Coagent J. Zhao, G. Ghebremeskel and J. Peasely Port Neches (USA) EPDM SBR Blends Peroxide cure Sulfur cure Coagent The objective of this study is to ad- dress the replacement of up to 30 parts of EPDM with SBR to reduce the cost of finished products and to improve selected blend properties using more efficient cure systems. Effects of sulfur, peroxide, and coa- gent curing systems on blend prop- erties were studied. It was found that the addition of a small amounts of sulfur as a coagent to the perox- ide cure system in EPDM/SBR com- pounds remarkably improved me- chanical properties of the blends. Important compound properties in- cluding: mechanical properties, compression set, heat aging, and ozone resistance of the EPDM/SBR blends are also compared with those of EPDM compounds. Eigenschaften von EPDM/SBR Mischungen vernetzt mit Per- oxid und Schwefelcoagenzien EPDM SBR Mischungen Per- oxidvernetzung Schwefelvernet- zung Coagentien Die Untersuchung zielt auf den Er- satz von 30 Teilen EPDM durch SBR, um die Kosten von Fertigprodukten zu senken und die Wirkung eines effizienten Vernetzungssystems auf die Eigenschaftsverbesserung zu bewerten. Die Wirkungen von Ver- netzungssystemen wie Schwefel, Peroxid und Coagentien wurden un- tersucht. Es wurde gefunden, da die Zugabe geringer Mengen Schwefel als Coagens von Peroxid- systemen zu einer beachtenswerten Verbesserung der mechanischen Ei- genschaften von EPDM/SBR-Com- pounds fu hrt. Letztlich wird ein Ver- gleich der wichtigen Vulkanisatei- genschaften wie Druckverfor- mungsrest, Hitzealterung und Ozonbesta ndigkeit von EPDM/SBR- und EPDM-Compounds vorgestellt. Crosslinking with peroxides has been known for a long time [1]. It became com- mercially important only with the develop- ment of the saturated and highly satu- rated polymers, such as EPM and EPDM. Curing of EPDM (EPM) rubbers have been accomplished largely by the use of peroxide alone or in conjunction with co-curing agents [24]. Peroxide curing of EPDM (EPM) elastomers not only can improve performance and long- er service life, but can also improve high- temperature resistance, and reduce compression set. Peroxide curing, how- ever, has been confined to special appli- cations because of the limited compound and processing flexibility and typically higher cost relative to sulfur cure systems. EPDM like SBR can be vulcanized with sulfur cure systems. However, differences in the solubility of sulfur and the level of unsaturation in the two elastomers create cure incompatibility in blends of these elastomers [2, 57]. The purpose of this study is to investi- gate the effects of peroxide and coagent on the curing behavior and mechanical properties of 70/30 EPDM/SBR blends. The effect of cure system on important compound properties including: me- chanical properties, compression set, heat aging, and ozone resistance were in- vestigated. Experimental Materials The SBR used in this study is SBR1502 type from the Ameripol Synpol Copora- tion. EPDM with differing levels of diene and ethylene content were obtained from various suppliers. Carbon Black, N330, was obtained from Engineered Carbons, Inc. (ECI). Oil (Sunpar 2280) was obtained from Sun Company. Dicu- myl peroxide, ZnO, sulfur, accelerators, stearic acid, and stabilizers used in this study were of commmercial grade and sources. Formulations and mixing Table 1 and Table 2 showthe general rec- ipe used in this study. Compounding was carried out in a small-scale laboratory Brabender Plasti-corder or a laboratory size Banbury mixer. The speed of the ro- tor in the Brabender and Banbury mixers was set at 80 rpm. The total volume of each mix in the Brabender mixer was kept constant at about 60 cm 3 . Recipes Table 1. General formulation Sample # P (phr) S (phr) C (phr) EPDM 70 70 70 SBR1502 30 30 30 CB (N330) 80 80 80 Sunpar 2280 50 50 50 ZnO 5 5 5 Stearic Acid 1 1 Sulfur 1.5 0.3 TMTD 1.0 0.10 MBT 0.5 0.12 DCP40 2.0 3.0 KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 5/2001 223 ELASTOMERE UND KUNSTSTOFFE ELASTOMERS AND PLASTICS in the Banbury mixer were adjusted to give equal mixing volumes of 1200 cm 3 times the specific gravity for each com- pound. Mixing was done in two stages. All ingredients except for curing agents were mixed in the Banbury or Brabender. Curatives were added to the batch on a mill. Cure characterization was carried out with a