-KONTAKT 39 Information for the Rubber Industry

Transcription

1 -KONTAKT 39 Information for the Rubber Industry Deolink Silane Preparations Content 1. Introduction / History 2. Advantages of the DOG carrier systems 3. Sulphur silanes Deolink / Deolink 4. silanes Deolink / Deolink 5. Appendix Complete overview of all test series

2 -KONTAKT 39 Content Page 1. Introduction / History General chemical structure Chemical reactions during the silanization process Silane categories Interactions between filler and silanes Deolink Silane Preparations / Deolink Liquid Silanes Sulphur silanes silanes Applications for technical rubber compounds 7 2. Advantages of the DOG carrier systems 7 3. Sulphur silanes Deolink / Deolink Effects in various elastomers SBR / Silica EPDM / Silica CR / Silica Influence of the time of addition Effects of the silane dosage on various filler SBR / Silica SBR / Clay Influence of different mixing temperatures 15 Page EPDM / Aluminiumhydroxide Influence of different mixing temperatures Electrical properties Appendix Complete overview of all test series Sulphur silanes Deolink / Deolink SBR / Silica NR / Silica EPDM / Silica EPDM / Clay NBR / Silica CR / Silica SBR / Clay SBR / Silica silanes Deolink / Deolink EPDM / Silica H-NBR (fully saturated) / Silica H-NBR (partly saturated) / Silica EVA / Aluminiumhydroxide CPE / Clay / Silica NBR / Silica EPDM / Clay EPDM / Aluminiumhydroxide EPDM / Silica silanes Deolink / Deolink Effects in various elastomers EPDM / Silica H-NBR (fully saturated) / Silica EVA / Aluminiumhydroxide Effects of vinyl silanes on various filler EPDM / Silica EPDM / Clay 23 Imprint Editor: DOG DEUTSCHE OELFABRIK Gesellschaft für chemische Erzeugnisse mbh & Co. KG info@dog-chemie.de Authors: Henry Ahrens, Dr. Bernd Bornemann, John Chapman, Manfred Heide, Stephan Müller, André Rittmann, Stefan Oettlein Layout/Production: EHRENBERG WERBUNG info@ehrenberg-werbung.de 2

3 1. Introduction / History Silanes have been known for about 5 years. They were originally used in an industrial scale for adhesives and coatings. In the 7 s silanes found their way into the rubber industry as coupling agents for white filler. During the early 9 s, sulphur silanes gained more and more importance due to the increasing acceptance of the Green Tyre. Meanwhile, silanes are used in the rubber industry in a large variety of applications. From the chemical point of view, silanes are seen as a parallel to organic molecules. The main difference being, that instead of the carbon, the chemically similar silicium atom is bound in the molecule. This fact enables the silanes to work as bifunctionally active linking molecules. These can link on one side with the hydroxyl group of the filler and on the other side they can connect to the polymer. By using these properties, it is possible to connect an anorganic filler directly to the elastomer. Before silanes were commonly used connections with filler only consisted of relatively weak bonds, such as Van-der-Waalsinteractions, adhesion or absorption. 1.1 General formula Y (CH ² ) Si OR n OR OR R= organic group Y= organofunctional group Although the chemical theory is sufficiently researched, the selection of the most suitable silane for specific elastomers and their vulcanization systems requires much know-how. Through the use of silanes, not only a physical process takes place inside the mixing chamber, but also at the same time a chemical reaction called silanization: For these chemical reactions the mixing parameters play an important role. Certain compound ingredients may promote the silanization or disturb this process. Therefore the physical properties of the compound may be affected. THE MIXER BECOMES A REACTOR. 3

4 -KONTAKT Chemical reactions during the silanization process During the past years, many studies have been conducted to support the understanding how silanes react. Generally, there are two theories in discussion. The first one describes a direct condensation, whilst the second is based on the pre-hydrolysis of the silane. The actual studies are in favour of a two-step-reaction with the following pre-reaction: Pre-reaction Hydrolysis (example: alkoxysilane) The alcoxy groups of the silicium are subject to hydrolysis. The necessary water is generally available on the surface of inorganic filler. Y Si OR OR OR + 3 H O ² Y Si + 3 R Y = organofunctional group Step 1 Connection with the mineral surface (example: silica) The silanol groups which are formed by the hydrolysis of the silane, condense with the hydroxyl groups of the filler and form stable Si-O-Si bonds by splitting off water. Si O Si O Si Si O Si O Si HO O H H O Si O H H O HO O H Si O H - nh ² O HO O Si Y O O Si Y O Y Y Y = organofunctional group Step 2 Linking with the polymer matrix (example: mercapto silane) The organofunctional group (Y) is relevant for the reaction with the polymer. This reactive group must be suitable for the chosen vulcanization system, to enable cross-linking during the vulcanization process. Using this mechanism, it is possible to form a silane bridge through a chemical reaction between the polymer chains and the filler particles. This process results in the formation of a polymerfiller-network. 4

