties of rubber

    Oxygen degradation results in hardening

    (SBR, NBR, CR, EPDM ) or softening (NR, IR, IIR) throughout the rubber article Rubbers that do not contain C=C unsaturation are less sensitive to oxidation than diene rubbers

    Ozone degradation results in discoloration


    and eventual cracking of samples Ozone degradation is primarily a surface phenomenon

    Mechanism of rubber oxidation


    Initiation
    RH R-R R* + O2 R* + 2R* ROO* H*

    Shear, T
    Shear, T

    Propagation ROO* + RH ROOH ROOH + RH RO* + RH OH* + RH

    R* + ROOH RO* + OH* ROH + R* +H2O ROH + R* HOH + R*

    Termination ROO* + R*
    RO* + R*

    ROOR ROR

    R* + R*

    RR

    The key to the process is the initial


    formation of a free-radical species.

    At high temperatures and at large shear

    forces, free radical formation takes place by cleavage of carbon-carbon and carbonhydrogen bonds

    trace impurities present in the polymer

    systems could account for the relative ease of oxidation Due to the high reactivity of free radicals, only trace amounts of these peroxides need to be present to provide initiation of the oxidative chain process

    The rate of peroxide decomposition and the resultant rate of oxidation is markedly increased by the presence of ions of metals such as iron, copper, manganese, and cobalt

    ROOH + Fe2+ ROOH + Fe3+

    RO* + Fe3+ + OHROO* + Fe2+ + H+

    It is important to control and limit the amounts of metal impurities in raw rubber

    Probably an important pro-oxidant for all


    rubbers is ultraviolet light

    Stabilization mechanism of antioxidants


    Five general modes of oxidation inhibition are commonly recognized: - Metal deactivators (EDTA)

    - Light absorbers (ZnO, TiO2, C.B) - Peroxide decomposers (Mercaptants, thiophenol , other organic sulfur compounds) - Free radical chain stoppers - Inhibitor regenerators

    Termination of propagating radicals during


    the oxidative chain reaction is believe to be the dominant mechanism by which amine and phenolic antioxidant operate. The resulting antioxidant radical is more stable than the initial peroxy radical and terminates by reaction with another radical in the system

    It is important that the level of antioxidant be kept at the optimum, since excess antioxidant can result in a pro-oxidant effect (A-H + O2 AOOH).

    The secondary antioxidant react with the hydroperoxide resulting in an oxidized antioxidant and an alcohol

    Free radicals develop in a polymer system

    and react with oxygen yielding a free radical peroxy. This free radical, in turn, reacts with a C-H linkage yielding a peroxide and another free radical. This is the chain reaction which continues until it is halted.

    It is generally agreed that antioxidant-free


    radicals are not reactive and are, thus, effective chain stoppers.

    Methods of studying the oxidation resistance of rubber


    Accelerated aging DSC TGA Spectroscopic techniques SEM techniques

    Ozone and Antiozonant Chemistry

    Mechanism of ozone attack on elastomers

    Ozone reacts with double bond of rubber to form ozonide (I). These ozonide cleave as soon as they are formed to give an aldehyde or ketone and a zwitterion (carbonyl oxide)

    Although the cracking of rubbers is related to

    the reaction of ozone on the double bond, it must be mentioned that ozone reacts also with sulfur crosslinks.

    These reactions however are much slower.


    The reaction of ozone with di- and polysulfides is
    at least 50 times slower than the corresponding reaction with olefins.

    RSSSR + O3 SO2 + RSO2-O-SO2R (+ H2O) 2 RSO2H

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