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Elastomer Technology Development Society, New Delhi CAUSE OF FAILURE OF RUBBER PRODUCTS - TYRE & NON-TYRE Dr. S. N. Chakravarty * President Elastomer Technology.

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Presentation on theme: "Elastomer Technology Development Society, New Delhi CAUSE OF FAILURE OF RUBBER PRODUCTS - TYRE & NON-TYRE Dr. S. N. Chakravarty * President Elastomer Technology."— Presentation transcript:

1 Elastomer Technology Development Society, New Delhi CAUSE OF FAILURE OF RUBBER PRODUCTS - TYRE & NON-TYRE Dr. S. N. Chakravarty * President Elastomer Technology Development Society © Copyright by the Author

2 Elastomer Technology Development Society, New Delhi2 Usage of Rubber Products Rubber products, both Tyre & Non-Tyre, are used in indoor & outdoor application under various conditions. Some are expected to withstand atmospheric conditions (Oxygen, Ozone, Sunlight & UV), others under dynamic condition (flex fatigue, typical example is Tyre which goes thru million cycle of compression & deflection), still some other products need to withstand high temperature and / or in contact to oil & solvent (e.g. automotive components under the hood application).

3 Elastomer Technology Development Society, New Delhi3 Failed Product

4 Elastomer Technology Development Society, New Delhi4 Failed Tyre

5 Elastomer Technology Development Society, New Delhi5 Failed Rubber Seal

6 Elastomer Technology Development Society, New Delhi6 While developing & manufacturing a rubber product all these factors are kept in mind while formulating the compound & curing of the products. Let us see what are different factors which could be the cause of failure of rubber products during usage.

7 Elastomer Technology Development Society, New Delhi7 Application / Service related factors To develop a rubber product most important information required are its application / usage pattern. To find out whether the product is a) subjected to weather conditions – Oxygen / Ozone / UV / Sun Light / UV etc. b) Temperature of usage e) Dynamic application (Flex Fatigue ) d) Abrasion / Wear condition e) Contact with Oil & Solvents, Chemicals, Acid & Alkali etc.

8 Elastomer Technology Development Society, New Delhi8 Specification To develop a product to meet application requirement, basic specification given is followed. It is supposed to give all requirement of properties (e.g. TS, M, SH, Sp. Gr., Abrasion, Flex, Ozone & Oil resistance etc) & retention of these properties over the usage period, judged by carrying out ageing at an elevated temperature.

9 Elastomer Technology Development Society, New Delhi9 Material - Polymer / Elastomer & Ingredients. Depending on requirement from the Product during usage base Elastomer in chosen e.g. a)For normal applications, temp. limited to 70º / 80ºC & no Ozone & Oil resistance etc requirement, NR / SBR / BR rubbers may satisfy. b) In case of higher temp. limit for usage – to go for CR, NBR, CPE, EPDM, HNBR, Silicone & ultimately FKM. c) In case of product coming in contact with Fats & Oils, Solvent etc. choice may be NBR, HNBR, Arcylate & FKM depending on application combination.

10 Elastomer Technology Development Society, New Delhi10 d) For Ozone resistance the choice would be CR, CPE, EPDM, Silicone, FKM depending on severity of application. e) In case of high temp. & Oil / Solvent contact as well as Ozone resistance requirement, choice is limited to FKM. f) For both high & very low temp. application Silicone rubber may be the choice. g) For electrical insulation & resistance property requirement, ECO may be preferred.

11 Elastomer Technology Development Society, New Delhi11 h) Retention of gas / air ( impermeability) property is met by Butyl / Halo butyl rubber. ( Automotive inner tube & inner liner application). i) For high chemical resistance choice are CSM, FKM etc. Wrong choice of base polymer for specific application often is the vital cause of product failure.

12 Elastomer Technology Development Society, New Delhi12 Choice of Polymer as per Temp.

13 Elastomer Technology Development Society, New Delhi13 Compounding Compounding formulation play important role in a product’s performance & life expectancy. Vital are the reinforcement of the product to achieve desired level of physical properties (fillers like Carbon Black gives best protection against deterioration, also Silica / Siliane Coupling agent system provides high ageing resistance) and Curing system (S & Accelerators / Activator choice & phr level in case of diene rubber or other curing agents for special SR).