5 Reaction of a silanized filler with the polymer (example: mercapto silane) Filler (after silanization) HO filler O Si CH 2 CH 2 CH 2 SH + CH 2 C CH CH 2 HO parallel to the vulcanization HO filler O Si CH 2 CH 2 CH 2 S CH HO H 3 C CH 2 CH CH 2 Diene-Polymer [ ] [ ] CH 3 n untreated microsphere silane treated microsphere Source: Presentation A new filler treatment for HFFR systems, GE Advanced Materials GE Silicones, Tarrytown, NY 1.3 Silane categories Depending upon the chemical composition, the following main categories of silanes are available: Sulphur Epoxy Amino Methacryl Isocyanato Chloro Thiocyanato In the rubber industry, sulphur and vinyl silanes are commonly used, whereas amino-, chloro-, and other silanes are rarely utilized. 5

6 -KONTAKT Interactions between filler and silanes Increasing Effect Filler Silica Clay Aluminiumhydroxide Talc Inorganic oxides (e.g. Titaniumdioxide) No Effect Filler Whiting Barium sulfate (Baryte) Carbon black Not all filler are equally suitable for linking with silanes. The chemical connection with a silane requires the presence of hydroxyl groups in the filler. Under these conditions, the physical properties of vulcanizates are improved by the use of silanes. 1.5 Deolink Silane Preparations / Deolink Liquid Silanes Sulphur silanes Deolink [bis(triethoxysilylpropyl)tetrasulfane] is a preparation with 5% active substance on a polymer / wax carrier system. It can be used in almost all elastomers which are suitable for sulphur vulcanization. DOG also offers the liquid tetrasulfane silane under the name Deolink -1. Deolink is a preparation of a thiocarboxysilane with 5% active substance. In comparison to the tetrasulfane silanes, Deolink can be processed over a broad temperature range without the risk of scorch. Deolink can often be used even at lower dosages without loss of effectiveness. Deolink has a blocked mercapto group and can be chosen as an alternative to conventional mercapto silanes. The protective group is removed during processing releasing the mercapto silane. By using Deolink, optimized processing properties can be achieved and the unpleasant odour of mercaptanes is avoided. Deolink is suitable for all elastomers, which can be crosslinked by sulphur vulcanization. DOG also offers the liquid thiocarboxysilane under the name Deolink silanes Deolink [tris(2-methoxyethoxy)vinylsilane] and Deolink [alkoxysilane] are preparations with 5% active substance on a polymer / wax system. By using Deolink the electrical and mechanical properties can be improved. Deolink is suitable for all elastomers which can be crosslinked by peroxide vulcanization. DOG offers the liquid tris(2-methoxyethoxy)- vinylsilane under the name Deolink -1. By using Deolink, the mechanical and electrical properties can be optimized. In comparison with conventional vinyl silanes Deolink can improve the long-term electrical properties to a higher extent. Deolink does not form any hazardous methoxyethanol (EGME)*. Furthermore, the processing of the unvulcanized compound can be facilitated by the use of Deolink. Under the name Deolink -1, DOG also supplies the liquid alkoxysilane. *Ethyleneglycolmonomethylether 6

7 1.6 Applications for technical rubber compounds Cables / cable accessories Improved electrical properties (insulation, water absorption-, swelling, dielectrical strength) Improved mechanical properties (tensile strength, abrasion) Roller coverings Reduced abrasion Improved compression set Improved dynamic properties (heat build up) Optimized processing properties Sealings / O-rings Improved compression set Optimized processing properties Improved mechanical properties Reduced abrasion, for dynamically stressed sealings V-belts / conveyor belts Reduced abrasion Improved dynamic properties Improved adhesion with the reinforcing fabric Shoe soles Reduced abrasion Optimized processing properties Improved dynamic properties (flex cracking resistance) Moulded articles Improved dynamic properties Optimized processing properties Improved mechanical properties Hoses and tubes Reduced abrasion of surfaces Improved mechanical properties Improved adhesion with the reinforcing fabric 2. Advantages of the DOG carrier systems The Deolink Silane Preparations contain 5% of the active substance on a polymer / wax carrier system. In comparison to liquid silanes, or preparations on inorganic carriers, Deolink Silane Preparations provide the following advantages: Improved protection against hydrolysis through moisture Excellent dispersion and handling Easy incorporation without spots, no formation of agglomerates No dust development by fines Prolonged storage stability without loss of activity Cost savings due to complete use of opened boxes, no disposal of ineffective hydrolized residues 7

