EXPERIMENT 7: RUBBER AGING

7.1 7.1.1 7.1.2

Objective: To follow the oxidative and thermal degradation of several rubber vulcanizates. To study the physical properties of different vulcanizates after they undergo oxidative and thermal degradation.

7.1.3

To compare the result for tensile and tear test before and after aging for all compounds.

7.2

Introduction

The properties and performance of a rubber product depend on many factors including the chemical nature of the rubber, the amount of various kind of ingredients incorporated into the rubber compound, vulcanizing systems, processing condition, design of the product and service conditions. The physical and chemical properties of elastomeric parts will undergo progressive change with time due to aging properties that usually marked by deterioration. Factors that contribute to the deterioration of elastomeric materials include ozone, heat, oxygen, sunlight, certain metal ions, high humidity, high energy radiation, microorganism and pollutants. (Azura, Ahmad & Rohana, 2011)

Rubber compound properties change with time at ambient temperature or at a faster rate from exposure to heat. Therefore, heat aging tests are commonly performed to measure the change in physical properties for a rubber product at a higher temperature which may approximate the actual service temperature or to use heat aging as accelerated aging tests to relate the actual product life at lower temperature and to estimate the degree of change which would take place over much longer times at normal ambient temperature. The degree to which accelerated tests are successful in predicting long term life at ambient temperature is highly debatable but, nevertheless, single point accelerated tests are very widely in specification to give an indication of ageing performance. (John, 2001)

However, there are several reasons heat aging tests do not correlate well with actual service life at lower temperature. First, at elevated temperatures, oxidative effects are

more dominant. Second, oxygen diffusion rates are faster at elevated temperature. Third, the geometry of the test specimens is different from the rubber product, so that exposed surface area-to-volume ratio is different from the quantity of oxygen that diffuse into the test specimens is different from the quantity that can diffuse into the product. This factor explains why there can be poor correlation of a heat aging test only to product performance at lower temperature. (Sadhan & White, 2001)

ASTM D573 describes a standard method for aging of rubber specimens in air ovens. Multiple dumbbell specimens from each of the compounds tested are placed in the oven chamber. Here, dumbbell specimens are aged usually at 70 to 100 c. Some of the test specimens from each compound are tested for tensile properties usually of 2, 4, 7, and 14 days. The percent change from the original un-aged values can be tabulated. In this method, when different test specimens are in the same oven chamber, volatile compounding ingredients such as plasticizers can migrate from one test sample to another, affecting the aging test results. ISO method A is somewhat similar to AST D573, except that the ISO method allows for either single chamber or multi-cell oven. Also, the ISO method is not restricted to only tensile testing. Other tests method includes BS903: Part A 19, DIN 53508 and ASTM D685. (John, 2001) 7.3 Equipments: Oven and Instron tensometer 7.4 Materials: Testing specimens for tensile and tear tests prepared in experiment 4 for all compounds

7.5

Methods: 1. The rubber testing specimens were put in air oven at 100C for 72 hours. 2. After 72 hours had passed, the oven was left for 30 minutes to achieve equilibrium temperature. 3. Then the specimens were cooled slowly at room temperature for 1 hour before cut into dumbbell and trouser shape.

4. Tensile and tear tests were then carried out using Instron tensile machine. 5. For each test, the specimens were run and the value was reported. 6. The condition of the testing specimens was observed. 7.6 Result and Discussion

The rubber aging is reported as the percentage of deviation before and after aging for the following selected mechanical property. The heat aging is generally marked by the deterioration due to action of heat and oxygen in the molecular chain. The degradation of rubbers involves two types of reactions. Softening-type reactions include a decrease in the molecular weight of the polymers due to the main chain scission, while the hardening-type one involves cross-linking reactions.

7.6.1

The tensile and tear properties before and after aging test for all compounds

7.6.1.1 Tensile properties

Tensile strength (MPa)

15 10 5

13.9

3.642 1.011 0.495 1.0592 B Rubber Compound C 1.567

Before Aging After Aging

0 A

Figure 1: The comparison of tensile strength before and after aging for 72 hours for different vulcanization rubber compounds.

