International Conference Organised by Rapra Technology Lid raprg Berlin, Germany 14-15 September 2005 o: (ii nny YGWF-7S-SZRZISBN: 1 85957 5250 © Rapra Technology Ltd, 2005 All tights reserved. No port of this publication may be reproduced, stored in a retrieval system, or transmitted in any form by any means, electronic, mechanical, photocopying, recording or otherwise, without prior written permission of the publisher, Rapra Technology ltd, Shawbury, Shrewsbury, Shropshire, SY¥4 4NR. UK. The views expressed in this publication ae those of the individual outhors and do not necessorlly corresoond to those of Rapra Technology Lid. This publication is published on the basis that no responsibiity or liability of any nature shall attach to Rapra Technology Ltd arising out of or in connection with eny vilization in any form any material contained in this publication,Papert pe 2005 14-15 September 2005 Hotel Grande Esplanade, Berlin, Germany Contents ‘The thermoplastic elastomer scene in 2005 Bary Statham, Consultant, UK ‘SESSION 1, DEVELOPMENTS IN TPVS Peper 2 Paper 3 Paper 4 Paper 5 A new thermoplastic vulcanizate (TPV) with differentiated properties with EPDM based TPV Danie! Milesi & Pierre Rousseau, Multbase SAS a Dow Coming Company, France comparison Engineering TPV for extrusion applications Anke Sutschek, Orvar Otterstedt, Mark Jacobs, Coreen Lee & H. Chul Lee, DuPont de Nemours Intl. S.A, Switzer'and Si-based technology for thermoplastic vulcanizates Valérie Smits & Thierry Materne, Dow Coming S.A., Belgium ‘An Innovative way of dynamic vulcanization of EVAIn the presence of PP: chemical, processing and mechanical properties Prot. Philippe Cessagnau, Dr. Catherine Joubert and Dr. Alain Michel, University of Lyon, France ‘SESSION 2. TPES FOR AUTOMOTIVE APPLICATIONS Paper 6 Paper 7 Paper 8 Paper 9 Polyolefin resin for airbag application - morphology of soft resin and parts performance Nadeem Bothar, Autoliv North America; hiroshi Toyoda & Kousuke Ohteni, ‘Sumtomo Chemical Co., Ltd, Japan The influence of painting systems on TPVs in low temperature deployment behaviour of airbag doors Herman Vos, DSM Thermoplastic Elastomers, The Netherlands Development of new TPV sponge materials and foaming systems for dynamic automotive weatherseals Jere Anderson, Trexel Inc., USA & Erie Jourdain, Santoprene specialty products of ExxonMobil Chemical, Belgium TPV for hidden door frames Ger Vroomen, DSM Thermoplastic Elastomers, The Netherlands & Klaus-Peter Mass, GDX-Grefrath, Germany SESSION 3. NATURAL RUBBER BASED TPVS Paper 10 Natural rubber based TPVs for improved performance Dr. Stuart Cook, J. Patel & Dr. Andrew Tinker, Tun Abdul Rezak Research Centre (TARRC), UKimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableimage not availableTPE 2005 14-18 September 2005- Berlin, Germany aw Kalrez® a5 250 Viton® nas Silicone 200 Fluorosilicone AEM 175 Heat resistance (°C) EPDM ETPY 1 150 EVA Hypalon® a a ns {high vay py Fnlehlorafiysrine (E60) a NBR 100 FEES neopredl Nitrite (NBR) 8 50 SBR &NR No req. 140% 120% 100% 80% 50% 30% 20% 10% Swell in ASTM #3 Oil Figure 1: Overall performance of ETPV vs. cross-linked rubbers according to ASTM D2000/SAE J200 Speetfications In Figure 1 the TPE, TPV and thermoset materials are classified according to their swell in ASTM oil #3 and their temperature resistance. PRODUCT RANGE ETPV is a material in the Shore A hardness range currently available in Shore A 60, 70, 80 and 90. These graces can be used for any standard injection molding or extrusion process, for blow molding specifically designed grades have been developed, information is available upon request For a long-term use (above 1000 h) at elevated temperature, i.e. 150°C, heat stabilization is required. Therefore ETPV Shore A 60 and 90 are also available as heat stabilized grades as they are able to resist more than150°C in air for 3.000 hours (less than 50% retention of elongation at break & tensile strength) in combination with good oil resistance. in Table 1 the mechanical properties of the different ETPV grades are shown. Property Method | ETPV60A | ETPV70A | ETPVS0A | ETPVS0A Shore A hardness (nominal) ‘ASTM D224 © 70 80 30 Specific Gravity (gicm’) 180 R1163 7.08 7.08 7.10 112 Tensile sirength (Mpa) 1$0 527 5 52 78 3 Elongation at broak (%) 180 527, 760 208 210 200. Compression set, 100°C, 22hrs, (%») | ASTMD395-5 35 60 65 35 ‘After annealing 150°, thr (%) Ey) 42 48 res Compression set, 150°C, TOhrs, (%) | ASTMD305-5 & 8 ‘After annealing 150°C, thr (%) 50 80 Brittleness temperature (°C) 1S0.812 =40 40 0 40 Service temperature (°C) 165°C and beyond Resistance to oll n°9 (150°C/70hrs) | ASTM D477 50% volume change Table 1: Mechanical properties of ETPV More information, including aging properties, OMA curves, Rheology date, datasheets, processing recommendations and material safety data sheets (MSDS) are available upon request. Page 2 of 6 pages Peper 3image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 - Berin, Germany SUMMARY Engineering TPV is a thermoplastic vulcanizate that can be processed like any other thermoplastic material using the standard injection molding, 2K molding, blow molding and extrusion techniques. The extrusion process for ETPV has been described in this paper. The excellent heat and oil resistance of ETPV is ‘extending the range of applications for TPV's and is succeeding in closing the gap between TPE’s and high performance thermoset rubbers. REFERENCES 4. DuPont™ETPV Extrusion guide ~ DuPont 2. DuPont™ ETPV Product guide and properties - DuPont DISCLAIMER ‘The information provided in this docurventaiion corresponds to our knowledge on the subject at the date of its publication. This informetion may be subject to revision at new knawledge and experience becomes avaiable, The dats provided fall within the normal range of product properties and relate only to the specific material designated; these data may not be valid for such material used in