8 -KONTAKT Sulphur silanes Deolink / Deolink The in situ modification or in other words the hydrophobation of the mineral surface during the mixing process is the most frequently used method of silanization. As already mentioned, mixing temperature, filler-, silane types and the general compound formulation have a significant influence on the degree of silanization. 3.1 Effects in various elastomers The various polarities of the different elastomers can have an influence on the silanization, due to the different affinity of the filler to the elastomer. The following studies support the effects of Deolink and Deolink. The linking of the filler to the rubber matrix provides positive influences in respect to the mechanical dynamical values and the processing properties. These effectes in SBR, EPDM and CR are illustrated in the following pages. In these tests Deolink is particularly effective in EPDM and CR, since this silane preparation already gives a high efficiency at lower mixing temperatures. As a result of this, processing (higher injection volume) and processability (scorch safety) are improved. Name Deolink / -1 Deolink / -1 Description activator for filler activator for filler Active substance bis(3-triethoxysilylpropyl)- thiocarboxysilane tetrasulfane () Silane content [%] Appearance yellow pellets yellow liquid white pellets clear liquid Analytical values Total sulphur [%] ASTM D 1552 (LECO) Density at 2 C [g/cm 3 ] DIN ISO 787 T1A Dropping point, [ C] 72±5 115±5 Mettler-apparatus DIN ISO 2176 Dosage in relation to filler [%] ca German Food Legislation (BfR recommendation XXI) not approved not approved Storage stability in originally sealed package in cool and dry places min. 1 year min. 1 year Classification and labelling labelled as irritant (Xi) according to EEC directives Supply form Deolink / Supply form Deolink -1 Supply form Deolink -1 2 kg in cardboard boxes with PE-inliner in pre-weighed packaging available on request 2 kg steel drums and 1 l containers 195 kg steel drums 8

9 3.1.1 SBR / Silica* Recipe 451S Deolink Deolink Buna SBR Silica (BET 175 m 2 /g) Naphthenic oil ZnO Stearic acid 1.5 1,5 1.5 PEG Antioxidant SPH Deolink 4 Deolink 4 MBTS DPG Sulphur Total phr The use of Deolink and Deolink provides substantially improved physical data. The most favourable advantages of Deolink take effect in EPDM (3.1.2) and CR (3.3.3) DIN Abrasion 12 Modulus 3 % 1 8 mm Mooney ML 1+4, 1 C 15 Tensile strength [24 h/7 C] 4 Injection volume (capillary/piston 1 C, mould 18 C) 2 3 % cm * The process parameters are documented in the appendix 9

10 -KONTAKT EPDM / Silica* Recipe 93E Deolink Deolink EPDM Buna EPG Silica (BET 125 m 2 /g) Paraffin oil ZnO Stearic acid PEG Deolink 4 Deolink 4 Deovulc TP MBTS DPG Deovulc ZBEC Sulphur Total phr In addition to the improved physical properties (see 3.1.1), the use of Deolink enables a higher injection volume DIN Abrasion Modulus 3 % mm Mooney ML 1+4, 1 C 12 Tensile strength [24h/7 C] 1,5 Injection volume (capillary/piston 1 C, mould 18 C) 15 1, % 1 cm 3 5,5, 1 * The process parameters are documented in the appendix

11 3.1.3 CR / Silica* Recipe 248C Deolink Deolink Baypren Silica (BET 125 m 2 /g) Ester plasticizer MgO Stearic acid Controzon GP Antioxidant ODPA Deolink 2 Deolink 2 ZnO MBTS ETU Total phr In addition to the improved physical properties, the use of Deolink leads to a better processing safety. 2 DIN Abrasion Modulus 3 % 15 mm Mooney ML 1+4, 1 C 19 Tensile strength [24h/7 C] 1, Injection volume (capillary/piston 1 C, mould 18 C) 3,8 % 2 cm 3,6,4 1,2, * The process parameters are documented in the appendix 11