Theoretically, the rubber compound will be deteriorated and experience drop in properties especially tensile strength. However, from the figure 1, compound B show an abnormal increase of tensile strength after aging. This can be explained by the problem arise in the CV cured compound B that undergo reversion on prolonged heating in the

experiment 4 (molding). The test specimens prepared by the CV cured compound B is sticky and soft like plastics. Therefore, when come into the aging test, the test specimens can make use of residual curatives to undergo continuous cross linkage and this will increase its tensile properties. However, we can see that the increase in tensile strength is very small from 0.495 MPa to 1.0592 MPa. This is because sulfur that are continuously broken and reformed in compression set test and aging test will make sulfur less active and small amount of agitated sulfur can be activated by the thermal action to create radical on the main polymer chain and the pendant group.

Elongation-at-break (%)

800 600 400 200 0

720.85 560.80 357.5 80 A B Rubber compound C 379.53 341.3 Before Aging After Aging

Figure 2: The comparison of elongation-at-break before and after aging for 72 hours for different vulcanization rubber compounds.

From figure 2, it shows that the Elongation-at-break (EB) for compound C experience the lowest change after subjected to aging process. This can be explained by the thermal stability of C-C bond in peroxide cured system. The small drop in elongation-at-break indicates that some of C-C bond break by the thermal action. Basically, compound A and C experience the decrease of EB while compound B experience a positive deviation of EB value which also indicate an increment. The elongation-at-break drops from 720.85% to 80% in test specimens compound A because most number of C-S2-C bond in disulphidic linkage broken which is lower in bond dissociation energy and the remaining of C-S-C bond in monosulphidic linkage which is higher in bond dissociation energy. The breakage of disulphidic linkage instantaneously at lower bond dissociation energy will account for huge drop in EB. The positive increment in elongation-at-break for CV cured compound B can be explained by the same reason as tensile strength.

Referring to the appendix, each compound experiences different trend of change from M100 to M500. Compound B shows an obviously increase of deviation of modulus which mean increasing of modulus after aging while compound C show a decreasing slope of modulus meaning that the modulus drop after aging process. For compound A, there is no modulus obtained at 100%, 300% and 500% elongation. This is because the test specimen compound breaks at 80% elongation and no modulus obtained for modulus exceed M 80. The modulus increased in CV cured compound B in M100 and M300 shows that the test specimens become stiffer after aging due to continuous cross-linking and its modulus reach M500 before break at M 560.80.

7.6.1.2 Tear properties

Tear resistance (N/mm)

10 8 6 4 2 0

8.7478

3.6564 2.032 2.499 0.5932 A B Rubber compound C 2.121

Before Aging After Aging

Figure 3: The comparison of tear resistance before and after aging for 72 hours for different vulcanization rubber compounds.

The tear resistance of rubber compound A and C decrease after subjected to heat aging which means a lower force is now able to tear the specimen into 2 pieces. However, the CV cured compound B shows abnormal slight increase in tear resistance as the increase in tensile strength for that compound. Tear resistance is strongly affected by degree of vulcanization where low vulcanization temperature and short cure time give high tear resistance. From figure 4, compound C shows the least deviation of tear resistance compared to another two compounds. This can be explained by the thermal stability of the bond to retain the chemical cross linkage to resist the tear stress.

7.6.2

The effect of heat aging on different types vulcanization systems used

The mechanical properties of elastomeric materials before and after aging is highly depend on the type of cross-links formed which is controlled by the different types of vulcanization systems used. The CV cured compound B will exhibit low thermal stability toward aging due to low bond dissociation energy of the CSXC bond in the long sulfur linkage. The low dissociation energy is caused by the flexible nature of sulfur and the bond angle. The long nature of chemical linkage is responsible for the strain-induced crystallization when external forces applied. The rubber chains will slide past on each other on stretching to allow stress relaxation at high stress concentrations. Hence, the stress is distributed uniformly along the 3-D network structures and this phenomenon accounts for high tensile properties and tear properties. However, the heat aging tends to destroy the long sulfur linkage and reform into short sulfur linkage assembly the EV cured system. The CV cured rubber compounds after aging is then expected to show large drop in mechanical property because the formation of lower sulfur rank linkage will inhibit strain-induced crystallization.