Combination with any other materials or additives cr in any process, unless expressly indicated otherwise. The daia provided should not be used to establish specticaton limits nor used alone as the basis of design; they are not intended to substitute fer any tesing you ‘may need to conduct to determine for yourself the sulabilly of a specific material for your particular purposes. Since DuPont cannot articipate al variations in actual enc-use concitions DuPont makes no waranties and assumes no liabilty in connection with any use of {hs information, Nothing in ths publcatien is to be considered as a license to operate uncer or a recommencation to infringe any patent rights. Page 6 of 6 pages Paper 3image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 ~ Berin, Germany Activated phenol-formaldehyde resins To overcome the melt stagnation issue, Sabet and Fath [™’] and Coran and Patel [*“ have proved the used ofa resol type phenolic resin as a crosslinking agent. Itis assumed that activated resol cure proceeds via a carbio-cationic mechanism. SnCl, activates the scission of the dimethylol ether of the phenol/formalcehyde oligomer (resol). A reactive specie, the benzilic cation, is formed and will further react with EPDM chains. The final cross-links, consisting of mono-phenol units attached to two ENB-EPDM moieties via one methylene bridge and one chroman ting [™, ™, "). Unsaturation seems to be essential for reaction with resol, which excludes the possibility of a reaction of resol with saturated PP chains. Today, resol-resins are stil the most commonly used crosslinking system for the production of EPDM/PP TPV's. Resol-resin crosslinking technology provides better thermal stability compared to suphur vulcanization and does not affect the polypropylene matrix ["]. The two major drawbacks associated with this technology are (a) moisture uptake of the so-produced TPV's, even at room temperature and (b) discoloration. Peroxide and co-agents assisted peroxides To address the moisture uptake and discoloration issue of resol resins and thermal stability of the sulphur bridge in sulphur vulcanization, peroxide crosslinking technology has been investigated, Peroxide crosslinking involves a free radical mechanism which is initiated by the thermal decomposition of the peroxide itsel. The free radicals formed are very energetic and will abstract H-atoms from EPDM chain to form macro-radicals. These macro-racicals can be combined together to form a crosslink. Dicumy! peroxide is one of the best peroxide cross-linking system for PP/EPDM TPV's [° However, when peroxide is added to PPEPDM blend, two competing mechanisms take place simultaneously: EPDM crosslinking and PP degradation via B-scission. Since PP degradation reduces properties of the final product, B-scission is an undesirable reaction. This phenomenon can be partially overcome by the use of a suitable co-agent's in the presence of peroxide [™"]. The improvement of cross- linking efficiency can be explained by the co-agents influence on suppressing unwantod side reactions of the, elastomer and polymer radical [""]. Examples of co-agents are triallyl cyanurate, methacrylates, bismaleimides and vinyl esters [oii Despite the use of co-agents, the peroxide cross-linking is facing other major drawbacks such as lower tensile and tear strength properties, processing limitations (scorch and cure time less flexible) and odour and safety issues. Table 1 summarises chemical and technological aspects as well as major advantages and disadvantages of each crosslinking technique described above. Page 4 of 12 pages Paper 4image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 ~ Berin, Germany ‘Several patents or papers describe the following: + ["]:A process to produce a crosslinkable polyolefin thermoplastic elastomer in a twin screw extruder having superior rubbery elasticity, mechanical properties and also having improved processing fluidity. Soft segment components are EPM or EPDM with a crystalline ethyiene-propylene block or random copolymer. The crosslinking system used is an organosilane with an organic radical generator. The silane is grafted to the resin by a free radical generator and a crosslinking reaction take place through reaction of the hydrolyzable organic group of the silane (methoxy, ethoxy groups) with moisture in air. In this process all the ingredients, including extender oil, are mixed in a twin- screw extruder and simultaneously dynamically vulcanized. This study shows also that alll corganosilane are not performing the same. (“", "J: An improvement of the above process has been patented where EPM or EPDM is first grafted and then mixed with the thermoplastic matrix and a crosslinking additive comprising water. The same process was elso disclosed for VLDPE and ULDPE. + [| TPV’s are produced using two polymers, a carboxylic acid anhydride either pre-grafted onto the polymer or grafted in-situ via free-radical generator and an aminosilane. Without silane, no ‘crosslinking of the soft component is observed. In the examples it is also clear that all types of aminosilane do not provide the same level of crossiinking. + P|: Moisture cure silane crosslinking technology seems to be the most appropriate curing system in terms of cure rate and final cure state for saturated copolymer such as ethyiene-butene and ethylene-octene copolymer compared to the peroxide curing system. Organosilane without a free-radical generator has also been used as a crosslinking agent to prepare TPV's based on a thermoplastic polymer having vinyl acetate units (e.9. EVA) in the presence of a second thermoplastic polymer [*]. This example is quite interesting as it describes the fact that silane is not just acting as a crossiinking agent but acts also as reinforcing agent. The method for obtaining a hybrid organic- inorganic material consists in an inorganic network form by inducing hydrolysis-condensation of the organosilane dispersed and