12 -KONTAKT Influence of the time of addition For the majority of the technical rubber compounds, the influence of the time of silane addition during the mixing process is of relatively minor importance. Generally, a homogenous dispersion of the raw compound is mandatory. As mentioned in 3.4, special mixing procedures are often used in the tyre industry. For technical rubber compounds the conventional mixing method is adviseable. We recommend the addition of the silane together with the (first) dosage of light filler. It is not recommended to add the silane at the start of the mixing cycle together with the rubber, as in some cases, a deterioration of the physical values has been found. The upside down process, commonly used for EPDM, is also possible with all Deolink grades. For the so-called one-stage mixing procedure with sulphur curing systems, Deolink is of benefit since it shows its advantages already at lower mixing temperatures. 3.3 Effects of the silane dosage on various filler The degree of modification is certainly influenced by the quantity of silane used. The rubber technologist can adjust the silane dosage to the requirements of the particular application. Furthermore, the silane dosage should be adjusted to the filler. Higher dosages of silanes are recommended, if the full potential of high active filler (e.g. silica) needs to be used. An increased quantity of Deolink releases additional quantities of sulphur, which can influence the vulcanization process. Medium active filler (e.g. clay) often require only reduced silane dosages to provide the maximum reinforcement strength. Deolink provides significant improvements of the physical properties even at low dosages. 12

13 3.3.1 SBR / Silica* Recipe 451S Deolink Deolink Buna SBR Silica (BET 175 m 2 /g) Naphthenic oil ZnO Stearic acid PEG Antioxidant SPH Deolink Deolink MBTS DPG Sulphur Total phr If Deolink is used at higher dosages, it needs to be taken into consideration, that additional quantities of sulphur will be released, which will affect the vulcanization process. 2 DIN Abrasion Modulus 3 % 12 mm (8 phr) (8 phr) 7 Mooney ML 1+4, 1 C 14 Tensile strength (8 phr) (8 phr) 3 [24 h/7 C] 5 Injection volume (capillary/piston 1 C, mould 18 C) 25 4 % cm (8 phr) (8 phr) * The process parameters are documented in the appendix 13

14 -KONTAKT SBR / Clay* Recipe 456S Deolink Buna SBR Clay Naphthenic oil ZnO Stearic acid PEG Antioxidant SPH Deolink MBTS DPG Sulphur Total phr In comparison to silica, the use of silane with the medium active clay provides a relatively lower degree of reinforcement. If silanes are used in higher dosages, it should be considered, that additional quantities of sulphur will be released which will affect the vulcanization process. The use of Deolink leads to similar test results (see 3.3.1), without releasing sulphur DIN Abrasion Modulus 3 % 8 6 mm (8 phr) (8 phr) 46 Mooney ML 1+4, 1 C 18 Tensile strength (8 phr) (8 phr) 35 3 [24 h/7 C] 2,2 Injection volume (capillary/piston 1 C, mould 18 C) % cm 3 2,1 2, 1,9 5 1,8 (8 phr) 1,7 (8 phr) 14 * The process parameters are documented in the appendix

15 3.4 Influence of different mixing temperatures* The reaction speed of the silanization is dependent on the processing temperature. For the effective use of sulphur silanes, a dumping temperature of 13 C 15 C is recommended. The tyre industry achieves their required silanization effects through a longer mixing process or with higher mixing temperatures of around 16 C. Typical silica tread compounds are produced in a three-pass procedure to ensure that the silane is used to its best potential. For technical rubber compounds these processes with several steps are usually not necessary. When using Deolink, mixing temperatures of > 16 C should be avoided to exclude the risk of pre-scorch of the raw compound through the poly-sulfane groups of the silane. Alternatively, Deolink can be used in these cases, as mixing temperatures of 17 C are easily possible. For a representative illustration of the influence of the mixing temperature on the silanization, the following temperature ranges have been chosen. Open mill: Mixing temperature 8 C Banbury: Dumping temperature 115 C Banbury: Dumping temperature 14 C Already at 8 C on an open mill both Deolink grades provide a silanization of the raw compound and an improvement of the physical properties. At this low temperature, Deolink shows an even higher activity than Deolink. At a dumping temperature of 115 C, the silanization effects are more significant and again, Deolink still presents advantages in comparison to conventional sulphur silanes. At a dumping temperature of 14 C abrasion and processing (injection volume) are further improved. Recipe 451S Deolink Deolink Buna SBR Silica (BET 175 m 2 /g) Naphthenic oil ZnO Stearic acid PEG Antioxidant SPH Deolink 4 Deolink 4 MBTS DPG Sulphur Total phr * The process parameters are documented in the appendix 15

16 -KONTAKT 39 mm C 8 C 8 C DIN Abrasion 115 C 115 C 115 C 14 C 14 C 14 C 12 Modulus 3 % C 8 C 8 C 115 C 115 C 115 C 14 C 14 C 14 C 14 Mooney ML 1+4, 1 C C 8 C 8 C 115 C 115 C 115 C 14 C 14 C 14 C 16 Tensile strength C 8 C 8 C 115 C 115 C 115 C 14 C 14 C 14 C 16

