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Mechanical and Oil Resistance Characteristics of Rubber Blends

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Mechanical and Oil Resistance Characteristics of Rubber Blends ELASTOMERE UND KUNSTSTOFFE ELASTOMERS AND PLASTICS NBR · CR · PVC · Rubber blends · Mechanical and Oil Resistance Vulcanizing system · Oil resistance Different rubber blends based on nitrile butadiene rubber, NBR (N3980–39% Characteristics of Rubber acrylonitrile) have been prepared to get a product with high oil resistant and good mechanical properties. The Blends Based on Nitrile obtained mixes included NBR, chloro- prene rubber (CR) and polyvinyl chlo- 1 ride (PVC). The ratio of each component Butadiene Rubber (NBR, CR and PVC) as binary or ternary blend system has been varied and the corresponding vulcanizing systems have been carefully selected. It has been found that the type of rubber and the composition of blends markedly affect their oil resistance. In contrast, the type of crosslinks and crosslinking Blending of polymers has gained much in- (NR). The elastomeric composite has excel- density slightly affect the oil resistance terest, since about 3-4 decades ago, due to lent compatibility between two rubbers of of the corresponding vulcanizates. the fact that, it can be used to produce new different polarity when properly com- polymeric materials, i.e, compositions with pounded and processed. Anmin, et al. [12] specific properties suitable for certain spe- prepared hydrogenated nitrile rubber Mechanische Eigenschaften und cial application. Nitrile rubber (NBR) is wide- (HNBR)/clay nanocomposites using conven- Ölbeständigkeit von NBR ly used in many applications like oil seals, tional two-roll mill mixing technique. They Verschnitten gaskets, etc. The performance of NBR can found that adding organoclay in HNBR be improved by blending with various poly- elastomer greatly improves material ther- NBR · CR · PVC · Kautschukverschnitte · mers [1-4]. The interaction of polymeric ma- mal stability and aging performance in dif- Vulkanisationssysteme · terials with different solvents or liquids is a ferent medium at elevated temperature. Ölbeständigkeit problem from both the academic and tech- Severe, et al. [13] produced dynamic vul- Verschnitte aus NBR und CR bzw. PVC nological points of view. In the literature, canizates from HNBR and three different wurden hergestellt um eine hohe there is a noticeable shortage of reports oil resistant elastomers. These are CR, EIR, Ölbeständigkeit und gute mechanische dealing with the influence of oils on the me- and carboxylated nitrile rubber (XNBR). Eigenschaften zu erzielen. Das Ver- chanical and the properties of polar diene They concluded that the dynamically vul- schnittverhältnis wurde variert und das rubbers, e.g., the chloroprene and the nitrile canized blends held up better under oil ag- Vernetzungssystem angepasst. Es rubbers. The vulcanizates based on these ing than under air aging. Sulekha and wurde gefunden, dass die Konstitution rubbers swelled in oils only to a limited de- Joseph [14] studied the efficiency and per- des Polymeren und das Verschnittver- hältnis die Ölbeständigkeit maßgeblich gree, although the aforementioned publica- manence of polymer hound antioxidants beeinflussen. Im Gegensatz hierzu tions show that even limited swelling may like polyisobutylene bound paraphenylen- haben die Art der Vernetzung und die cause hazardous changes of rubber parts ediamine (PIB-PD) and chlorinated paraffin Vernetzungsdicht eine untergeordnete performance [5-7]. wax bound paraphenylene diamine (CPW- Wirkung. Magryta Jacek, et al. [8] showed that even a PD) in NBR vulcanizates. The vulcanizates small degree of swelling of the vulcanizates showed improved aging resistance in com- causes decrease of their mechanical prop- parison to vulcanizates containing conven- erties and considerable changes of the dy- tional antioxidant. The liquid polymer namic characteristics of CR and NBR. Patil bound antioxidants reduce the amount of and Coolbaugh [9] summarized some of the plasticizer required for compounding. The advantages and limitations of commercial elastomers with special emphasis on their oil-resistant character Oyama, et al. [10] re- late invented an oil-resistant rubber com- position having excellent solvent crack re- sistance comprising a partially hydrogenat- Authors ed unsaturated nitrile/conjugated diene A.M.Omran, A.M.Youssef, copolymer rubber and a liquid unsaturated M.M.Ahmed, and E.M.Abdel-Bary, nitrile/conjugated diene copolymer. Telang R.T.L.Hellipolis Cairo, (Egypt) and Manjanath [11] made the rubber com- posite from a unique blend of nitrile rubber, Corresponding author: polychloroprene (neoprene), epoxidised Prof. E.M.Abdel-Bary German University in Cairo natural