grafted to an organic network. For example, the organofunctional silane is grafted first to a thermoplastic polymer containing vinyl acetate units. The grafted organosilane belonging to the organic network and the organosilane present in excess will then form an inorganic network by hydrolysis-condensation. An interpenetrated network is formed and crosslinked to an organic network as illustrated in figure 6. ‘Organic Network Inorganic IPN Inorganic IPN dispersed dispersed in an and crosslinked to an Organic Network Organic Network Figure 6 - Interpenetrated network and crosslinked interpenetrated network. Similar method could be performed in the presence of another thermoplastic polymer to produce a TPV. The potential of such technology remains to be explored. BENEFITS OF ORGANOSILANE IN TPV'S The selection of a crosslinking process and chemicals depends on various considerations: processing requirements (e.g. reaction rate at the processing temperature) to avoid scorch and reach optimal properties, compatibiity with the elastomer, efficiency of the crosslinking agents, side reactions with thermoplastic, absence of undesired reactions, toxicity and hazards, colour, odour and final product performance. To address all these considerations and reach an optimum between processability and performance, organosilanes provide a lot of flexibility. In fact, the chemical structure of the organofunctional silane can be adjusted to optimize both the compatibility and the reactivity of the silane to crosslink an elastomer. Page 8 of 12 pages Paper 4image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 - Berlin, Germany CT me ea ey oa a ri rf ry rl 4 Ansarifar, M. A.; Chong, L. K.; Zhang, J.; Bell, A; Elis, R. J., “Effect of bifunctional organosilane on the joint strength of some natural rubber compounds to nylon 6,6,” int. J. of Adhesion and Adhesives, 23(3), 177-188 (2003). Miller, A. C.; Berg, J. C., “Predicting adhesion between a crystalline polymer and silane-treated glass surfaces in filed composites,” J. of Adhes. Sci. and Tech., 16(14), 1949-1956 (2002). GL. Witucki, “A Silane Primer: Chemistry and Applications of Alkoxy Sianes” J. of Coatings Technology, 65(822), 57-60 (1993). M.N. Sathyanarayana, M. Yaseen, “Role of promoters in improving adhesion of organic coatings to a substrate.” Progress in Organic Coatings 26, 275-313 (1995). M. Guichenuy, M.-L. Abel, M. Audenaert, A. Vineer. J. F. Watts, “Mechanism of Delamination of a Thick Coating on Untreated Steel,” Proceedings of the 27th Annual Meeting of The Adhesion Society, Inc. 200-201 (2004). F.J. Boerio, P. Shah, “Adhesion of Injection Molded PVC to Stee! Substrates’, J. of Adhesion, 81(6), 645-675, (2005). H. Scott. J. Humphries, “Novel crosslinking method for polyethylene,” Modern Plastic, 50(3), 82 (1973). M. S. Hearn, J.D. Baird, L.P. Nethsinghe, M. Gilbert, “Silane Crosslinking of Plasticized Polyvinyl chloride, Polymer Communications 31(5), 194-197 (1990). F. de Buyl, “Silicone Sealant and Structural Adhesives” Int. J. Adhesives and Adhesion, 21(5), 411 422 (2001). J. Comyn, F. de Buyi, N.E. Shephard, C. Subramaniam, “Kinetics of cure, crosslink density and adhesion of water-reactive alkoxysilicone sealants’, Int J. of Adhesion and Adhesives, 22(5), 385- 393 (2002). M, Sautrot, M.-L. Abel, J.F. Watts, J. Powell, “Incorporation of an adhesion promoter in a structural Adhesive: Aspects of Durability and Interface Chemistry’, J. of Adhesion, 81(2), 163-187 (2005) N-L. Abel, J.F. Watts, A Ottenwelter, J. Powell, “The Use of An Epoxy Silane within an Adhesive Formulation”, Proceedings of the 28th Annual Meeting of The Adhesion Society, Inc. 155-157 (2005), R.L. Cuthbert, E.D. Plueddemann, Dow Corning Corporation, US 5,073,195 (1991). T. Nobuchika, S. Fumikazu, |. Hisao, N. Yutaka, EP patent 409,642 A2, July 17 (1990). F. Rothemeyer, S. Lupfert, H-G. Fritz, R. Anderlk, EP patent 510,559 B1, April (1992). HG. Fritz, R. Anderik, C. Thumm, DE patent 4402943C2, Feb (1994). J. F. Schombourg, P. Kraxner, W. Furrer, A. Adberrazig, US patent 6,448,343, Sept 10 (2002). S. Cree, J. Pillow, V. Kotian, Novel polyolefin elastomers: properties, cure performance and sekected applications, IRC 2005, 7-9" June, 423-435 (2005). A Michel, A. Verbois, M. Bert, C. Angelloz, P. Blanc, X. Pages, P. Cassagnau, D. Milesi, WO Patent 00/58213, Sept 20 (2000). Page 12 of 12 pages Paper 4image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 — Berlin, Germany elastomer domains and we can expect better mechanical properties for TPV processed by twin screw extruder. Then, the new chemical way of EVA crosslinking is suitable for tailoring EVA/Kraton®/PP in twin screw extruder. However, this process was developed in two processing steps. The first one is the VTMOS grafting onto EVA followed by a second one which consists in crossinking EVA in presence of PP at high temperature. Nevertheless, we can imagine to substitute these two processing steps for only one by using a longer extruder, for example an extruder with a L/D around 56. Indeed, Fritz (8) showed that TPV processing that requires two successive chemical steps can take place in an adequately long extruder. Nipm Cs% = % oy MPa 120 53 210 75 230 56 215 et 325 54 225 84 Tablet : influence of the screw rotational speed on mechanical properties of the TPV made with EVAVKraton®/PP (55/18/27) cross-linked by VTMOS grafting followed by exchange reaction. Plastol oll: 50 hr. CONCLUSION Inan innovative way, EVA was crosslinked by a two step process including a radical grafting of silane groups onto ethylene EVA chains and an exchange reaction between the so-grafted silane functions and the acetate functions of EVA. Different formulations was tested in order to improve different mechanical properties. It ‘was shown that such a TPV has better compression set (Cs=55%) properties than the one in which EVA phase was crosslinked by exchange reaction only (Cs=90%). However, to improve ultimate tensile strength properties, a third component (SEBS, Kraton®) was added. Furthermore, a more compatible effect of the plastol oll through Kraton® phase explains the improvement of the tensile mechanical properties (£+220% and o,=8Mpa). According to morphology analysis, compression set and tensile mechanical propertias, TPV processing in twin screw extruder is the best way from a tailoring point of view. REFERENCES 1 Joubert C., P. Cassagnau , A. Michel, L. Choplin, Polym. Eng. Sci, 42(11), 2222-2233 (2002) 2 Verbois A., P. Cassagnau, A; Michel, J. Guillet and C. Raveyre, int. Polymer, In press, (2004) 3 Pesneaul., Champagne M. and Huneault MA, Polym. Eng. Sci., 42(10), 2016-2031, (2002) 4 Joubert C., P. Cassagnau, A. Michel A., L. Choplin, J. Polym. Sci., Part B: Polym.Physics, 41, 1779- 1790, (2003) 5 Ohisson B., H. Hassander, B. Témell, Polym. Eng. Sci., 36(4), 501-510, (1996). 