17 3 25 [24h/7 C] % C 8 C 8 C 115 C 115 C 115 C 14 C 14 C 14 C 3,5 3, Injection volume (capillary/piston 1 C, mould 18 C) 2,5 cm 3 2, 1,5 1,,5, 8 C 8 C 8 C 115 C 115 C 115 C 14 C 14 C 14 C 17

18 -KONTAKT Silanes Deolink / Deolink 4.1 Effects in various elastomers In point 3.1 the influence of the elastomer on the silanization has already been shown. For the selection of rubber grades the standard products for peroxide vulcanization processes have been chosen. Again, the positive effects of the silanization can clearly be found. DOG offers two vinyl silane preparations, which differ in the active substance and in the carrier system. Deolink is a 5% preparation of a tris(2-methoxyethoxy)vinylsilane on an EVA / paraffin wax carrier system and is well established in the rubber industry. Deolink cannot develop any hazardous methoxyethanol during the processing, since it is based on a special alkoxysilane. The reinforcement effects of Deolink are more distinct than those of Deolink. With regards to the positive influence on processing, Deolink provides additional benefits. DOG also offers boths grades in liquid form as Deolink -1 and Deolink -1. Name Deolink / -1 Deolink / -1 Description activator for filler activator for filler Active substance tris(2-methoxyethoxy)- alkoxysilane vinylsilane Silane content [%] Appearance white pellets clear liquid white pellets clear liquid Analytical values Density at 2 C [g/cm 3 ] DIN ISO 787 T1A Dropping point, [ C] 72±5 11±5 Mettler-apparatus DIN ISO 2176 Dosage in relation to filler [%] German Food Legislation (BfR recommendation XXI) not approved not approved Storage stability in originally sealed package in cool and dry places min. 1 year min. 1 year Classification and labelling labelled as irritant (Xi) according to EEC directives Supply form Deolink / Supply form Deolink -1 Supply form Deolink -1 2 kg in cardboard boxes with PE-inliner in pre-weighed packaging available on request 2 kg steel drums and 1 l containers 186 kg steel drums 18

19 4.1.1 EPDM / Silica* Recipe 94E Deolink Deolink EPDM Buna EPG Silica (BET 125 m 2 /g) Paraffin oil PEG ZnO Deolink 2 Deolink 2 TAC DL Perkadox Total phr As mentioned in 4.1, the reinforcement effects of Deolink are more distinct than those of Deolink. With regard to the processing, Deolink provides certain benefits DIN Abrasion Modulus 3 % 12 1 mm Mooney ML 1+4, 1 C 15 Tensile strength [24 h/1 C] 1,5 Injection volume (capillary/piston 1 C, mould 18 C) 15 1, % 1 cm 3 5,5, * The process parameters are documented in the appendix 19

20 -KONTAKT H-NBR (fully saturated) / Silica* Recipe 3T Deolink Deolink H-NBR Therban Vulkasil A MgO ZnO Antioxidant SDPA Vulkanox ZMB Deoflow Deolink 2 Deolink 2 TAIC Perkadox Total phr As mentioned in 4.1, the reinforcement effects of Deolink are more distinct than those of Deolink. Deolink provides certain benefits regarding the processing. 2 DIN Abrasion Modulus 2 % mm Mooney ML 1+4, 1 C 2, Tensile strength 11 19, , 18,5 18, 17,5 9 17, 5 [7 h/15 C] 2, Injection volume (capillary/piston 1 C, mould 18 C) 4 1,5 % 3 2 cm 3 1, 1,5, 2 * The process parameters are documented in the appendix

21 4.1.3 EVA / Aluminiumhydroxide* Recipe 12L Deolink Deolink Levapren 5HV Aluminiumhydroxide Zinc borate Vulkanox DDA Plasticizer DOS Deolink 3 Deolink 3 TAC Perkadox Total phr In EVA the reinforcement effects of Deolink are significantly stronger than those of Deolink DIN Abrasion Modulus 1 % mm Mooney ML 1+4, 1 C 16 Tensile strength [24 h/1 C] 3, Injection volume (capillary/piston 1 C, mould 18 C) 2,5 1 2, % cm 3 1,5 5 1,,5, * The process parameters are documented in the appendix 21