rubber (EIR) and natural rubber New Cairo City, Egypt Tel. +20 |2| 185665479 1 Paper given at IRC 2009, Nuremberg, june 29. to E-mail: july 02.,2009 [email protected] KGK · Mai 2010 197 ELASTOMERE UND KUNSTSTOFFE ELASTOMERS AND PLASTICS present work is aiming to study the charac- 1 Formulations of NBR and CR with different vulcanizing systems. teristics of NBR belnded with polychloro- MIXTURE CODE MN1 MN2 MN3 MN4 MN5 MN6 MN7 MN8 MC1 MC2 prene (CR) or polyvinylchloride ( PVC). Thus, NBR 100 100 100 100 100 100 100 100 - - the properties of the corresponding rubber CR - - - - - - - - 100 100 mixes and vulcanites as well as the effects St. Acid 1 1 1 1 1 1 1 1 1 1 of blend compositions on their oil and fuel Zn O 5 5 5 5 5 5 5 5 5 5 resistant are evaluated. ZA 4010 1 1 1 1 1 1 1 1 1 1 Mg O - - - - - - - - 4 4 Experimental C.B.(GPF) 45 45 45 45 45 45 45 45 45 45 DBP 5 5 5 5 5 5 5 5 5 5 Materials The basic materials used in this work are: CBS 0.7 - - - - - - - - - Acrylonitrile butadiene rubber (NBR, MBT - - - - 1 - - - - - N3980 – 39% acrylonitrile, Mooney Viscos- MBTS - 1 0.5 - 1 - - - - - ity (ML-4 (100oC): 80, EINE CHEM, ITALY), DOTG - - - - - 1 1 - - - Chloroprene rubber (CR, Mooney Viscosity TMTD - - 0.7 2 2.5 3 3 - - - (ML-4 (100oC): 75-90, Bayer, Germany), Poly- S 2.5 2.5 2.5 0.5 - 0.5 - - - - vinyl Chloride (PVC, K-Value 70, SABIC mar- ETU - - - - - - - - 2 3 keting ltd. An affiliate of SABIC, KSA), Zinc DCP - - - - - - - 3 - - Oxide (ZnO, Bayer, Germany), Magnesium Oxide (MgO, Bayer, Germany), sulphur (S, 2 Formulations of NBR and CR with different blend ratios. Dammam, KSA), tetramethylthiuram disul- BLEND CODE B1 B2 B3 B4 B5 B6 B7 phide (TMTD, Bayer, Germany), ethylene NBR 100 90 70 50 30 10 - thiourea of 2-mercapto imidazole (ETU, CR - 10 30 50 70 90 100 Bayer, Germany), 2-mercaptobenzthiazol St. Acid 1 1 1 1 1 1 1 (MBT, Bayer, Germany), dibenzothiazyl di- Zn O 5 5 5 5 5 5 5 sulphide (MBTS, Bayer, Germany), N-cy- ZA 4010 1 1 1 1 1 1 1 clohexyl-1,2-benzothiazyl sulphenamide Mg O - 0.4 1.2 2 2.8 3.6 4 (CBS, Bayer, Germany), diortho-tolyl guani- C.B.(GPF) 45 45 45 45 45 45 45 dine (DOTG, Bayer, Germany), dicumyl per- DBP 5 5 5 5 5 5 5 oxide (DCP, TAIpel, Taiwan). MBTS 0.5 0.45 0.35 0.25 0.15 0.05 - TMTD 0.7 0.63 0.49 0.35 0.21 0.07 - Recipes S 2.5 2.25 1.75 1.25 0.75 0.25 - Basic formulations used for choose the vul- ETU - 0.2 0.6 1 1.4 1.8 2 canizing system for NBR and CR mixtures, and those for determining the best blend Formulations of NBR with different ratios of PVC compositions of NBR/CR and NBR/PVC 3 BLEND CODE B B B B B B B blends are shown in Table 1. 11 22 33 44 55 66 77 NBR 100 100 100 100 100 100 100 Techniques and methods PVC 0 10 30 50 70 90 100 St. Acid 1 1 1 1 1 1 1 Mixing and compounding Zn O 5 5 5 5 5 5 5 Mixing of NBR and CR mixtures were car- ZA 4010 1 1 1 1 1 1 1 ried out on a laboratory open two roll mill C.B.(GPF) 45 45 45 45 45 45 45 (400mm. diameters and 600mm. working DBP 5 6.7 10.2 13.6 17 20.5 22.2 length). The gear friction of the mill is 1:1.4. MBTS 0.5 0.5 0.5 0.5 0.5 0.5 0.5 The hollow rolls were cooled by using flush- TMTD 0.7 0.7 0.7 0.7 0.7 0.7 0.7 ing water in order to regulate the tempera- S 2.5 2.5 2.5 2.5 2.5 2.5 2.5 ture not exceeding 60 oC during the differ- ent stages of mixing according to ASTM D-15-627. The rubber mixes obtained were ing Disc Rheometer (ODR) model 4308 from R[ MC90 ML tC90 tL ](2) sheeted and left for a period of at least 6 hrs Zwick, Germany. The measured parameters before testing. are: ML – minimum torque, MH – maximum Where – tL is the time of ML. The addition of ingredients during mixing torque, tS2 – time to 2 units of torque in- These measurements were accomplished was carried following the same order and crease above minimum, MC90 – torque at according to ASTM D-2084. conditions of mixing. The used rubber for- 90% of full torque development, where mulations are given in Tables1-3. Preparation of the test samples MC90 ML [ MH ML ¸90100] (1) The rubber mixes were compression mold- Rheology measurements ed at 150o2˚C, using an electrically heated The cure characteristics of rubber com- In addition tC90 was measured – equivalent hydraulic press at their optimum cure time pounds were carried out using an Oscillat- to optimum cure time, the cure rate: derived from rheological measurements. 198 KGK · Mai 2010 1 2 1 Rheometric characteristics of NBR/CR blends 2 Physico-mechanical properties of the different NBR/CR blends 3 4 3 Equilibrium swelling percent % in engine and hydraulic oils of the 4 Equilibrium swelling percent % in Diesel and gasoline of the different NBR/CR blends different NBR/CR blends The applied hydraulic force during vulcani- Physico-mechanical properties of the Swelling of the test samples zation attained 50 Kgf/cm2.
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