6 Bounor V., P. Cassagnau, A. Verbois, A. Michel, Polymer, 43(23), 6085-6092, (2002) 7 Joubert C., Choplin L., Michel A., and Cassagnau P..J. Polym. Eng,, 25(1), 59-80, (2005) 8 —FritzH.G., Pure Applied Chemistry, A36 (11), 1683-1698 (1999) ACKNOWLEDGEMENTS This work has been done as part of the CPR (reactive extrusion program contract of the CNRS, the Centre National de la Recherche Scientifique). The authors gratefully acknowledge Multibase Company for making this work possible. Discussions with Daniel Milési, scientist of Mullibase research and development department, were especially fruitful Page 4 of 4 pages Paper 5image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 - Beri, Germany s Figure 2. TEM photograph of non-cross- Figure 3. Phase formation criteria in binary linked TPO(TPO-1), including 35 wt% PP polymers, expressed by volume fraction and each viscosity Figure 4 and 5 show TEM photographs of cross-linked TPOs(TPO-2 and TPO-3), which indicates PP matrix and dark rubber's domain. The amount of PP in TPO-2 and TPO-3 is 35 wt%, which is equal to that of the non-cross-linked TPO(TPO-1). This suggests that the phase reversal is caused by dynamic vulcanization. As effect of PP-matrix morphology like this, the cross-linked TPOs’ demolding and heat distortion are far better than those of non-cross-inked TPO. In the cross-linked TPOs, ethylene-propylene-diene terpolymer(EPDN) is incorporated to enhance cross-linking efficiency with ethylene-c-olefin copolymer as rubber. In these samples, an obvious difference in rubber particles’ size is observed, depending on type of the ethylene-a-olefin copolymer. Figure 4 shows TEM photograph of cross-linked TPO(TPO-2) with ethylene- ceolefin copolymer of type A. Figure 5 shows that of TPO-3 with ethylene-a-olefin copolymer of type B. The rubber particles’ size of cross-linked TPO with ethylene-a-olefin copolymer of type A is smaller than that of type 8. The two figures suggests that type of ethyiene-a-olefin copolymer has effect on morphology formation of TPOs containing PP, EPDM and ethylene-c-olefin copolymer. For applying airbag cover applications as a soft material, mechani linked TPOs (TPO-2 and TPO-3) are shown in Table 2 and Figure 6. in comparison with non-cross-linked TPO (TPO-1). Although all three TPOs satisfied mechanical properties for airbag cover applications, it is demonstrated that the TPO-2 and TPO-3 is superior to TPO-ibased on flowabilily in Figure 6, demolding and heat distortion. The impact resistance at cold temperature of cross-linked TPO(TPO-2) with ethylene-a- olefin copolymer of type A, is higher than that of cross-linked TPO(TPO-3) with ethylene-c-olefin copolymer of Type Bas shown in Table 2. roperties and flowability of the cross- Page 4 of 8 pages Paper 6image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 - Beriin, Germany Figure 12: WT487X, in-chamber Figure 13: Another WT487X, in- deployed cover at -35°C (no delay) chamber deployed cover at -35°C (no delay) 5. Conclusion Cross-linked TPO with fine rubber particle is obtained by raw materials’ modification in soft airbag cover materials. The TPO named “WT487X' salisfies essential properties and provides superior deployment performance with actual airbag parts. 6. References 4) 2). 3). 4). 5). Hamanaka, T., Ooyama, H., Kojima, K., Kikuchi, T.. and Hikasa, T.. SUMITOMOKAGAKU, 1), 24(1997) ™ ™ Imai, A., Hamanaka, T., Sugimoto, H., and Ooyama, H., “Sumitomo TPE and ESPOLEX - Olefinic Thermoplastic Eistomer for Injection Molding, Extruding and Slush Molding-", Proceedings of ‘SPE Automotive TPO Global Conference 2001, 77, (2001) Ultracki, L. POLYMER ALLOY AND BLENDS, (Translated by Nishi, T.), Published by Tokyo Kagakudojin, 217, (1991) Naskar, K., et al., “Thermoplastic Elastomers by Dynamic Vulcanization” Progress in Rubber, Plastics and Recycling Technology, Vol.21, No.1, (2005) Bokhari, N., Hamangka, T., and ljichi Y., "Polyolefin Resin for Airbag Application -Polymer Design and Parts Performance-*, Proceedings of annual meeting of JSPP 2005, Tokyo, 243, (2005) Page 8 of 8 pages Paper 6image not availableimage not availableimage not availableTPE 2005 14-18 September 2005 ~ Berlin, Germany 2.4 Testing methods 2.4.1 Flat Falling Dart Impact test 2.4.1.1 Background and Theoretical explanation Exact material benavior in Altbaas can only be tested in Al loyment under mperatur conditions. However: itis unrealistic to (let) do such expensive tests for substrate product development or for testing the behavior of substrate/paint system combinations. So for cur study an alternative test method to discriminate had to be used. ‘The super high speed of the airbag deployment has such a huge impact on the tough/biitle transition temperature, that ‘all” materials become more or less brittle already at relatively high temp (for instance — 40C in stead of -60C). Instead of high-speed also much lower test temperature will give more britle behavior of substrates. So instead of much higher speed we tested under much lower temperature as substitution for super high speed. ‘This