22 -KONTAKT Effects of vinyl silanes on various filler As already mentioned in 3.2, the silane dosage should be adjusted to the filler. Compared with sulphur silanes, vinyl silanes are used in much lower dosages. In all suitable filler, the positive effects even at low dosages can be noticed. Some differences can be observed depending on filler and Deolink grade EPDM / Silica* Recipe 94E Deolink Deolink EPDM Buna EPG Silica (BET 125 m 2 /g) Paraffin oil PEG ZnO Deolink Deolink TAC DL Perkadox Total phr DIN Abrasion Modulus 3 % 12 1 mm (1 phr) (1 phr) 15 Mooney ML 1+4, 1 C 15 Tensile strength (1 phr) (1 phr) 2 [24h/1 C] 1,5 Injection volume (capillary/piston 1 C, mould 18 C) 15 1, % 1 cm 3 5,5 (1 phr), (1 phr) 22 * The process parameters are documented in the appendix

23 4.2.2 EPDM / Clay* Recipe 941E Deolink Deolink EPDM Buna EPG Clay Paraffin oil PEG ZnO Deolink Deolink TAC DL Perkadox Total phr DIN Abrasion Modulus 3 % mm (1 phr) (1 phr) ( 4 phr) 8 Mooney ML 1+4, 1 C 15 Tensile strength (1 phr) (1 phr) 2 [24h/1 C] 3, Injection volume (capillary/piston 1 C, mould 18 C) 15 2,5 2, % 1 cm 3 1,5 5 1,,5 (1 phr), (1 phr) * The process parameters are documented in the appendix 23

24 -KONTAKT EPDM / Aluminiumhydroxide* Recipe 95E Deolink Deolink EPDM Buna EPG Aluminiumhydroxide Paraffin oil ZnO Deolink 1,5 3 Deolink 1,5 3 TAC DL Perkadox Total phr DIN Abrasion Modulus 1 % mm (1,5 phr) (3 phr) (1,5 phr) (3 phr) 8 Mooney ML 1+4, 1 C 15 Tensile strength (1,5 phr) (3 phr) (1,5 phr) (3 phr) 12 [24h/1 C] 3, Injection volume (capillary/piston 1 C, mould 18 C) 1 2,5 8 2, % 6 cm 3 1,5 4 1, 2,5 (1,5 phr) (3 phr), (1,5 phr) (3 phr) 24 * The process parameters are documented in the appendix

25 4.3 Influence of different mixing temperatures* The influence of the processing temperature is compared with sulphur silanes of minor importance. To provide a representative illustration of the processing temperature on the silanization in a Banbury, the following temperatures have been chosen 11 C, 125 C, 145 C. Recipe 939E Deolink Deolink EPDM Buna EPG Silica (BET 125 m 2 /g) Paraffin oil PEG ZnO Deolink 2 Deolink 2 TAC DL Perkadox Total phr DIN Abrasion Modulus 3 % 12 1 mm C 11 C 11 C 125 C 125 C 145 C 145 C 11 C 11 C 11 C 125 C 125 C 145 C 145 C 12 Mooney ML 1+4, 1 C 14 Tensile strength C 11 C 11 C 125 C 125 C 145 C 145 C 11 C 11 C 11 C 125 C 125 C 145 C 145 C [24 h/1 C] 1,5 1,25 1, Injection volume (capillary/piston 1 C, mould 18 C) % 8 cm 3, ,5,25 11 C 11 C 11 C 125 C 125 C 145 C 145 C, 11 C 11 C 11 C 125 C 125 C 145 C 145 C * The process parameters are documented in the appendix 25

26 -KONTAKT Electrical Properties In articles made for the electronical industry, the electrical properties are of particular importance. Silanes can provide a significant input to improve the required performance. For unaged samples, the addition of silanes only show a small influence on the electrical properties. The major advantage of silanes can be observed, when measuring the electrical data after an ageing process. The control compound with unsilanized filler absorbs moisture and therefore reduces the insulation properties. Compounds containing silanes show extreme improvements. The hydrophobation of the filler and the increased cross-linking density reduce the water absorption and keep the insulation properties constant. Recipe 926E Deolink Deolink EPDM Keltan Suprex Clay Paraffin oil Controzon ZnO TMQ Deolink 2 Deolink 2 TAC DL Perkadox Total phr EPDM Cable Insulation 926E Room temperature 3 Days in 9 C water bath Dielectric Constant ASTM D 151 without Deolink phr Deolink phr Deolink Dissipation Factor ASTM D 15 without Deolink phr Deolink phr Deolink Volume Resistivity ASTM D 267 without Deolink Ωcm Ωcm 2 phr Deolink Ωcm Ωcm 2 phr Deolink Ωcm Ωcm Dielectric Strength ASTM D 149 without Deolink 228 kv/cm 61 kv/cm 2 phr Deolink 166 kv/cm 173 kv/cm 2 phr Deolink 26 kv/cm 142 kv/cm The electrical values have been measured on 2 mm test plates, and provide a general indication of the positive wet electrical properties. 26