14 Elastomer Technology Development Society, New Delhi14 E.V.System Efficient vulcanizing (EV) systems are defined as those in which no sulphur or sulphur donor is used for crosslinking purposes. Such vulcanizates are normally associated with a high proportion of monosulphidic and dissulphidic crosslinks in the network. EV system gives vulcanizate with exceptionally good resistance both to reversion and to heat ageing. They are of particular interest for

15 Elastomer Technology Development Society, New Delhi15 -Manufacture of thick articles to avoid uneven cure (e.g. in injection moulding) - Resistance to heat ageing required beyond the capability of antioxidants. -Alternative to expensive non-discolouring antioxidants. Both high accelerator / low sulphur system and the sulphur donor system give good processing safety and excellent resistance to reversion and to ageing.

16 Elastomer Technology Development Society, New Delhi16 Semi-Ev System ( Partial replacement of Sulphur ) Good retention of vulcanizate properties during ageing. With mainly monosulphidic or disulphidic crosslinks these are more resistant to oxidative and thermal degradation than conventional vulcanizates which have a high proportion of polysulphidic cross-links. The efficient systems have low initial fatigue life, but are very stable and show no significant change on ageing. Sulphur- Free Vulcanization System for Diene Rubber Vulcanization with Sulphur Compounds without Free Sulphur

17 Elastomer Technology Development Society, New Delhi17 Vulcanization with Sulphur Donors Crosslininking mechanism which, though not dependent on additions of sulphur nevertheless form effective crosslink sites containing sulphur atoms. These choice & dosage level have bearing on physico – mechanical properties ( SH / TS / M / Tear, Abrasion loss / Wear characteristics, ageing at a higher temp., flex fatigue etc.

18 Elastomer Technology Development Society, New Delhi18 Anti - degredants Choice & dosage level of anti-degredants (antioxidants / antiozonants, M.C. Wax) play important role in product life & performance, Aminic type of anti-degredants are more effective against heat ageing where as p-plylenediamine types are effective against ozone & flex fatigue resistance. In case of non-black products bisphenolic & MBI type are used to a level of success.

19 Elastomer Technology Development Society, New Delhi19 contd. On ageing, vulcanizate (product) degrades & physical properties drop, ultimately to a point that the product fails. Ageing is primarily oxidative (ozone) degradation; heat / sunlight / UV / Copper / Iron in ionic form / flexing all have catalytic effect on degradation. Oxidative ageing breaks down the rubber chain ( unsaturation point ) causing drop in physical properties. Hence, while compounding, one has to protect the product against oxidative and other ageing factors.

20 Elastomer Technology Development Society, New Delhi20 Ageing Mechanism. Initiation ROOH RO + OH Ki. 2 ROOH RO + RO 2 + H 2 O. Kp. Propagation RO + RH ROOH + R. fast. R + O 2 RO 2. Termination 2 R R – R.. R + RO 2 RO 2 R Ki 2 RO 2 Non Radical Products

21 Elastomer Technology Development Society, New Delhi21 Oxidative Ageing of NR The oxidation of a rubber molecule is shown below. CH 3 CH 3 I I. - CH 2 - C = CH – CH 2 – CH 2 – C = CH – CH RO 2 CH 3 CH 3 I I - CH 3 – C = CH – CH – CH 2 – C = CH – CH 2 – CH 3 02 CH 3 I I - CH 2 - C = CH – CH – CH 2 – C = CH – CH 2 – I O O* CH 3 CH 3 I I - CH 2 – C = CH - CH – CH 2 – C – CH – CH 2 – I I O O

22 Elastomer Technology Development Society, New Delhi22 NR & SR are attacked by oxygen even at room temperature and the reaction is accelerated by heat, light and the presence of certain metallic impurities which catalyse the decomposition of the peroxides to form free radicals. Consequently, the addition of an antioxidant is required to minimize oxidative degradation. All hydrocarbon polymers undergo scission as a consequence of thermal oxidation.

