20 6. REFERENCES [1] Maurice Morton, Rubber Technology, Robert E. Krieger Publishing Company Inc., Krieger Drive, Malabar, Florida [2] W.F. Billmeyer, “Chemistry of Natural and Synthetic Rubber”, in Textbook of Polymer Science. Wiley inter-science Pub., New York, 1981 [3] F.E. Okiemen, J.E. Imanah, “Characterization of agricultural waste products as fillers in natural rubber formulation”. Nig. J. Polymer. Technology, 2003 [4] F. Lyon, K. Burgess, Encyclopedia of Polymer Science and Engineering, 2nd Ed., Vol. 2, John Wiley & Sons, New York, 1985 [5] J.J. Brennan, T.E. Jermyn, “Properties of black reinforced blends of natural rubber and butadiene rubber”, Journal of Applied Science, Volume. 9, 1965 [6] V.M. Murty, S.K. De, Rubber Chemistry and Technology, 1982 [7] G.A. Prentice, M.C. Williams, “Numerical evaluation of the state of cure in a vulcanizing article”, in Rubber Chemistry & Technology, 1980 [8] “Carbon black”. IARC Monograph. Vol. 93, 2010 [9] Tyre technology international - 2007, published by UKIP media and events Ltd., Abinger house, Church Street, Dorking surrey RH4 1DF, UK, 2007 [10] A.Y. Coran. J.E. Mark. B. Erman. F.R. Enrich. “Science and Technology of Rubber, 2nd edition”, Academic press, 1994 [11] Meng-Jiao Wang. “The effect of polymer-filler and filler-filler interactions on dynamic properties of rubber application”, Rubber Chemistry and Technology, 1997 [12] “Reinforcement of Elastomers”, G. Kraus, Inter science publisher, 1965, Chap 3, pp. 69-114 [13] “The physics of rubber elasticity”, Treloar L. R. G., Third edition, Oxford, Clarinda Press (1975) [14] G.E. Warnaka. “Dynamic strain effects in Elastomers”, Rubber Chemistry and Technology, 1963, Vol. 36 [15] J.B. Putman and M.C. Putman. “A simplified approach to QC testing”, Rubber World, Vol. 229, Jan. 2004 21 APPENDICES Appendix - A ASTM Test Method of Iodine Adsorption Number This method covers a procedure for determining the iodine number of carbon blacks. It is indicative of the surface area of black and serves to differentiate between the various grades of carbon blacks. Equipment: 1. 50ml centrifuge tube with ground glass stopper or suitable alternative 2. Centrifuge or sintered glass crucible, G4 3. 19 x 150mm test tubes 4. 10ml pipettes 5. 25ml pipettes 6. 25ml Burette 7. 50ml Erlenmeyer Flasks 8. Oven 9. Desiccators 10. Analytical Balance 11. 1000 ml Filtering Flask Reagents: 1. Iodine crystals, A.R. 2. Potassium Iodide, A.R. 3. Sodium Thiosulphate Pentahydrate crystals, A.R. 4. Iodine Solution (Approximately 0.0473N) – Dissolve 6g of Iodine and 57.0g of potassium iodide in 30ml of distilled water in one liter volumetric flask. Shake thoroughly to ensure complete dissolution and then dilute it to 1000ml with distilled water. 5. Sodium Thiosulphate solution (0.0394N) – Dissolve 9.781g of Sodium Thiosulphate Pentahydrate (Na2S2O3.5H2O) in approximately 500ml of distilled water in one liter volumetric flask. Add 5ml of n-methyl Alcohol and dilute 1000ml with distilled water. 6. Starch reagent grade 7. Starch indicator solution – Dissolve 2.5g of starch in 1000ml of distilled water. Boil well to ensure proper solution before storage in bottle. 