27 5. Appendix Complete overview of all test series 5.1. Sulphur silanes Deolink / Deolink SBR / Silica (Recipe to and and 3.4) Recipe 451S 3) 3) 3) 1) 2) 3) 2) 1) 2) 3) 2) 2) 1) 2) 3) 2) Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] Buna SBR Silica (BET 175 m 2 /g) Naphthenic oil ZnO Stearic acid Antioxidant SPH PEG Deolink Deolink MBTS DPG Sulphur Total phr Rheometer MDR 2 (17 C/12 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 2 min/16 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 3 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (168 h/7 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/7 C [%] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s] ) Recipe to of page 9 2) Recipe to of page 13 3) Recipe to 3.4 of page

28 -KONTAKT NR / Silica Recipe 925N Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] 6 6 Speed [rpm] 7 7 Dumping temperature [ C] NR Pale Crepe 1 1 Silica (BET 175 m 2 /g) 5 5 Naphthenic oil 5 5 ZnO Stearic acid 2 2 Antioxidant SPH 1 1 Deolink 4 MBTS DPG.4.4 Sulphur 2 2 Total phr Rheometer Göttfert (17 C/12 min) F min [Nm] F max [Nm] t 1 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 15 min/16 C) Hardness [Shore A] 5 51 Tensile strength [] Elongation at break [%] Modulus 3 % [] Tear resistance [N/mm] Rebound [%] h/7 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

29 5.1.3 EPDM / Silica (Batch to 3.1.2) Recipe 93E1 Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] EPDM Buna EPG Silica (BET 125 m 2 /g) Paraffin oil ZnO Stearic acid PEG Deolink 2 4 Deolink 2 4 Deovulc TP MBTS DPG Deovulc ZBEC Sulphur Total phr Rheometer MDR 2 (18 C/6 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 2 min/16 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 3 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (72 h/12 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/7 C [%] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

30 -KONTAKT EPDM / Clay Recipe 93E2 Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] EPDM Buna EPG EPDM Buna EPG Clay Paraffin oil ZnO Stearic acid PEG Deolink 2 4 Deolink 2 4 Deovulc TP MBTS DPG Deovulc ZBEC Sulphur Total phr Rheometer MDR 2 (18 C/6 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 2 min/16 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 3 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (72 h/1 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/7 C [%] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

31 5.1.5 NBR / Silica Recipe 448A Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] 6 6 Speed [rpm] 7 7 Dumping temperature [ C] Perbunan NT Silica (BET 175 m 2 /g) 5 5 Ester plasticizer 1 1 ZnO Stearic acid.5.5 PEG Antioxidant SPH 1 1 Deolink 4 MBTS DPG.4.4 Sulphur 2 2 Total phr Rheometer Göttfert (17 C/12 min) F min [Nm].5.37 F max [Nm] t 1 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 15 min/16 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 3 % [] Tear resistance [N/mm] Rebound [%] h/7 C [%] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

32 -KONTAKT CR / Silica (Batch to 3.1.3) Recipe 248C Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] Baypren Silica (BET 125 m 2 /g) Ester plasticizer MgO Stearic acid Controzon GP Antioxidant ODPA Deolink 2 Deolink 2 ZnO MBTS ETU Total phr Rheometer MDR 2 (17 C/12 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 2 min/16 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 3 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (72 h/1 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/7 C [%] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

33 5.1.7 SBR / Clay (Batch to 3.3.2) Recipe 456S Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] Buna SBR Clay Naphthenic oil ZnO Stearic acid PEG Antioxidant SPH Deolink MBTS DPG Sulphur Total phr Rheometer MDR 2 (17 C/12 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 2 min/16 C min) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 3 % [] Tear resistance [N/mm] Rebound [%] h/7 C [%] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

34 -KONTAKT SBR / Silica (Batch to 3.4) Recipe 451S Mixing conditions: Roller mixer 26 mm, friction 1 : 1.1 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] Buna SBR Silica (BET 175 m 2 /g) Naphthenic oil ZnO Stearic acid Antioxidant SPH PEG Deolink 4 Deolink 4 MBTS DPG Sulphur Total phr Rheometer MDR 2 (17 C/12 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 2 min/16 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 3 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (168 h/7 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/7 C [%] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