The EV cure compound A contains the C-S-C bond with higher bond dissociation energy compared to C- SX-C bond. Before aging, they have the lower mechanical performances than the CV cured compounds because the short cross linkages are easily destroyed by the external load. In addition, the strain-induced crystallization is impossible in EV cured rubber compound. In contrast, they have little drop in mechanical properties after heat aging because more energy have to be gained to overcome the interaction between the stronger C-S-C bond. Hence, the bond tends to be stable and only some bonds that are agitated are broken and this will accounts for lower mechanical drop such as tensile strength.

Peroxide cured compound C shows the lowest deterioration in term of mechanical properties among other compound after aging. Peroxide vulcanization system is a free radical process that leads to the formation of C-C crosslink network. The C-C bond has higher dissociation energy than C-S bond in EV cured compound and S-S bond in CV cured compound and hence better thermal stability. Undoubtedly, stronger bond will

result to a thermal and oxidative stable compound. Thus, it shows the best aging resistance amongst all the compounds.

Density and type of cross-links are changed continuously because new cross-links are formed and the existing cross-links are dissociated by thermal aging. Reversion of the compound with the sulfur cure systems especially EV system for the aging can be explained with the remained curative residues and pendent sulphide groups remaining in the compound. Formation of new cross-links in rubber vulcanize by the thermal aging comes from curative complex and pendent sulphide groups terminated with cure accelerator residues as well as the free sulfur. The remained curatives residues also able to generate more pendent sulphide group which may reduce the strain induced crystallization and thus reduce the mechanical properties. On the other hand, in sulfur cured compound may contain free elemental sulfur due to poor homogenize mixing under-cured condition and enable it to generate the curative complex during been subjected to a higher temperature and thus form more cross-link in the compound. This may explain why the compound B experiences an increase of tensile property although been subjected to aging process.

7.6.3

The effect of increasing oven temperature used from 100C to 150C for 72 hours to the rubber compound A and B

The mechanical property of rubber compound that cured with EV system and CV system have notable difference in aging test that done in 100C and 150C for 72 hours. At higher temperature, the rubber chains that are in random coiled conformation are able to undergo larger extent of segmental motion from one reference point to the other point. The higher thermal activity of the polymer chain will cause the breakage of cross-link chain by collision and vibration of the bond.

The dissociation reactions of the sulfur linkages will be more and more activated by increasing the temperature. The dissociation reactions of the existing sulfur cross-links are more activated than the combination reactions as the aging temperature increases and the combination reactions between the pendent groups can occur even at low

temperature. Thus, the crosslink density of the vulcanize decreases for the thermal aging at higher temperature (150C) but it increases for the thermal aging at lower temperature (100C).

In CV cured compound B, the sulfur linkage tends to break and reform into the linkage of lower sulfur rank with chain modification, thereby increasing the total number of crosslinks. The lack of long flexible sulfur linkage reduces the tendency of strain-induced crystallization when the external load applied. The higher aging temperature will make a very great drop in tensile properties and the tear properties in rubber compound B. This is because high temperature will contribute more kinetic energy transmitted along main backbone chain and each backbone will attain more kinetic energy relatively. The S-S bond will break easily due to higher kinetic energy obtained by the bond. This will reduce the number of polysulphidic linkages that are responsible for mechanical performance due to ability of strain-induced crystallization.

Since compound A with monosulphidic linkages are more resistance to thermal degradation compare with polysulphidic crosslink in compound B as discussed

previously, compound A will show lower drop in the mechanical property if the temperature used change from 100C and 150C. Whereas, peroxide cured compound C that comprise of C-C bond are very stable and higher thermal energy must be acquired to break the bonds. This means that compound C will shows little drop in mechanical property in a wide range of temperature from 100C and 150C.