technique is known as a superposition principle, in this case the SpeediTemperature superposition principle. For a relative comparison of low temperature behavior of substrates, the notched Izod measurement has been successfully used to discriminate between materials. This method has proven to be a successful method in the product development of $3939DB-01 and other substrates. A Brittle/Tough transition temperature cf -50C measured in Izod, showed a Brittle/Tough transition temperature of < -35C in real airbag deployment. See attachment 3 Unfortunately, the notched Izod test method cannot be used to test painted plaques; since Izod testing is. done ‘from the side” of the plaque, and the influence of the paint surface is not tasted only the substrate like unpainted That is the reason that we chose the Falling Dart Impact Test as an altemative test method to discriminate. The felling speed of the dart combined with the 5 Kg. Weight of the dart, brings in a lot of energy by Penetrating the painted plaque, but by far not as much energy as a real airbag deployment. That's why also here we made use of the Speed/Temperature superposition principle by testing much lower temperatures from -40C downwards to -60 in order to “imitate” the relative behaviour of the substrates under “normal” low temperature airbag deployment. (Around -35C). For description of the falling dart impact test, which have been used: See attachment 4, 2.4.1.2. Testing conditions The methodology of the Falling Dart Impact test is well described in the following international standards: ISO 6603-02 2000-10 ISO 7765-2 In deviance from these norms, we have been made use of a flat striker tip, instead of a hemispherical one, for the following reasons: High speed impact like airbag deployment does not give the substrate the “chance” to yield The contact surface of a hemispherical tip increases during the impact process and provokes yielding The contact surface of a flat tip is constant during the process of penetration of the dart. ‘The Flat striker tip imitates this “non-yielding-behaviour” in the best way: All the absorbed energy is related to the breakage of the (painted) substrate, rather than being partly absorbed by yielding, ‘The painted plaques have been tested from the backside, le in real airbag deployment takes place For hemispherical vs. Flat Striker tip: See attachment 5. ¥ Further in deviance from these norms, the results of the testing are not expressed in the absorbed Energy value, but the Absorbed Energy value divided by the Maximum Force at which the breakage ‘occurs. KAAS < Page 4 of 20 pages Paper 7image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 — Berin, Germany ATTACHMENT 4 Flame treatment and flame treatment conditions. Due to the inherent poor adhesion properties of untreated PP-compounds, attributed to its low surface free energy and lack of polar functions, the adhesion behavior has to be improved. One of the pre-treatment techniques available is flame treatment. Flame treatment can be use to oxidize the polymer surface in a controlled way. It is hoped to get as many specific chemical groups at the modified surface as possible. Important parameters for flame treatment are: = Gas - Air ratio - Distance between flame and part surface - Flame speed (residence time) Concerning gas ~ air ratic The heat of the flame will abstract hydrogen from the surface. The resulting radicals react directly with ‘oxygen. Mainly propane or methane is used as gas. Methane is often used while itis available by city supply. (Attention City gas composition can differ: A correction needs to be made for actual CH, content (Mostly around 80%)) The Chemical reaction burning of gas burning: For propane: 502 + C3Hy-> 3CO2 + 4H,0 For methane: 20; + CH, > CO; + 2H0 Ar contains 20.95 % O2. So, buming 1 liter of propane means you need 100/20.95 x 5 = 23.87 liter of air. For 1 liter of methane you need 9.55 liter. This is called the stochiometric balance. Using less air compared to the slochiometric balance results in a colder flame and a reducing environment. More air results in an oxidizing environment. It is both possible to use reducing or oxidizing conditions to achieve good adhesion. The best conditions have to be found by practical testing. Page 8 of 20 pages Paper 7image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 ~ Bertin, Germany ATTACHMENT 4 MECHANICAL PROPERTIES - IMPACT FALLING DART [VEM] Pdf version Title: [ Determination of multiaxial impact punctures behaviour of plastics, instrumented test Scope: ‘The High Speed Impact test is used to determine toughness, load- deflection curves and total energy absorption of impact events. This (uy impact test provides full force and energy curves during the mili- LP seconds of the impact. Specmen Standards: DADC Standard Applicable ISO 6603- 2000-4 Standards iso 776! Procedure: ‘The apparatus used is a PC controlled J&B Impact falling dart tester. ‘The test specimen is clamped onto the testing platform, The ‘crosshead, with the falling weight (1kg, 5kg or 23 kg) and attached ‘artis raised to the appropriate height (1000 mm) and is released so it impacts ata specified speed (4,4 m/sec). A hemispherical dart with a preferred diameter of 20 mm is used, alteratively 10 mm. The clamping ring, recommended inside diameter 40 mm, alternatively a 20 mm diameter can be used. ‘The test can be performed with a clamped or unclamped specimen, with or without lubrication of the dart. ‘Since many thermoplastics exhibit lower impact strength at reduced temperatures, itis sometimes appropriate to test materials at temperatures that simulate the intended end use environment. Test specimens: Plate dimersions 65 x 65 x 1-4mm, or any size or shape that will fit into the impact tester. Number of tests: 5 Page 12 of 20 pages Paper 7image not availableimage not availableimage not availableTPE 2005 ATTACHMENT 7A Results Flat falling Dart Impact test (Table) For Graphs: See next page 14-15 September 2005 — Bertin, Germany Page 16 of 20 pages sorve 4 5 ° 7 Subsite Ss80B.0 Smsg0B.0r ssee0Bo1MEWOs} OOS aie 38 38 341-48 Temo.