Monsanto ODR2000E Rheometer in accordance with ASTM2084. Samples were compression molded at 160 8C for an optimum curing condition. The proce- dure used to determine tensile, hardness, tear, compression set, and heat aging has been described in detail in previous work [8]. The procedure used to deter- mine brittleness temperature and ozone resistance is discribed below. Brittle point measurement Brittleness temperature was measured by a Scott Tester according to ASTMD746-79. A modified T-50 speci- men was die punched. A solution of mixed solid carbon dioxide with acetone was used to achieve low temperatures and an electric immersion heater was used for raising the temperature. When the test temperature reached equilibrium, the specimens were installed and im- mersed into the bath for 3 minutes at the test temperature. After immersing specimens for 3 minutes, the tempera- ture was recorded and a single impact blow was delivered to the specimens. Brittleness temperature was calculated as follows: T b T h DT S 100
1 2
1 where T b is the brittleness temperature; T h is the highest temperature at which failure of all the specimens occurs; DT is a temperature increment; and S is the sum of the percentage of the broken specimens at each temperature. Ozone resistance Ozone resistance was carried out under both static and dynamic conditions. In the static test, ozone resistance was performed in accordance with ASTMD1149-91. The cracking resistance of samples was determined by exposing the samples to an atmosphere containing 50 pphm ozone at 40 8C. The specimens were kept under a surface tensile strain. The time elapsed for visible cracking to occur was determined using a magnification X10. Dynamic ozone resistance was performed in accordance with ASTM D3395-86 method A using die C dumb- bell specimens. The cracking resistance of samples was estimated by exposing test samples to 50 pphm of ozone at 40 8C under dynamic strain conditions (from 0 to 25 % strain at a rate of 0.5 Hz). The time elapsed for the first visi- ble crack to appear and the changes in the stress-strain curves due to the ozone exposure were monitored. Results and discussions The purpose of this study was to evaluate the effects of sulfur, peroxide, and coa- gent on the curing, mechanical and phy- sical properties of EPDM/SBR blends. Performance of the end-products cured with peroxide and sulfur coagent as de- termined by mechanical properties, ozone resistance, heat aging, and com- pression set was also investigated. Cure systems In this section, a comparative study of sulfur, peroxide and coagent cure sys- tems is presented. Curing behavior Table 3 shows the cure characteristics of the EPDM/SBR blends cured with di- cumyl peroxide (P), sulfur (S), and coa- gent (C). Scorch time, T50, T90, and the cure rate showed the following trends: Scorch time, T50, and T90: P > C > S Cure rate: P < C < S The compound cured with the coagent system showed higher maximum torque (34 dNm) than those cured with peroxide or sulfur cure system (26 dNm). The ad- dition of a relatively small amounts of sul- fur (0.26 mole of sulfur/mole of peroxide) to the peroxide cure systemimproved the peroxide efficiency significantly. Mechanical properties Figure 1 shows the stress-strain curves of EPDM/SBR compounds cured with per- oxide cure system (PCS), sulfur cure sys- tem (SCS) and coagent cure systems (CCS). Mechanical properties and hard- ness of the compounds are given in Ta- ble 4. Comparison of the stress-strain curves of PCS, SCS, and CCS show that there is no significant difference in the modulus of CCS and PCS at the low- er strain region (up to 200%). The mod- ulus of SCS was slightly higher than that of CCS and PCS. This observation can be explained by the fact that the crosslink Table 2. General formulation of EPDM and EPDM/SBR blends Sample # EPDM (phr) EPDM/SBR (phr) EPDM 100 70 SBR1502 30 CB (N330) 80 80 Sunpar 2280 50 50 ZnO 5 5 Stearic Acid 01 01 Sulfur 0.30.5 0.30.5 TMTD 0.180.3 0.180.3 MBT 0.120.2 0.120.2 DCP40 35 35 Table 3. Cure characterization of the SBR/EPDM blends with varying cure systems Sample # P S C Max. Torque, dNm 26.7 25.9 33.9 Min. Torque, dNm 5.9 6.2 6.7 Delta Torque, dNm 20.80 19.68 27.24 Scorch time, minutes 2.46 1.90 2.05 T50, minutes 7.12 3.10 5.03 T90, minutes 18.17 7.62 15.42 Cure rate index, 1/min 6.37 17.48 7.48 P: peroxide system, S: sulfur