7.7

Conclusion

After aging, changes in the cross-link densities negatively affect the tensile and tear properties. Generally, after aging, tensile properties and tear resistant values for compound A and C will decrease but abnormal increase in these properties are observed in compound A. Among all compounds, peroxide cured compound C shows the lowest deterioration in term of mechanical properties. Vulcanizes with high bond strength crosslink (CC, peroxide cured compound C) are superior in thermal stability than those of sulfur-cured compounds, with lower bond strength (CSXC and C-S-C bonds in compound B and A respectively) based on change in ultimate elongation. This

gives compound C the best aging resistance amongst all the compounds. Crosslink breakage and reformation in natural rubber cured with CV systems lead to scission and modification of the chains, thus reducing their strain-induced crystallization and lead to drop of properties. Increasing the temperature of aging will accelerate the aging process and give poorer tensile and tear properties to the rubber compounds. This is because the increase in temperature will provide more energy for chain scission and reformation. Reference (1) John. S. D (2001). Rubber Technology: Compounding and Testing for Performances. USA: Hanser Gardner Publication (2) Y.S. Rohana Yahya, A.R. Azura* and Z. Ahmad (2011). Effect of curing systems on thermal degradation behavior of natural rubber (SMR CV 60). Journal of Physical Science, Vol. 22(2), 1-14 (3) White. J.R & Sadhan K.De. (2002). Rubber Technologists Handbook. United Kingdom: Rapra Technology Ltd.

Appendix Table 1: Tensile properties of compounds A, B, C before and after aging at 100oC for 72 hours Compound Tensile Strength (MPa) A Before After B Before After C Before After 0.495 1.0592 3.642 1.567 357.50 560.8 379.18 341.13 0.151 0.1791 0.618 0.4619 0.359 0.4445 2.352 1.3067 0.8527 3.642 13.900 1.011 720.85 80.00 0.636 2.162 3.923 Elongation at Break (%) M100 (MPa) M300 (MPa) M500 (MPa)

Table 2: Tear properties of compounds A, B, C before and after aging at 100oC for 72 hours Compound Vulcanization System Maximum Load (kN) Maximum Load Thickness (N/mm)

A B

Before After Before After

Efficient (EV) Conventional (CV) Peroxide

0.01604 0.00075 0.00037 0.00450 0.00728 0.00420

8.7478 0.5392 2.0320 2.4990 3.6564 2.1210

Before After

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Table 3: Tensile properties of every specimen of compound A, B and C after aging at 100C for 72 hour Compound Test Piece Tensile Stress (MPa) Maximum Strain (%) M100 (MPa) M300 (MPa) M500 (MPa)

1 0.5701 40.00 2 1.2070 91.67 3 1.1420 93.33 4 1.0700 81.67 5 1.0670 93.33 Average 1.011 80.00 B 1 0.9204 543.3 0.1822 0.4474 0.8126 2* 1.0760 605.0 0.2284 0.4797 0.8126 3* 0.7469 481.7 0.1371 0.4035 -0..0946 4 1.1980 578.3 0.1760 0.4416 0.8927 5* 1.0930 618.3 0.1890 0.4409 0.7868 Average 1.0592 560.8 0.1791 0.4445 0.8527 C 1 1.756 366.7 0.4814 1.320 2 1.531 345.0 0.4457 1.260 3 1.414 311.7 0.4587 1.340 4* 1.222 286.7 0.4599 Average 1.567 341.13 0.4619 1.3067 (* indicates the results obtained is invalid because it does not break at gauge length region)

This means that the tensile properties like tensile strength, tensile modulus and elongation-at-break is averaged only for the test pieces that break at gauge length region because the respective area used to calculate the tensile stress is lie between the gauge length region.

For example,

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Table 4: Tear properties of every specimens of compound A, B and C after aging at 100C for 72 hour Compound Sample Maximum Load (kN) 0.0009 0.0009 0.0010 0.0012 0.00075 0.0046 0.0042 0.0047 0.00450 0.0046 0.0036 0.0043 0.00420 Maximum Load / Thickness (N/mm) 0.5051 0.4287 0.5824 0.6407 0.5392 2.5550 2.3720 2.5700 2.4990 2.311 1.839 2.213 2.1210

1 2 3 4 Average 1 2 3 Average 1 2 3 Average

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