Optimum use of Processing Additives in Rubber compounds. Basic principles and applications
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1 Optimum use of Processing Additives in Rubber compounds Basic principles and applications Dr. J. Bertrand VKRT meeting of 7 th December 2006 in Bilthoven, NL
2 Agenda Optimum use of Processing Additives Basic principles dominating the function of Processing Additives Interactions of Compound components Physico-chemical principles Specific and combined effects Applications Product classes Point of additive addition Conclusion
3 Basic principles dominating the function of Processing Additives Interaction of Compound components Influenced by: Strength of interaction (enthalpy driven): Van-der-Waals forces Hydrogen bonding Polar forces Ionic forces Covalent bonding (-> network) Steric hindrance Polymer Polymer Interaction Possibilities to arrange (entropy driven): Molecular mass Number of permutations Affect: Glass transition, Modulus, Tear Strength, Elongation, Resilience, Abrasion, Viscosity, Processability, Polymer blending
4 Basic principles dominating the function of Processing Additives Interaction of Compound components Influenced by: Strength of interaction (enthalpy driven): Van-der-Waals forces Polar forces Ionic forces Covalent bonding forces Steric hindrance Polymer Filler Interaction Possibilities to arrange (entropy driven): Molecular mass Number of permutations Affect: Reinforcement, Modulus, Tear Strength, Elongation, Hardness, Resilience Abrasion, Viscosity, Heat built-up, Processability, Filler incorporation etc.
5 Basic principles dominating the function of Processing Additives Interaction of Compound components Influenced by: Strength of interaction (enthalpy driven): Van-der-Waals forces Hydrogen bonding Polar forces Surface structure Filler Filler Interaction Possibilities to arrange (entropy driven): Particle size Affect: Modulus, Tear Strength, Elongation, Abrasion, Viscosity, Resilience, Hardness, Heat Built-up, Processability, Filler incorporation / dispersion etc.
6 Basic principles dominating the function of Processing Additives Interaction of Compound to Equipment Compound flow Metal equipment Influenced by: Strength of interaction (enthalpy driven): Van-der-Waals forces Polar forces Ionic forces Covalent bonding forces Compound Metal Interaction Affect: Mill / calander tack, Extrusion Flow Rates, Mould Release, Mould fouling, Building tack, Rubber-to-Metal adhesion
7 Basic principles dominating the function of Processing Additives Solubility parameter concept: Hildebrand parameters (SI) Amides Alkylester Sulfates Ester Carbonates Fatty Acids Hydrophobic side Alkenes Arom. Hydrocarbons Ethers PPG/PEG Hydrophilic side PTFE PE PP PVAc PVC PS PMMA PAN PA 6.6 PET IIR NR, BR, SBR CR, NBR 25 ACN
8 Basic principles dominating the function of Processing Additives Specific effects Shear forces Micell formation of Metal soaps, eg.: Ultra-Flow 500 Ultra-Flow 800 Retarder,eg.: Ultra-Flow ZEH for PUR Ultra-Gard IMR for ECO
9 Basic principles dominating the function of Processing Additives Combined effects: Tackifier A good tackifier: Optimum use of Processing Additives Needs a good to excellent solubility / compatibility to both adhesion partners Must have a minimum Molecular weight to built-up enough bonds to bridge the two partners (about 500 gr/mol) Must be dosed higher than the solubility threshold to migrate to the surface Works best 10K above its softening temperature, gets brittle below, at higher temperature the intermolecular forces get overruled by thermal movement Aromatic groups in tackifiers build forces to aromatics, filler surfaces and metal elements -> most widely used (C9, Phenolic resins, Xylene, Coumarone/Indene etc.)