system, C: coagent system 224 KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 5/2001 Properties of EPDM/SBR Blends . . . KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 5/2001 225 Properties of EPDM/SBR Blends . . . density in the SBR domains is signifi- cantly higher than of the EPDM domain in the SCS. This behavior is due to the dif- fusion of the accelerator into the more po- lar and/or faster curing phase of the elas- tomer blend. In support of this conclu- sion, Woods and Davidon [9] have found sulfur and accelerators from the EPDM phase diffuse to the NBR phase during the vulcanization process. The modulus at higher strain for the PCS was higher than SCS because the EPDM matrix of the blends cured with sulfur did not have a high enough cross- link density to support the higher stress. The accelerator loss from the EPDM phase results in lower crosslink density in this phase resulting in decrease of elon- gation at high the stress. The tensile strength and the energy at break of the CCS was about 18 MPa and 12.2 J, while the tensile strength and the energy at break of the compound PCS was 15 MPa and 10.7 J. The tensile strength and the energy at break of the SCS were found about 11.5 MPa and 9.18 J, respectively. The ultimate elonga- tion of CCS, PCS, and SCSwere found to be almost identical. The higher tensile strength and the higher energy at break for CCS indicates that the compounds cured with peroxide and sulfur have stronger and better network properties. The addition of a relatively small amount of sulfur as a coagent to the peroxide cure system (0.26 moles of sulfur/mole of per- oxide) showed a remarkable influence on the mechanical properties of the blends. Tensile strength, energy at break, elonga- tion at break and modulus at high strain increased significantly (Figure 2). The coagent cure system(combination of sul- fur and peroxide cure system) covulcan- ized the continuous phase (EPDM), the dispersed phase (SBR), and phase boundary of the elastomers. This result in increase in the interfacial strength so that the blend properties are similar to those attributed to a single polymer. The polysulfidic crosslinks are generally stronger than the C-C or monosulfide crosslinks [1015]. Vulcanizates with the appropriate mix of crosslink types have superior strength and fatigue resis- tance compared to networks containing only the stronger monosulfide or C-C bonds. Polysulfidic bonds are weaker and more readily broken than C-Cbonds, and thus, high stresses in the molecular network are relieved by fracture of at least some of these crosslinks before back- bone chains are broken. The broken S-S- bonds may either reform again un- der load [16] or link up with the carbon black to form either chemical carbon- gel bonds or physical carbon-gel link- ages. The reformed bonds can continue to support stress and to generate more energy dissipation due to chain slippage as the deformation is increased. Hardness and the modulus at low strain of the compounds cured with the coagent were not affected by the addition of the sulfur. Since the amount of sulfur added to the peroxide cure package is very small, only the C-C bonds (peroxide cure) play the major role in determining the hardness and modulus at low strain. In addition, the coagents improve the ef- ficiency of peroxide crosslinking by sup- pressing unwanted side reactions of polymer radicals [17]. The cure behavior and mechanical properties of the blends cured with coa- gent and sulfur cure systems are dis- cussed below in further detail. Table 4. Mechanical Properties of the EPDM/SBR compounds Sample # P S C Tensile Strength (MPa) 15.0 11.5 18.0 Elongation at Break (%) 428 428 432 100 % Modulus (MPa) 2.69 3.43 2.61 200 % Modulus (MPa) 6.58 6.37 6.77 300 % Modulus (MPa) 11.3 9.22 12.3 Hardness Shore A 68 72 67 Energy at Break (J) 10.7 9.18 12.2 Figure 1. Stress-strain curves of EPDM/SBR (70/30) blends with dif- ferent cure systems Figure 2. Stress-strain curves of EPDM and EPDM/SBR blends with peroxide and sulfur coagent 226 KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 5/2001 Properties of EPDM/SBR Blends . . . Peroxide and sulfur coagent In the previous section, it was reported that EPDM/SBR blends cured with per- oxide and sulfur coagent have better cur- ing and mechanical properties. Com- pression set, heat aging, mechanical properties