(°C) —Elatty Factor “o 206 45 285 =o 288 288 28 214 284 308 278 35 253 1s 2a tar 208 283 262 0 2a ss 158 15 096 255 186 Teme.) Breakage Type st : = = - - _ “0 st : = = = = - as st 2 = = = : 2 st = so st st so so rt st ® 7 1 r st st 2 st va 18 vB ve st 1B Paper 7image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 - Berlin, Germany E-Modulus at low temperatures E-Modulus used substrates at High temperatures (DMTA) ‘Temperature (°C) Page 20 of 20 pages Paper 7 Telif hakki olan materyalimage not availableimage not availableimage not availableTPE 2005 14-15 September 2005 — Berin, Germany IV. 2 Extrusion line / SCF Delivery System wil ‘ Scf Injection System EPR MuCell TPV Screw MuCell Design Die Figure 2 : MuCell@ Extrusion line lay-out The TPV sponge profiles were prepared at Trexel laboratories. The extrusion system used for all sponge profile preparation is shown in Figure 2. The unit consists of a 63 mm diameter, 32 L/D extruder, with SCF injection port into which is mounted an injector and a TR-10 SCF system, capable of converting gases like CO, and N, into SCF state. The SCF was supplied at 20 bar (2 MPa) from a liquid nitrogen tank, SCF delivery pressure to the extruder was 250 bar (25 MPa) and flow rate was controlled to */-0.004 kg/hr within the set point of this system. The extruder screw used for the experiments was speciiically designed by Trexel for TPV extrusion and the direct injection of SCF. Process temperatures were similar to standard solid TPV processing temperatures but with additional cooling after SCF injection. The output for the experiments ranged from approximately 30 kg/hr to 50 kgihr. IV. 3 TPV material We used in this study a Santoprene TPV 121-60F 100 (F100), a TPV specially targeted for use with the Mucell® technology. F100 typical properties are described in Table 2. Properties Test Method Typical Value Specific Gravity ISO 1183 0.97 Hardness, ShoreA ISO 868 60 Table 2: dense TPV F100 typical properties (from data sheet) IV. 4 - Foam Profile Properties Profiles have been extruded in the line described in IV. 2. We have compared two different gases, Nitrogen (N,) and carbonic gas (CO,) with controlled injected levels. Foam profile properties are described in Table 3. The selected die has a “D" shape, the straight portion being the base. Profile wall thickness is about 1.5 mm. Page 4 of 14 pages Paper 8image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 ~ Berlin, Germany V.2-1 CO, foaming a b Figure 8: CO; foamed profiles a) density of 0.60 and b) density of 0.52 By increasing the gas concentration, profile specific gravity is reduced by creation of more cells that have a spherical shape and are generally closed (Figure 8 a and b), Cell size tends to increase too, enlarging the Void area, as confirmed by the lower profile SG (Figure 9). Cel Size Disuibuton in 100 Foamed Profle Section (C02 gor Profi SC Compareon ¥i . ; Bo : qa i — Se {ee | oe eae Figure 9: cell distribution of CO, foaming, calculated from the SEM image V.2-2 N, foaming In Figure 10, we observe that N, creates smaller cells and more numerous cells compared to CO, The process of density control by N, concentration is similar; more cells are created having a similar size. a b Figure 10: N2 foamed profile a) density of 0.65 and b) density of 0.63 Page 8 of 14 pages Paper 8 Telif hakki clan materyalimage not availableimage not availableimage not availableTPE 2005 14-15 September 2005 ~ Berlin, Germany ‘Specific Gravity Distribution ‘©O; in 121-60F100 ‘Specific Gravity (glee) *SG measured according to ISO 1183 Figure 14b: Profile SG distribution with CO, ‘The standard deviation for these results is 0.003 g/cc indicating an expected sample to sample density variation within £0.01 g/cc. Vi- Conclusion ‘The incentive in the automotive weatherseal market for converting parts from thermoset EPDM to TPV is based on the potential of producing sealing systems with a lower total cost. TPV simplifies the processing operations and equipment compared to current thermoset rubber. TPV also offers lower weight, recyclability and color consistency. In this paper, we have shown that foaming TPV by supercritical fluid offers the possibility of developing automotive door seals, with close cells and a controlled morphology. ‘Selected TPV compositions optimized for the Mucell® technique and using N, es SCF can achieve a cell morphology which is comparable to the one obtained with a chemically blown EPDM; therefore, similar dynamic compression load deflection can be expected. Another benefit of the Mucell® technique is the ability to on-line control the cell structure by the amount of injected gas. This is an improvement over the chemical blow system for a more capable extrusion process. TPV has a constant and better long term compression set in comparison with EPDM. This is a key advantage for designing door profiles with a better sealing performance over the lifetime of the car. With Mucell® SCF technique, TPV foamed seals can be produced with tight tolerances, thin walls and consistent density over long extrusion runs. This is a potential for scrap reduction for the transformer. Ahigher overall quality can be perceived by the consumer for TPV door seal foamed with SCF, since the potential odor from chemical residues of the blow syster ated We continue working to full ll automiotive primary door seal requirements. in particular, we believe that initial compression set value can be lowered by TPV formulation improvements, systematically developed with the Mucell® process. References 1 Cell Structure Control in EPDM Sponge Seals - 0. Georjon, E. P. Jourdain — International Rubber Conference - July 2002 2. Nicrocellular Foam TPV in automotive Weatherseals — K. Blizard, J. Anderson - RAPRA TPE Conference 2003 Page 12 of 14 pages Paper 