10 Basic principles dominating the function of Processing Additives Basic need: Distribution of the additive A good distribution of an additive can be achieved, if: it melts down at temperatures below the processing temperature at least one major component of the additive has to soften below the processing temperature (mill: max. 70 C, IM: max. 135 C) Example: Sulfur or metal oxides do not melt during mixing, sulfur and metal oxide pre-dispersions in a low-melting matrix distribute the material excellently during mixing
11 Application of Processing Additives Peptizer / Mastication systems: Reduction of molecular weight of Natural Rubber Chemical peptizer, eg.: Ultra-Pep 96, Ultra-Pep 148 Viscosity reduction of NR in peptisation step Quick reduction of viscosity and nerve by cleavage of polymer main chain Improvement of blending and processing properties of NR by lower viscosity Booster component adheres to fillers, therefore incorporation into NR mandatory before filler addition
12 Application of Processing Additives Homogenizer: Increase of Friction, levelling the compatibility of polymers eg.: Ultra-Blend 4000 (black), Ultra-Blend 6000 (light coloured), Ultra-Blend 5500 (blend of homogenizer and lubricant) Enhanced polymer blending Higher mixing efficiency (lower energy consumption at equal homogeneity) Lower scrap rates Higher storage stability Better dimension stability of uncured products
13 Application of Processing Additives Homogenizer: Increase of Friction, levelling the compatibility of polymers example: Ultra-Blend 5500 in NR/BR blend NR/BR blend without additive: NR/BR blend with 4 phr UB 5500:
14 Application of Processing Additives Internal Lubricants: Lowering polymer polymer and polymer filler interactions eg.: Ultra-Flow 500, 600 -> NR, CB compounds Ultra-Flow 440, 700S, 800 -> NR, CB and silica compounds Ultra-Lube 200, 220 -> general filler dispersants and lubricants Ultra-Lube 420: EPDM Lower compound viscosity Better filler incorporation Higher mixing efficiency (lower energy consumption at equal filler dispersion) Higher extrusion flow rates Lower viscosity rise upon storage Quicker compound relaxation behind extrusion die, better control over part dimensions
15 Application of Processing Additives External Lubricants: Lowering compound equipment interactions eg.: Ultra-Lube 160 -> general purpose Ultra-Lube IMX -> highly effective, polar polymers (ECO, ACM, AEM, HNBR, NBR, CSM etc.) Ultra-Lube 220, 420 -> SBR, EPDM Ultra-Lube 790 -> FPM compound viscosity less affected Less adhesion to mill, calander or mixer Excellent extrusion flow rates Excellent mould release Reduced mould fouling
16 Application of Processing Additives Plasticiser: Lowering polymer polymer and polymer filler interactions eg.: Optimum use of Processing Additives A) Ultra-Flex 750, 950 -> NBR, HNBR, ECO etc. Low temperature flexibility in high Tg polymers Low volatility at temperatures of use B) Ultra-Blend 3000 / DL -> non-migrating plastiziser for NBR not oil-extractable non-volatile C) Ultra-Flex AS -> brings antistatic properties Ultra-Flex AS: antistatic properties for rollers, flooring, cods etc.
17 Application of Processing Additives Tackifier resins: migrating, surface active, increase adhesion forces eg.: Ultra-Blend > Xylene resin blend, Sp.: 20 C Ultra-Blend > Pelletized colophony, Sp.: 80 C Ultra-Blend > Aromatic hydrocarbon resin blend, Sp.: C Ultra-Blend > Phenolic resin blend, Sp.: 135 C Migration velocity is steered by solubility and molecular weight The higher the MW, the slower the migration Low Softening point: high short term tack, low long term tack High Softening point: low short term tack, high long term tack
18 Pre-Dispersions: Optimum use of Processing Additives Application of Processing Additives eg.: Ultra-Sulph 950, 1050, 1090, 1200, > Sulfur pre-dispersions Ultra-Mag 9000, > Magnesium oxide pre-dispersions Ultra-Zinc > Zinc oxide pre-dispersions Low-melting matrix carries the non-melting product into the compound Matrix prevents reagglomeration of product Pre-dispersions ensure excellent dispersion in critical compounds, eg. soft roller compounds The full potential of more active Metal oxides is tapped
19 Point of additive addition: Optimum use of Processing Additives Application of Processing Additives Mastication step: Conventional chemical peptizer First masterbatch: Together with Polymers: Together with Fillers: Modern peptizer, Homogenizer, Internal lubricants Filler dispersants, Plastiziser Last mixing step: External lubricants, Tackifier
20 Application of Processing Additives Conclusion: Processing Additives are no magic but work based on scientific knowledge Processing Additives allow to process critical compounds Processing Additives increase process efficiency Processing Additives help to manage the counteracting requirements of compound performance and compound processing Solve your compound requirements by the choice of rubber, filler, curing system; solve your processing requirements by processing additives!
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