US20090064896A1 - Friction material and process for the production thereof - Google Patents
Friction material and process for the production thereof Download PDFInfo
- Publication number
- US20090064896A1 US20090064896A1 US11/995,173 US99517306A US2009064896A1 US 20090064896 A1 US20090064896 A1 US 20090064896A1 US 99517306 A US99517306 A US 99517306A US 2009064896 A1 US2009064896 A1 US 2009064896A1
- Authority
- US
- United States
- Prior art keywords
- tin
- source
- sulphur
- friction material
- friction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002783 friction material Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 131
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000005864 Sulphur Substances 0.000 claims abstract description 80
- 230000001050 lubricating effect Effects 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 238000010952 in-situ formation Methods 0.000 claims abstract description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 60
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 52
- 229910052960 marcasite Inorganic materials 0.000 claims description 50
- 229910052683 pyrite Inorganic materials 0.000 claims description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910000906 Bronze Inorganic materials 0.000 claims description 2
- 229910017755 Cu-Sn Inorganic materials 0.000 claims description 2
- 229910017927 Cu—Sn Inorganic materials 0.000 claims description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- 229910003092 TiS2 Inorganic materials 0.000 claims description 2
- 239000010974 bronze Substances 0.000 claims description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 239000004677 Nylon Substances 0.000 claims 1
- 239000005083 Zinc sulfide Substances 0.000 claims 1
- 229920001778 nylon Polymers 0.000 claims 1
- OCDVSJMWGCXRKO-UHFFFAOYSA-N titanium(4+);disulfide Chemical compound [S-2].[S-2].[Ti+4] OCDVSJMWGCXRKO-UHFFFAOYSA-N 0.000 claims 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 67
- 238000009472 formulation Methods 0.000 description 20
- 239000002243 precursor Substances 0.000 description 13
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 12
- 229910001887 tin oxide Inorganic materials 0.000 description 11
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical class [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229920002367 Polyisobutene Polymers 0.000 description 9
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 8
- 238000010979 pH adjustment Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000004763 sulfides Chemical class 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical class [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 3
- 229940095064 tartrate Drugs 0.000 description 3
- 101000624947 Homo sapiens Nesprin-1 Proteins 0.000 description 2
- 102100023306 Nesprin-1 Human genes 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052959 stibnite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- QUBMWJKTLKIJNN-UHFFFAOYSA-B tin(4+);tetraphosphate Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QUBMWJKTLKIJNN-UHFFFAOYSA-B 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/06—Metal compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/22—Compounds containing sulfur, selenium or tellurium
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
- F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
- F16D69/02—Composition of linings ; Methods of manufacturing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/043—Sulfur; Selenenium; Tellurium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/043—Sulfur; Selenenium; Tellurium
- C10M2201/0433—Sulfur; Selenenium; Tellurium used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/76—Reduction of noise, shudder, or vibrations
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/14—Composite materials or sliding materials in which lubricants are integrally molded
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
- F16D2200/00—Materials; Production methods therefor
- F16D2200/006—Materials; Production methods therefor containing fibres or particles
- F16D2200/0073—Materials; Production methods therefor containing fibres or particles having lubricating properties
Definitions
- the present invention relates to a friction material and a process for the production of a friction material.
- the present invention relates to a friction material that relies on a lubricating phase of a compound containing tin and sulphur.
- Friction materials are used in brake pads, brake shoes, brake linings and clutch linings for automobiles, heavy goods vehicles, trains and the like.
- the resistance to sliding motion between, for example, a brake pad and a brake disc results in the generation of heat.
- at least some of the energy of motion is converted to heat as the vehicle brakes.
- Friction materials are complicated multi-component materials and may comprise, for example, metal fibres, metal powders, organic or mineral fibres, binders, fillers and frictional components. Friction materials also often contain solid lubricants (also known as friction modifiers or stabilisers). The purpose of the lubricant is to improve the braking and wear characteristics of the friction material. For example, NVH (Noise, Vibration and Hardness) is an important parameter in many applications. The lubricant helps prevent wear, squeal and other undesirable effects.
- Known solid lubricants for use in friction material formulations include graphite and sulphides of molybdenum, lead, antimony and tin.
- Lead and antimony sulphides have been widely used as friction stabilisers in friction materials. However, lead and antimony sulphides are increasingly considered to be harmful to the environment.
- tin sulphides offer good performance and are considered less harmful than lead and antimony sulphides, these materials have a limited supply.
- the manufacturing process to form a friction formulation comprising a tin sulphide lubricating phase is also relatively expensive.
- tin sulphide costs approximately three to four times the cost of antimony and lead sulphides. This has limited the uptake of tin sulphide technology.
- the friction material according to the present invention is more environmentally friendly than conventional friction materials. It also represents the development of a commercially advantageous tin-based product.
