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   rec.crafts.metalworking      Metal working and metallurgy      215,319 messages   

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   Message 213,904 of 215,319   
   Clare Snyder to All   
   Re: 1991 ranger brake problem - CO2 & O3   
   14 Nov 24 20:55:24   
   
   From: clare@snyder.on.ca   
      
   On Thu, 14 Nov 2024 12:31:00 -0700, Bob La Londe    
   wrote:   
      
   >On 11/13/2024 4:58 PM, Jim Wilkins wrote:   
   >> "Bob La Londe"  wrote in message news:vh38u5$2dg8a$2@dont-email.me...   
   >>   
   >> On 11/13/2024 3:09 PM, Snag wrote:   
   >>   
   >>>    I thought it was exposure to sunlight/UV that caused most of the   
   >>> sidewall degradation ... or are those aftermarket tire covers (in   
   >>> particular for RV's and campers) just another scam ?   
   >>   
   >>   
   >> Yeah I don't know for sure.  UV is certainly capable of damaging a lot   
   >> of things.  I do know CO2 is an issue with some rubbers.  I was told   
   >> by... well somebody... that tires were among them.   
   >>   
   >   
   >Nobody likes to be wrong, so I did some look ups.   
   >   
   >CO2 is said to contribute to the breakdown of rubber on several sites.   
   >Some say "distressed" CO2 and others just generically say CO2.  O3 also   
   >contributes to the break down of rubbers and is more reactive.  Then I   
   >looked at concentrations per a few other references.  They say CO2 is   
   >present at ground level from 300 to 900 PPM (million) where as O3 is   
   >typically present at 20-30 PPB (billion).   
   >   
   >As to whether the difference in available molecules makes a real   
   >difference in which has more net affect I do not know, but the numbers   
   >do make you think.   
   >   
   >I recall now where I first ran across the reference to CO2 and its   
   >reactivity with rubbers.  I don't recall exactly who it was (could have   
   >been Bob Sterne), but it was in regards to tuning, building, and   
   >repairing airguns.  Admittedly air can be quite distressed in a spring   
   >piston gun generating enough sudden compression to detonate oils or in a   
   >PCP gun where air can be stored at pressures as high as 4500PSI.  Over   
   >300 bar for the metric crowd.   
   >   
   >I'm not saying I was right and you were wrong.  Not at all.  I could   
   >very well be wrong still.  My "expertise" with material science is   
   >limited to rote memory and blue collar experience.  I'm just stating it   
   >might not be as cut and dried as as it seems.  I would argue in full on   
   >flat Earther fashion... "Nothing is ever totally settled science."  LOL.   
   >   
   >--   
   >Bob La Londe   
   >CNC Molds N Stuff   
      
    From Wiki   
      
   iny traces of ozone in the air will attack double bonds in rubber   
   chains, with natural rubber, polybutadiene, styrene-butadiene rubber   
   and nitrile rubber being most sensitive to degradation.[1] Every   
   repeat unit in the first three materials has a double bond, so every   
   unit can be degraded by ozone. Nitrile rubber is a copolymer of   
   butadiene and acrylonitrile units, but the proportion of acrylonitrile   
   is usually lower than butadiene, so attack occurs. Butyl rubber is   
   more resistant but still has a small number of double bonds in its   
   chains, so attack is possible. Exposed surfaces are attacked first,   
   the density of cracks varying with ozone gas concentration. The higher   
   the concentration, the greater the number of cracks formed.   
      
   Ozone-resistant elastomers include EPDM, fluoroelastomers like Viton   
   and polychloroprene rubbers like Neoprene. Attack is less likely   
   because double bonds form a very small proportion of the chains, and   
   with the latter, the chlorination reduces the electron density in the   
   double bonds, therefore lowering their propensity to react with ozone.   
   Silicone rubber, Hypalon and polyurethanes are also ozone-resistant.   
   Form of cracking   
   Macrophotograph of ozone cracking in NBR (Nitrile Butadiene Rubber)   
   diaphragm seal   
      
   Ozone cracks form in products under tension, but the critical strain   
   is very small. The cracks are always oriented at right angles to the   
   strain axis, so will form around the circumference in a rubber tube   
   bent over. Such cracks are very dangerous when they occur in fuel   
   pipes because the cracks will grow from the outside exposed surfaces   
   into the bore of the pipe, so fuel leakage and fire may follow. Seals   
   are also susceptible to attack, such as diaphragm seals in air lines.   
   Such seals are often critical for the operation of pneumatic controls,   
   and if a crack penetrates the seal, all functions of the system can be   
   lost. Nitrile rubber seals are commonly used in pneumatic systems   
   because of its oil resistance. However, if ozone gas is present,   
   cracking will occur in the seals unless preventative measures are   
   taken. Ozone attack will occur at the most sensitive zones in a seal,   
   especially sharp corners where the strain is greatest when the seal is   
   flexing in use. The corners represent stress concentrations, so the   
   tension is at a maximum when the diaphragm of the seal is bent under   
   air pressure.   
      
   The reaction occurring between double bonds and ozone is known as   
   ozonolysis when one molecule of the gas reacts with the double bond:   
   A generalized scheme of ozonolysis   
      
   The immediate result is formation of an ozonide, which then decomposes   
   rapidly so that the double bond is cleaved. This is the critical step   
   in chain breakage when polymers are attacked. The strength of polymers   
   depends on the chain molecular weight or degree of polymerization, the   
   higher the chain length, the greater the mechanical strength (such as   
   tensile strength). By cleaving the chain, the molecular weight drops   
   rapidly and there comes a point when it has little strength   
   whatsoever, and a crack forms. Further attack occurs in the freshly   
   exposed crack surfaces and the crack grows steadily until it completes   
   a circuit and the product separates or fails. In the case of a seal or   
   a tube, failure occurs when the wall of the device is penetrated.   
      
   The carbonyl end groups which are formed are usually aldehydes or   
   ketones, which can oxidise further to carboxylic acids. The net result   
   is a high concentration of elemental oxygen on the crack surfaces,   
   which can be detected using energy-dispersive X-ray spectroscopy in   
   the environmental SEM, or ESEM. The spectrum at left shows the high   
   oxygen peak compared with a constant sulfur peak.   
      
   --- SoupGate-Win32 v1.05   
    * Origin: you cannot sedate... all the things you hate (1:229/2)   

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