and ozone resistance of the blend compounds were also compared to those of the EPDM compounds. The results are summarized below. Curing behavior Table 5 above shows the cure character- istics of EPDM and EPDM/SBR (70/30) compounds cured with peroxide and sul- fur coagent. Two levels of curatives were investigated (Table 2). The curing beha- vior of the blend compounds was not sig- nificantly different than that of the EPDM compounds. Due to the higher Mooney viscosity of the EPDM relative to that of the SBR used in this study, the maximum torque of the EPDM compounds was higher than that of the EPDM/SBR com- pounds. Mechanical properties Figure 2 shows the stress-strain curves of the EPDM and the EPDM/SBR com- pounds cured with peroxide and sulfur coagent. The mechanical and physical properties of the compounds are given in Table 6. Replacing 30 parts of the EPDM by SBR decreased the tensile strength and ultimate elongation by about 18 % and 15 % respectively. The tear strength decreased, while the modulus increased at the low strain region due to the increase in the crosslink density in the SBR domains. The SBR domains in the blends played a reinforcing role. Compression set The compression set of the EPDM and EPDM/SBR compounds cured with per- oxide and sulfur coagent were measured according to Method B of ASTMD395- 89. The compression set of the EPDM/ SBR compounds was not significantly different from that of the EPDM com- pounds (Table 7). The compression set of EPDM and EPDM/SBR compounds was higher at room temperature than at 1008C. When a sample is subjected to compres- sion, both physical and chemical stress relaxation can occur simultaneously. At room temperature, the physical stress re- laxation dominates over the chemical stress relaxation, while at a higher tem- perature the relaxation process is domi- nated by chemical reactions. Heat aging Changes in the mechanical properties of EPDM and EPDM/SBR compounds cured with peroxide and sulfur coagent after 7 days aging at 100 and 140 8C are given in Table 8 and Table 9. At 100 8C, tensile strength and ultimate elongation of both compounds did not change significantly. Modulus and hard- ness increased slightly. At 140 8C, the mechanical properties of the EPDM/SBR compounds were found to be significantly worse than those of the EPDM compounds. This is due to the fact that the heat resistance of EPDM vulcanizates is better than that of the SBR vulcanizates. Ozone resistance The EPDM and EPDM/SBR blends were exposed to ozone under dynamic strain conditions (from 0 to 25 % at a rate of 0.5 Hz) in an atmosphere containing 50 pphm of ozone at 40 8C. Optical mi- croscope analysis of the surface of all the samples after 12 days of dynamic and 14 days of static ozone aging showed no cracking. Other properties Table 10 shows that replacing 30 parts of EPDM with SBR decreased the com- pound Mooney by up to 10 points. This is a definite plus in the production of ex- truded goods. Other physical properties, such as brittleness, hardness, abrasion loss, rebound and heat build-up were Table 5. Cure behavior of EPDM and EPDM/SBR (70/30) blends with peroxide and sulfur coagent cure system Sample # EPDM1 EPDM/SBR1 EPDM2 EPDM/SBR2 Cure system High level Low level Max. Torque, dNm 46.1 41.9 38.8 34.8 Min. Torque, dNm 7.1 7.1 6.7 6.6 Delta Torque, dNm 39.0 34.9 32.1 28.2 Scorch time, minutes 1.72 1.68 2.20 1.98 T50, minutes 3.89 3.88 5.37 4.77 T90, minutes 12.4 13.2 15.5 14.9 Cure rate index, 1/min 9.35 8.67 7.55 7.73 The compounds contain 80 phr N330 and 50 phr Oil. Table 6. Mechanical properties Sample # EPDM1 EPDM/SBR1 EPDM2 EPDM/SBR2 Cure system High level Low level Stress-Strain Tensile Strength, (MPa) 23.7 19.2 22.2 18.4 Elongation at Break, (%) 391 338 529 443 100 % Modulus, (MPa) 3.03 4.15 2.54 3.04 200 % Modulus, (MPa) 9.21 10.5 6.34 7.49 300% Modulus, (MPa) 17.3 17.1 11.6 12.6 Die C-Tear Tear Strength, (kN/m) 49.2 44.3 54.8 44.9 Table 7. Compression set Sample # EPDM1 EPDM/SBR1 EPDM2 EPDM/SBR2 Cure system High level Low level Test Conditions 23 8C for 70 hours, % 35.8 31.9 42.4 37.3 100 8C for 70 hours, % 20.5 20.9 30.6 27.3 KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 5/2001 227 Properties of EPDM/SBR Blends . . . not significantly affected by the presence of the SBR. Summary The purpose of this study was to find a suitable cure system for replacing