8image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 ~ Bertin, Germany Major drivers for the replacement of EPDM by TPVs are: Total system cost reduction Improved seel quality and performance consistency Weight reduction Design and manufacturing flexil Good UV resistance Improved aesthetics Recyclability PV's are being validated and used for many years mainly in less demanding sealing system applications like inner waist beltlinas, hood to cowl seals and several trim seals. Currently semi-dynamic applications line glass run channels have been or being transferred from EPDM into TPVs. Due to design requirements more OEM's prefer to use hidden door frames for styling reasons. The function ofthe glass run channel for these kind of door frame concepts is more complex compared to the traditional designed glass run channel. This paper will describe the design and validation of a hidden door frame glass run channel (header) based ‘on Sarlink® TPV. 2. Automotive sealing systems ‘An automotive weather strip or sealing system is defined as a flexible interface between the parts of the car body or glass to prevent air, water, or noise passage. Vehicle performance requirements have increased dramatically over the years. As @ consequence the average length of sealing system has increased til appr. 80 till 100 meters per vehicle. Furthermore sealing system designs have become, and continue to be increasingly complex. This complexity has created differentiation between the weather strips used on a vehicle. Hence, sealing systems can in general be divided into various categories or subsystems. (Dynamic as well as static) Figure 1 shows an overview of the various seal groups found on an automobile. Door profiles, Under hood. Trunk seals. — Glas Re sm Ee -~.W. Hele ei Figure 1: Type and distribution of automotive seals utilized. Belt line seals and glass run channels are ideal applications for UV stable TPV grades with 65 and 75 Shore A hardness range .These products are an excellent choice for the elastic substrate material and can be easily used for these applications. This is because of their good long term elastic properties over a temperature range of -40 to 125 deg C, excellent heat, weathering, UV and chemical resistance. As already mentioned this paper will focus on the use and possibility of TPVs for glass run channel systems. Page 2 of 6 pages Paper 9image not availableimage not availableimage not availableTPE 2005 14-18 September 2005 — Beri, Germany The driver side on the Saab 9.3 is assembled with the TPV header glass run channel and the other side the ‘one based on EPDM. ‘A driving test has been performed under different road conditions and speed (more than 5000 km). No difference in noise transmission or noise generation could be observed. 5. Conclusion. The first obtained results are promising and justifies further development and validation of a full TPV based glass run channel for hidden door frames. The ultimate goal is to offer the automotive industy a complete TPV based glazing system as a module (same concept as Skoda Octavia). Page 6 of § pages Paper 9image not availableimage not availableimage not availableTPE 2005 14-15 September 2005 — Bertin, Germany CONCLUSIONS NRTPVs, in common with many other TPVs, exhibit a largely ‘co-continuous’ phase morphology across a wide hardness range. Whilst NRTPV compounds tend to be of lower modulus for a given hardness than other polypropylene based TPVs, the basic physical characteristics of NRTPVs are largely in keeping with TPVs derived from other elastomers. For TPVs in general, strength properties can be directly correlated to the modulus of the TPV, which is itself related to the thermoplastic content of the TPV. Although, in terms of recovery performance, TPVs in general have been regarded as having somewhat inferior performance when compared with thermoset elastomers, the recovery characteristics of NRTPV ‘compounds, including compression siress relaxation, have been shown to excel those of commercially available TPVs based on other elastomers. However, a significant improvement in recovery performance can be achieved following brief application of pre-strain. Such pre-strain is believed to permanently alter the thermoplastic phase of the blend in a way that results in reduced hardness and low strain modulus together with significantly improved recovery characteristics. Enhanced recovery behaviour, in conjunction with low fogging, good property retention after heat ageing at 135°C and good environmental resistance indicate that NRTPV compounds show suitability in a wide range of product areas, including automotive sealing applications. REFERENCES 1 AY. Coran and R. Patel, Rubber Chem and Technol., 53, 141, (1980) 2 A.J. Tinker, R. D. Icenogle and |. Whittle, Rubber World, 199, 25, (1989). 3 C.L. Riddiford and A. J. Tinker, Paper 33, presented at a meeting of the Rubber Division, ‘American Chemical S ty, Washington DC, October 9-12, 1990. 4 S.Cook, P.S. Brown, C. D. Forge. G. Sica and A. J. Tinker, Paper 11, presented at TPE 2003, Brussels, 16-17 September, 2003 5 C.J. Derham, J. Mat Science, 8 1023, 1973 6 — L Mullins and N. R. Tobin, Proc. 3° Rubb. Technol. Conf., London, 397, 1954. 7 —— S.de Vogel, C. G. Reid, K. G. Cai, H, Tran and N. Vennemann, Paper 16, presented at TPE 2003, Brussels, 16-17 September, 2003. 8 J. Oderkerk, G. de Schaetzen, B. Goderis, L. Hellemans and G. Groeninckx, Macromolecules, 35, 6623, 2002. 9 R. Abd. Rahim, unpublished PhD studies (TARRC/IPTME Loughborough University), 2005, Table 1. Basic physical properties of TPVS Physical Property NRTPV EPDM TPV__| EPDM TPV 201-64 3160 Hardness, Shore A (15sec) _| 53 Gl 73 4 63, ™50, MPa 1.5 2.0 29 24 24 ‘M100, MPa 22 27 3.7 34 36 Tensile Strength, Mpa 42 48 6.2 56 68 EB, % 270 285 340 365, 550 ‘Tear Strength, Nimm 162 1202 [27 24 32 Table 2. Comparison of property retention after hot air ageing ‘% Retention | NRTPV 59] NRTPV 59 | NR Thermoset™ | EPDM Thermoset” 3di125°C_| 3d/135°C_| 30/125°C 30/125°C, Mi00 107 90, 85 = TS, MPa__| 97. 