23 Elastomer Technology Development Society, New Delhi23 Processing - Dispersion of ingredients Processing steps – Mixing, Extrusion, Calendaring, etc. contribute towards incorporation/ distribution & dispersion of large quantity of fillers – both reinforcing & non- reinforcing in a compound, Dispersion of ingredients is important to achieve desired property level and product performance or premature failure. Improper dispersion of ingredients & presence of grits in a product subjected to flexing will fail prematurely because the stress factor on those points will be different causing failure. Abrasion / wear is also affected.

24 Elastomer Technology Development Society, New Delhi24 Dispersion

25 Elastomer Technology Development Society, New Delhi25 Rubber Stage

26 Elastomer Technology Development Society, New Delhi26 Vulcanizing system Curing system and curing process perhaps the most important criteria in a product’s property level and performance. Physical property level & product performance is based on the crosslink density and nature / type of crosslink formed by vulcanization. Higher Sulphur level in the compound produces more polysulphidic crosslinks which gives higher TS / M as well flex fatigue but has lower resistance to heat (oxidative) ageing by which polysulphidic crosslink’s breaks down to lower sulphidic crosslink and properties fall.

27 Elastomer Technology Development Society, New Delhi27 Stages of Vulcanization 1. Incubation Period 2. Induction stage ( Scorch ) 3. Crosslinking stage 4. Plateau 5. Reversion

28 Elastomer Technology Development Society, New Delhi28 Incubation period During this period, the rubber compound is heated to the curing temperature. Rubber is a bad conductor of heat. For thin walled goods, the incubation period is short but in case of thick-walled rubber goods, the interior of the article may take a fairly long time to get heated to the curing temperature.

29 Elastomer Technology Development Society, New Delhi29 Induction stage The time interval at the curing temperature at which no measurable crosslinking can be observed is know as the induction period. This period depends on the polymer and the curing system used. The induction period represents the safety margin in processing the stock and is an indication of the storage life of the stock. Every compound must have a sufficient induction period so that the compound processes satisfactorily.

30 Elastomer Technology Development Society, New Delhi30 Crosslinking / Plateau Crosslinking This is the period when crosslinking starts, the rate depending on the cure system, the compound and the temperature of cure. Plateau This is the period during which the physical property, after attaining the maximum value, remains constant with continued cure.

31 Elastomer Technology Development Society, New Delhi31 Reversion This occurs in the vulcanization of NR, polyisoprene and butyl rubbers. On prolonged cures, the physical properties of the vulcanizate will start deteriorating. Other SR like SBR, NBR, CR will not generally show reversion.. These five stages are exhibited when sulphur is used as the cross linking agent. When the cure systems other than elemental sulphur are used the reversion stage is generally absent. With sulphur the reversion occurs because of the fact that poysulphidic crosslinkages formed at the earlier stages are rather unstable and break up on continued heating.

32 Elastomer Technology Development Society, New Delhi32 Crosslink & Property Physical property level and product performance is based on the crosslink density and nature / type of crosslink formed by vulcanization. Higher Sulphur level in the compound produces more polysulphidic cross links which gives higher TS / M as well flex fatigue but has lower resistance to heat (oxidative) aging by which polysulphidic crosslink’s breaks down to lower sulphidic crosslink and properties fall.

33 Elastomer Technology Development Society, New Delhi33 contd. Lower sulphur & higher accelerators (specially sulphenamide types) produces more stable crosslink’s and sulphurless curing gives most stable structure which have very good resistance to heat ageing & retains the property level for longer period of product life. Similarly cure temp. & time also have bearing on vulcanizate structure and in turn on ageing effect.

34 Elastomer Technology Development Society, New Delhi34 Vulcanizate Structure

35 Elastomer Technology Development Society, New Delhi35 Vulcanizate Structure

36 Elastomer Technology Development Society, New Delhi36 Product Design - Geometry / Construction / Safety factor. It has been shown that the design of the product has pronounced effect on certain application behaviour / flex fatigue, wear characteristics, compression set etc. Higher the displacement from the “null” point during flexing of a product (e,g tyre sidewall), more pronounced is the oxidative (ozone) effect on the property, faster crack formation leading to failure. Geometry & design of products for specific application like Bridge Bearing Pad, Seismic Insulation Pad, and Railway rubber items are important. Sharp contour / curvature cause early failure. While designing a product adequate “Safety Factor” need to be built in.