22 Procedure: Standardize the iodine solution as follows: a). Weigh about 0.2g of Sodium Thiosulphate to nearest 0.0001g. b). Dissolve in about 50ml of distilled water in 250ml Erlenmeyer flask. c). Add about 5ml of starch indicator and titrate with the iodine solution until the solution changes from colorless to blue. d). Record the ml of Iodine solution used and then see “calculations” to determine the normality of the Iodine solution. e). Run a duplicate determination. Note: The Iodine solution must be standardized every day or every time used. 1. Dry an adequate sample of carbon black for 1 h at 105deg. C. 2. Cool the dry carbon black in a Desiccator. 3. Weigh exactly 0.5000g of dried sample into a 50ml centrifuge tube. Note: For SAF type carbon black weigh a 0.2500g sample. 4. Pipette 25.0ml of Iodine solution into the tube and stopper immediately. 5. Shake the Iodine-carbon black mix vigorously for one minute at no less than 120 strokes per minute. Note: Through mixing of carbon black and Iodine solution is necessary. 6. Centrifuge immediately for approximately two minutes. 7. If filtration is used instead of centrifuge, wait for five minutes after shaking, then filter. a). Filter with slight suction through a clean, dry, filter crucible into a clean, dry, 19 x 150mm. test tube placed under the end of the crucible holder inside a 1000ml filtering flask. b). The end of the crucible holder should be above the surface of the solution in the test tube after filtering. 8. If a centrifuge is used, filtration is not necessary and the solution may be decanted into a 50ml beaker. 9. Immediately after decanting or filtering the Iodine solution into the beaker, pipette 10.0ml into a 50ml Erlenmeyer flask. 10. Titrate the Iodine solution with 0.0394N Sodium Thiosulphate solution until pale yellow colour remains. 23 11. Add approximately 5ml of the starch indicator solution and continue titrating until one drop of Sodium Thiosulphate solution causes the blue colour to the change to colourless. Record the amount of Sodium Thiosulphate used in the titration. 12. Run duplicate blank determinations by taking 10ml portions of the standard Iodine solution and following steps 10, 11 and 12. 13. See calculations for determining the Iodine number. Calculations: 1. Normality of Iodine solution = Wt. of Sodium Thiosulphate ml of Iodine sol x 0.2482 2. Where 0.5000g sample is used: I = B-S x N x 50 x 126.91 B Where 0.2500g sample is used: I = B-S x N x 12691 B Where, I = Iodine adsorption number in mg of Iodine per g of carbon black. B = ml of Sodium Thiosulphate solution required for titration of the blank. S = ml of Sodium Thiosulphate solution required for titration of the sample. N = Normality of Iodine solution 24 To simplify calculations, the above formula can be modified as follows: When the blank titration is carried out 20ml of the Iodine solution is titrated against 0.0394 N Sodium Thiosulphate solution which can be considered as a standard solution. ∴ N x 20 = B x 0.0394 Hence, substituting “N” in the above formula by B x 0.0394 20 I = (B-S) x B x 0.0394 x 12691 B 20 i.e. I = (B-S) x 25.001 25 Appendix - B Designed Tyre Inner Liner Compound Formula for different proportionate in between N330 & PHCB Different ratios between N330 and PHCB are designed as following tables. Table A.2.1 Inner Liner Compound formula Sample 1 (Existing Tyre Inner Liner Formula) Sample 2 Ingredient Std. Wt. (kg) Batch Wt. (kg) Ingredient Std. Wt. (kg) Batch Wt. (kg) RSS4 70 0.06417 RSS4 70 0.06417 Reclaim 60 0.05500 Reclaim 60 0.05500 N-330 50 0.04584 N-330 40 0.03667 PHCB 0 0.00000 PHCB 10 0.00917 Process Oil 3 0.00275 Process Oil 3 0.00275 Kaolin 50 0.04584 Kaolin 50 0.04584 Peptizer 0.15 0.00014 Peptizer 0.15 0.00014 ZnO 5 0.00458 ZnO 5 0.00458 Stearic Acid 1 0.00092 Stearic Acid 1 0.00092 6ppd 0.75 0.00069 6ppd 0.75 0.00069 Pine Tar 2 0.00183 Pine Tar 2 0.00183 TBBS 0.9 0.00083 TBBS 0.9 0.00083 Sulphur 2.4 0.00220 Sulphur 2.4 0.00220 TMTD 0.1 0.00009 TMTD 0.1 0.00009 PVI 0.14 0.00013 PVI 0.14 0.00013 TOTAL 245.44 0.225 TOTAL 245.44 0.225 26 Table A.2.2 Inner Liner Compound formula Sample 3 Sample 4 Ingredient Std. Wt. (kg) Batch Wt. (kg) Ingredient Std. Wt. (kg) Batch Wt. (kg) RSS4 70 0.06417 RSS4 70 0.06417 Reclaim 60 0.05500 Reclaim 60 0.05500 N-330 30 0.02750 N-330 25 0.02292 PHCB 20 0.01833 PHCB 25 0.02292 Process Oil 3 0.00275 Process Oil 3 0.00275 Kaolin 50 0.04584 Kaolin 50 0.04584 Peptizer 0.15 0.00014 Peptizer 0.15 0.00014 ZnO 5 0.00458 ZnO 5 0.00458 Stearic Acid 1 0.00092 Stearic Acid 1 0.00092 6ppd 0.75 0.00069 6ppd 0.75 0.00069 Pine Tar 2 0.00183 Pine Tar 2 0.00183 TBBS 0.9 0.00083 TBBS 0.9 0.00083 Sulphur 2.4 0.00220 Sulphur 2.4 0.00220 TMTD 0.1 0.00009 TMTD 0.1 0.00009 PVI 0.14 0.00013 PVI 0.14 0.00013 TOTAL 245.44 0.225 TOTAL 245.44 0.225 27 Table A.2.3 Inner Liner Compound formula Sample 5 Sample 6 Ingredient Std. Wt. (kg) Batch Wt. (kg) Ingredient Std. Wt. (kg) Batch Wt. (kg) RSS4 70 0.06417 RSS4 70 0.06417 Reclaim 60 0.05500 Reclaim 60 0.05500 N-330 20 0.01833 N-330 10 0.00917 PHCB 30 0.02750 PHCB 40 0.03667 Process Oil 3 0.00275 Process Oil 3 0.00275 Kaolin 50 0.04584 Kaolin 50 0.04584 Peptizer 0.15 0.00014 Peptizer 0.15 0.00014 ZnO 5 0.00458 ZnO 5 0.00458 Stearic Acid 1 0.00092 Stearic Acid 1 0.00092 6ppd 0.75 0.00069 6ppd 0.75 0.00069 Pine Tar 2 0.00183 Pine Tar 2 0.00183 TBBS 0.9 0.00083 TBBS 0.9 0.00083 Sulphur 2.4 0.00220 Sulphur 2.4 0.00220 TMTD 0.1 0.00009 TMTD 0.1 0.00009 PVI 0.14 0.00013 PVI 0.14 0.00013 TOTAL 245.44 0.225 TOTAL 245.44 0.225 28 Table A.2.4 Inner Liner Compound formula (Only PHCB in place of N330) Sample 7 Ingredient Std. Wt. (kg) Batch Wt. (kg) RSS4 70 0.06417 Reclaim 60 0.05500 N-330 0 0.00000 PHCB 50 0.04584 Process Oil 3 0.00275 Kaolin 50 0.04584 Peptizer 0.15 0.00014 ZnO 5 0.00458 Stearic Acid 1 0.00092 6ppd 0.75 0.00069 Pine Tar 2 0.00183 TBBS 0.9 0.00083 Sulphur 2.4 0.00220 TMTD 0.1 0.00009 PVI 0.14 0.00013 TOTAL 245.44 0.225 29 Appendix - C Cost Saving Calculation PHCB Usage for inner liner compound 1kg Price for N330 180 LKR 1kg Price for PHCB 75 LKR N330 kg per batch existing formula (Sample 1) 50 kg N330 kg per batch new formula (Sample 3) 30 kg PHCB kg per batch new formula (Sample 3) 20 kg Existing formula (Sample 1)- N330 per batch cost 9000 LKR New formula (Sample 1)- N330 and PHCB per batch cost 6900 LKR Per batch saving 2100 LKR Per kg Saving 8.61 LKR Monthly average inner liner compound consumption 6000 kg Monthly total saving 51639 LKR 30 Appendix - D R h eo -g ra p h – S am p le 1 31 R h eo -g ra p h – S am p le 2 ,3 ,4 32 R h eo -g ra p h – S am p le 5 ,6 33 R h eo -g ra p h – S am p le 7