35 5.2 silanes Deolink / Deolink EPDM / Silica (Batch to and 4.2.1) Recipe 94E 1) 2) 2) 1) 2) 2) 2) 1) 2) 2) Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperarture [ C] Speed [rpm] Dumping temperature [ C] EPDM Buna EPG Silica (BET 125 m 2 /g) Paraffin oil PEG ZnO Deolink Deolink TAC DL Perkadox Total phr Rheometer MDR 2 (18 C/6 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 1 min/18 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 3 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (72 h/1 C) Tensile strength [] 8,1 8,2 8,7 9,2 8,6 9,3 9,4 Elongation at break [%] Change in hardness [Shore A] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s] ) Recipe to of page 19 2) Recipe to of page 22 35

36 -KONTAKT H-NBR (fully saturated) / Silica (Batch to 4.1.2) Recipe 3T Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] H-NBR Therban Vulkasil A MgO ZnO Antioxidant SDPA Vulkanox ZMB Deoflow Deolink 2 3 Deolink 2 3 TAIC Perkadox Total phr Rheometer MDR 2 (18 C/6 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (not tempered) (Vulcanization 1 min/18 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 1 % [] Modulus 2 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (168 h/15 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/15 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

37 5.2.3 H-NBR (partly saturated) / Silica Recipe 2T Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] H-NBR Zetpol 22 L Vulkasil A MgO ZnO Antioxidant SDPA Vulkanox ZMB Deoflow Deolink 2 3 Deolink 2 3 TAIC Perkadox Total phr Rheometer MDR 2 (18 C/6 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (not tempered) (Vulcanization 1 min/18 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 1 % [] Modulus 2 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (168 h/15 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/15 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

38 -KONTAKT EVA / Aluminiumhydroxide (Batch to 4.1.3) Recipe 12L Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] Levapren 5HV Aluminiumhydroxide Zinc borate Vulkanox DDA Plasticizer DOS Deolink Deolink TAC Perkadox Total phr Rheometer MDR 2 (18 C/6 min) S I min [dnm] S I max [dnm] t 1 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 1 min/18 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 1 % [] Hot Air Ageing (168 h/15 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

39 5.2.5 CPE / Clay / Silica Recipe 4CM Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.78 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] CPE DAKREN 135H Silica (BET 125 m 2 /g) Clay MgO Antioxidant TMQ Plasticizer Bisoflex T 81 T Deolink 2 Deolink 2 Deoflow S EDMA DL Perkadox Total phr Rheometer MDR 2 (18 C/6 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 1 min/18 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 2 % [] Modulus 3 % [] Tear resistance [N/mm] Hot Air Ageing (72 h/125 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/125 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

40 -KONTAKT NBR / Silica Recipe 452A Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] Perbunan NT Vulkasil A Silica (BET 125 m 2 /g) Ester plasticizer ZnO PEG Deolink 2 Deolink 2 Antioxidant ZMTI Perkadox BC Total phr Rheometer MDR 2 (18 C/6 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 12 min/17 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 1 % [] Modulus 2 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (72 h/1 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

41 5.2.7 EPDM / Kaolin (Batch to 4.2.2) Recipe 941E Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] EPDM Buna EPG Clay Paraffin oil PEG ZnO Deolink Deolink TAC DL Perkadox Total phr Rheometer MDR 2 (18 C/6 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 1 min/18 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 3 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (72 h/1 C) Tensile strength [] 9,6 12, 1,7 1,1 11, 11,3 11,2 Elongation at break [%] Change in hardness [Shore A] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]

42 -KONTAKT EPDM / Aluminiumhydroxide (Batch to 4.2.3) Recipe 95E Mixing conditions: Farrel BR Banbury Mixer/Vol. 1.6 litre/fill factor.73 Starting temperature [ C] Speed [rpm] Dumping temperature [ C] EPDM Buna EPG Aluminiumhydroxide Paraffin oil ZnO Deolink Deolink TAC DL Perkadox Total phr Rheometer MDR 2 (18 C/6 min) S I min [dnm] S I max [dnm] t 1 [min] t 5 [min] t 9 [min] ML 1+4, 1 C Physical Properties (Vulcanization 1 min/18 C) Hardness [Shore A] Tensile strength [] Elongation at break [%] Modulus 1 % [] Tear resistance [N/mm] Rebound [%] Hot Air Ageing (72 h/1 C) Ret. Tensile strength [%] Ret. Elongation at break [%] Change in hardness [Shore A] h/1 C [%] DIN Abrasion Abrasion [mm 3 ] Rheovulkameter injection moulding test, capillary/piston 1 C, mould 18 C Volume [cm 3 /7 sec] Volume Speed [mm 3 /s]