up to 30 parts of EPDM in some products by the lower cost emulsion-SBR without de- terioration in the mechanical and physical properties of the end-products. The re- sults of our study show that the addition of a small amount of sulfur as a coagent to the peroxide cure systemin the EPDM/ SBR compounds have a remarkable po- sitive influence on all the mechanical properties. When 30 parts of the EPDM was re- placed by the lower cost emulsion SBR cured with the peroxide and sulfur coa- gent, compression set, 100 % modulus and 300 % modulus were improved by 10 %, 20 %, and 9%respectively. No sig- nificant change in hardness, brittleness temperature, heat aging, and ozone re- sistance properties were observed. The blend compounds, however, showed slight reduction in tensile strength, elongation and tear strength compared to the EPDM compounds. Also, the high temperature (140 8C) heat aging properties of these blends was also not comparable to the EPDM compounds. Acknowledgment The authors wish to acknowledge the support and encouragement given for this work by the Ameripol Synpol Corporation. References [1] I.I. Ostromyslenski, J. Russ. Phys. Chem. Soc., 47 (1915) 1467. [2] J. Brooke Gardener, Rubber Chem. Technol. 41 (1968) 1312; 42 (1969) 1058; 43 (1970) 370. [3] A. Robinson, J. Moore and L. Amberg, Rubber World, 144, No.4 (1961) 86. [4] P. Wei and J. Rehner, Jr., Rubber Chem. Tech- nol., 35 (1962) 133. [5] F.-X. Gullaumond, Rubber Chem. Technol., 49 (1976) 105. [6] O. Olabisi, L.M. Robeson and M.T. Shaw, Poly- mer-Polymer Miscibility, Academic Press Inc., New York (1979) Chp 2. [7] C.M. Roland, Rubber Chem. Technol. 62 (1989) 456. [8] J. Zhao, G.N. Ghebremeskel and J. Peasey, Rubber World, 219, No. 3 (1998) 37. [9] M.E. Woods and J.A. Davidson, Rubber Chem. Technol., 49 (1976) 112. [10] G.J. Lake and P.B. Lindley, J. Appl. Polym. Sci. 9 (1965) 1233. [11] R.J. Chang and A.N. Gent, J. Polym. Sci., Polym. Phys. Ed., 19 (1981) 1619. [12] L. Yanyo, Int. J. Tract. 39 (1989) 103. [13] A.N. Gent and S.-M. Lai, J. Polym. Sci., Part B: Polym. Phys. 32 (1994) 1543 [14] A.N. Gent and S.-M. Lai, C. Nah and C. Wong, Rubber Chem. Technol. 67 (1994) 649. [15] E. Southern, in Elastomers: Criteria for Engineer- ing Design, C. Hepburn and R.J.W. Reynolds, Eds., Applied Science Publishers, London (1979) 273 [16] A.G. Thomas, J. Polym. Sci., 31 (1958) 467. [17] L.D. Loan, Rubber Chem. Technol., 40 (1967) 149. The authors All the authors are employees of the Ameripol Synpol Corporation, Research & Development Department. Dr. Zhao is a Materials Research Scientist, Dr. Gheb- remeskel is the manger of the Materials and Analylical Division, and J. Peasely is a technican in the Materials Group. Corresponding author Junling Zhao R + D Ameriol Synpol Corporation P. O. Box 667 1215 Main Strat Port Neches USA Texas 77651 Table 8. Heat aging* studies Sample # EPDM1 EPDM/SBR1 EPDM2 EPDM/SBR2 Cure system High level Low level Stress-Strain Tensile Strength Retention, (%) 2.53 0.52 5.41 1.63 Strain at Break Retention, (%) 1.28 2.37 4.54 8.80 100 % Modulus Retention, (%) 10.23 21.20 17.7 22.0 200 % Modulus Retention, (%) 5.97 8.57 21.8 11.8 300 % Modulus Retention, (%) 3.47 3.51 15.5 10.3 Hardness Hardness Retention, (%) 2.86 4.17 1.39 2.82 * The compounds were aged at 100 8C for 7 days. Table 9. Heat aging* studies Sample # EPDM1 EPDM/SBR1 EPDM2 EPDM/SBR2 Cure system High level Low level Stress-Strain Tensile Strength Retention, (%) 4.22 39.58 7.21 41.85 Strain at Break Retention, (%) 16.1 60.1 18.9 62.5 10% Modulus Retention, (%) 38.0 153 50.0 212 200 % Modulus Retention, (%) 300 % Modulus Retention, (%) Hardness Hardness Retention, (%) 7.14 30.5 4.17 29.6 * The compounds were aged at 140 8C for 7 days. Table 10. Comparison of compound properties Sample # EPDM1 EPDM/SBR1 EPDM2 EPDM/SBR2 Cure system High level Low level Compound Mooney Mooney (1 4min) 100 8C 57.3 53.9 65.4 56.8 Hardness Hardness Shore A 70 72 72 71 Brittleness Temperature Temperature, 8C > 60* > 60* > 60* > 60* DIN Abrasion Vol. Loss, mm 3 79.9 79.9 80.1 86 Zwick Rebound 238C, % 54.1 47.5 52.3 48.3 708C, % 62.3 54.3 56.1 50.9 Goodrich Flexometer Delta T, 8C 47.5 59.7 70.8 80.2 Permanent Set, % 2.1 2.8 6.6 6.3 *At that temperature (608C), zero specimen was failed. No further tested. 228 KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 5/2001 Properties of EPDM/SBR Blends . . .