85, 50. 124 EB. % 97 85, 50. a7. NR Thermoset* ‘Semi EV, engineering compound for moderate/elevated temperature applications with high resistance to set (TARRC Formulary) EPDM Thermoset” General Weatherstripping (Dupont Dow in ‘The Rubber Formulary’) Page 4 of 8 pages Paper 10image not availableTPE 2005 14-15 September 2005 — Berin, Germany ao | AENRTPV & ,[ cePDMTPV o@ 4 ‘© 7 @NRTPV Be 2 8 5 B4 23 £2 ea o 0 1 2 9 4 5 6 M100, MPa Figure 2 Relationship between Tensile strength and M100 for TPVs 40 GNRTPV ° 30 EPDM TPV # a@e i Tensile strength, MPa = 8 M100, MPa Figure 3 Relationship between Tear Strength and M100 for TPVs Page 6 of 8 pages Paper 10TPE 2005 14-15 September 2005 — Berlin, Germany Figure 4 Compression stress relaxation test jig Transducer Test Pisco Figure 5 Compression stress relaxation at 40°C (15% compression). Log Time, mins Page 7 of 8 pages Paper 10TPE 2005 Figure 6 Figure 7 Figure 8 14-15 September 2005 ~ Bertin, Germany Typical extension - retraction curves for TPVs OCycle 1 4b acyciez o @ Stress, MPa 0 10 20 30 Strain, Effect of 200% pre-strain on tensile behaviour of NRTPV 53 DBelore pre-strain After pre-strain Stress, MPa 0 100 200 300 400 500 Strain, % Effect of 200% pre-strain on tensile behaviour of EPDM TPV 101-64 TT OBefore pre-strain 8 | oatter pro-strain g3 & =4 Bs B2 1 ° o 100 200 300 400 500 Strain, % Page 8 of 8 pages Paper 10TPE 2005 14-15 September 2005 — Bertin, Germany FURTHER ADVANCES IN DEVELOPING QUALITY AUTOMOTIVE PRODUCTS BY INCORPORATING END OF LIFE VEHICLE PARTS Gary Pollard Vita Thermoplastic Compounds Lid., UK BIOGRAPHICAL NOTE Gary Pollard BSc.(Hon). M.A. is a graduate from Manchester Polytechnic Polymer Science Dept. Gary has worked with British Vita for 20 years in the roles of development, production, sales and business management. All in the field of polymeric compounding. ABSTRACT Increasing environmental awareness an¢ legislation within the automotive industry is encouraging the use of recyciable materials such as TPE. This paper reviews the further progress made by Vita Thermoplastic Compounds Ltd, in developing high quality recyclable products which incorporate materials for end of life vehicles. Automotive parts made from these materials are discussed. The paper concludes with a discussion on the use of recycled car tyres in TPE automotive products. Figure 1 dryflex® vitaprene® mediprene™ NY 6 veorie A World Leader in Specialist Polymer Technology Page 1 of 26 pages Paper 11aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.TPE 2005 14-15 September 2005 — Berlin, Germany Figure 4 dryflex® vitaprene® mediprene™ Vita Thermoplastic Compounds TPE Group Vita Thermoplastic Polymers. VTC Elastoteknik. VTC France. VTC Eranceschetti Elastomeri — We ee Page 3 of 26 pages Paper 11aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.TPE 2005 14-15 September 2005 ~ Berlin, Germany Figure 8 dryflex® vitaprene® mediprene™ Our Product Area + We manufacture Thermoplastic Elastomer Compounds (TPE) in pellet form for sale to the Injection Moulding, Extrusion & Sheeting Industries. Figure 9 dryflex® vitaprene® mediprene™ Performance vs Cost Vitaprene+Dryfiex Me oe oy aS Performance LO SS Cost Per Tonne Page 5 of 25 pages Paper 11TPE 2005 14-15 September 2005 — Berin, Germany Figure 10 tec ei) Figure 14 a Ail Vel ele hem lg bi Why use recycled car parts? * OEM requests ! + Price stability. + Improved environmental image. + Increased sales. Page 6 of 26 pages Paper 11TPE 2005 14-15 September 2005 — Bertin, Germany Figure 12 dryflex® vitaprene® mediprene™ Plastic Phase Replacement vtc> Figure 13 dryflex® vitaprene® mediprene™ Concerns that needed to be addressed. * Cleanliness. * Consistency. + Availability. + Surface finish. + Performance. * Cost Page 7 of 26 pages Paper 11TPE 2005 14-18 September 2005 - Bertin, Germany Figure 14 Cadi emcee ett 1 Concerns that needed to be addressed. + Cleanliness. * Consistency. * Availability. + Surface finish. + Performance. * Cost Figure 15 + Reprocessed Polypropylene. * Material sourced with guaranteed ‘specification, i.e. tolerance on MFR, Strength, Impact, Melt Flow, ash content, volatiles etc. + Has a controlled and acceptable level of restricted substances v4 Page 8 of 25 pages Paper 11aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.TPE 2005 14-15 September 2005 - Berin, Germany Figure 18 ‘yilex® vitaprene® medipr Quality Control + Compound manufacture is Quality Controlled using consistent feedstock, with ingredients within a 1% weighment tolerance * Mixing cycle is identical for ‘like’ compounds to the customers agreed quality plan, typically including MFR, hardness, S.G. and stress/strain parameters vte 5 * COA included on every batch delivered x Figure 20 Ge Se al ee ohalnl VITAPRENE 45709 Property Typical Value Units Tost method Hantress 2 Shore A 0.888 Hardness 6 Shore D 0.888 Elongetion@ Break 470 % \soa7 Tensile srengh 15 MPa soa? Tear strength 58 MPa S037 Ozone Resistance __No Cracking Visual _ 50 4methodC Page 10 of 26 pages Paper 11aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.TPE 2005 14-15 September 2005 - Berlin, Germany Figure 23 Eee o Discovery Figure 24 dryflex® vitaprene® mediprene™ Market Applications + Automotive interior and exterior trim parts for many of the European car manufacturers Page 12 of 26 pages Paper 11 Telif hakki olan maieryalTPE 2005 14-15 September 2005 ~ Berin, Germany Figure 25 a Vtstietacd Figure 26 dryfilex® vitaprene® mediprene™ Plastic Phase Summary + Materials meet product requirements. + No compromise on quality. + Sustained availability. + Excellent in service performance. * OEM confidence and repeat business. 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limit for this book.Capture the impossible. Silane Solutions Distinctly Dow Corning. When inspration partner, With our full range of sia We help you invent the future”