37 Elastomer Technology Development Society, New Delhi37 Product Design

38 Elastomer Technology Development Society, New Delhi38

39 Elastomer Technology Development Society, New Delhi39

40 Elastomer Technology Development Society, New Delhi40 Storage conditions Storage conditions are important for product usage after longer storing. Ageing effect continues even at room temperature albeit very slow. Hence it is advised to store the rubber product away from heat, Sunlight & moisture, preferably covered with black poly. Contact with grease, solvent, oil etc. should be strictly avoided. Also FIFO system and storage stack height / rotation should be followed if stored for longer time to avoid any de-shaping.

41 Elastomer Technology Development Society, New Delhi41 Factors playing role in failure of products Till now we saw that following factors play paramount role in the failure of rubber products. 1. Selection of Elastomer / Blend. 2. Reinforcing fillers and Ingredients as well as their proportion in the compound. 3. Curing agents and vulcanization system (proportion, temperature, time & pressure). 4. Reinforcing agent like Cord / Fabric.& Metal / Steel cord.

42 Elastomer Technology Development Society, New Delhi42 Composite Products 1. Tyre ( Most important Example ) 2.Conveyor belt 3.Hose ( braiding / reinforcement )

43 Elastomer Technology Development Society, New Delhi43 Pneumatic Tyre Pneumatic tyre is the most prominent rubber product as the sector consume about 50% of total rubber consumption of the country. Air pumped inside the tyre (body or carcass) carries load of the vehicle. It is air inside the carcass made of rubberized tyre cord – nylon / polyester / steel, is the load bearing part of the tyre. Load bearing capacity increases with increasing air pressure till rupture point (cord strength limit) is reached. Hence, load & inflation pressure are embossed on tyre sidewall as specified in the standard. Tyre designer build in necessary safety factor ( SF ) above this level.

44 Elastomer Technology Development Society, New Delhi44 Pneumatic Tyre

45 Elastomer Technology Development Society, New Delhi45 Improper choice of tyre cord (denier / strength / twist / etc.),design ( not building in required SF etc.) & compounding will lead to premature tyre failure. Wear characteristics of a tyre will have impact on users (customers) of the tyre. Fast wear, tear, crack development will shorten tyre life. Proper choice of polymer, vulcanizing system and protective agents usage can eliminate these.

46 Elastomer Technology Development Society, New Delhi46 Conveyor Belt

47 Elastomer Technology Development Society, New Delhi47 Hose

48 Elastomer Technology Development Society, New Delhi48 Composite Vital factor for product performance is adhesion between rubber & reinforcing cord ( cotton, Nylon Rayon, Polyester, Aramide, and Steel Cord ). Bond failure will lead to product failure due to separation between rubber layer & reinforcing cord / fabric. No adhesion problem is encountered with cotton which can be used for low strength reinforcement. Adhesion becomes critical with Aramid and Steel Cord.These need pretreatment and special additives in the compound to achieve proper bond strength. Important is bond strength under dynamic condition at an elevated temperature.

49 Elastomer Technology Development Society, New Delhi49 Gaskets / Seal / Bush / Car Channels / Engine Mount / Load Bearing Pads – Bridge / Seismic isolation / Railway items. One property i.e. compression set & compression deflection, play vital role in the function of these items, especially at an elevated temperature and in contact with grease / oil / solvent.

50 Elastomer Technology Development Society, New Delhi50 Contact with grease / oil / solvent causes swelling and shrinks on drying, looses sealing property,causing leakage. Many of these products are exposed to weather conditions (Oxygen / Ozone / Sunlight / UV light etc.) which will affect compression set. Besides,crack formation takes place which on propagation, ultimately leads to product failure.

51 Elastomer Technology Development Society, New Delhi51 Elastomer Technology Development Society C/o. Polym Consultants 812, Devika Tower 6, Nehru Place, New Delhi (India) Tel: , Fax: Web:


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