- the present invention provides a process for the in-situ formation of a lubricating phase comprising sulphur and tin in a friction material, wherein reaction of a sulphur source with a tin source in said friction material results in the formation of said lubricating phase, and wherein said reaction is initiated or effected by heat resulting, in use, from the generation of friction, wherein said sulphur source is selected from one or both of sulphur and/or a metal sulphide selected from one or more of iron, copper, zinc, titanium and bismuth, and wherein said tin source is selected from one or more of tin, a tin-containing compound and/or a tin-containing alloy.
- the lubricating phase is or includes a sulphide of tin.
- the sulphide of tin will typically have the general formula Sn x S y , where x is form 0.5 to 5 and y is from 1 to 10.
- x is form 1 to 5.
- y is from 5 to 10.
- Suitable examples include one or more of SnS, SnS 2 and Sn 2 S s .
- SnS 2 is the preferred lubricating phase, although it will be appreciated that a complex combination of sulphides may be present.
- SnS 2 will typically be formed if there is an excess of sulphur over tin at the reaction site. If there is insufficient sulphur, then a lower sulphide may be formed such as, for example, SnS or Sn 2 S 3 .
- SnS 2 the minimum (mole) ratio of sulphur to tin is 2:1. An excess above this stoichiometric ratio is, however, preferred so as to account for non-ideal solid state mixing.
- an excess of said sulphur source above the stoichiometric level required to form a lubricating phase comprising a sulphide of tin.
- an excess of said first precursor for example FeS 2
- FeS 2 is provided so as to convert all of the tin to SnS 2 .
- mixtures containing a two-fold ratio of FeS 2 to Sn may be used.
- two or more different sulphur sources and/or two or more different tin sources may be included.
- the sulphur source may be one or both of sulphur and/or a metal sulphide.
- metal sulphides include one or more of iron, copper, zinc, titanium and bismuth, including combinations of two or more thereof.
- the preferred metal sulphides are one or more of FeS, FeS 2 , Cu 2 S, ZnS, TiS 2 and Bi 2 S 3 .
- the metal sulphide may be provided in the form of a fine (for example micron-sized) powder.
- the metal sulphide may be encapsulated with a carbon source (for example a polymer) during blending.
- the tin source may be selected from one or more of tin, a compound containing tin and an alloy containing tin. Suitable examples include one or more of SnO, SnO 2 and a Cu—Sn bronze.
- the tin source may also be provided in the form of a fine (for example micron-sized) powder.
- the tin source may also be encapsulated with a carbon source (for example a polymer) during blending.
- the friction material preferably further comprises a carbon source.
- the carbon source if present, may be selected from one or both of graphite and/or a polymer.
- suitable polymers include polyisobutylene (PIB) and phenolic resins. While not wishing to be restricted by theory it is considered that the presence of carbon prevents or restricts the burn-off of sulphur to, for example, SO 2 .
- the carbon source may reduce the tin oxide to metallic tin, which makes it more reactive with the sulphur source to form, for example, SnS 2 .
- the sulphur source and/or the tin source(s) is/are encapsulated in a carbon source, for example a polymer such as polyisobutylene (PIB).
- a carbon source for example a polymer such as polyisobutylene (PIB).
- the carbon source preferably a polymer, more preferably PIB
- the friction material may further comprises one or both of a reducing agent and/or a catalyst.
- Graphite if present, may function as both a lubricant and a reducing agent.
- sulphides of tin can be accelerated in a reducing environment.
- the reaction of tin or tin oxide and sulphur or FeS 2 is accelerated in a reducing environment.
- the underlying mechanisms are believed to involve complex intermediates, redox and disproportionation.
- reducing agents such as graphite, for example, may affect the chemistry by controlling the extent and reversibility of oxidation reactions.
- reducing agents such as graphite, for example, may affect the chemistry by controlling the extent and reversibility of oxidation reactions.
- tin oxide will reduce to tin metal in the presence of carbon, while tin metal will combine with sulphur under pressure and appropriate conditions to produce mixed complex sulphides.
- the sulphur source and the tin source will typically be present in the friction material in a combined total amount of up to 15% by weight and preferably in an amount of from 0.5 to 10% by weight, more preferably from 2 to 8% by weight, still more preferably from 4 to 6% by weight. Approximately 5% by weight is the optimum amount.
- the friction material may comprise, in addition to the lubricating phase, one or more of metal fibres, metal powders, organic or mineral fibres, binders, fillers and frictional components.
- the lubricating phase may act as a friction stabiliser and/or modifier.
- the term lubricating phases is intended to encompass these terms as well.
- the friction material may be or may be comprised in a brake pad, a brake shoe, a brake lining or a clutch lining.
- the lubricating phase is formed in the friction material in-situ during the friction-generating process, for example the braking process. This is in contrast to conventional methods where the lubricating phase is formed during the manufacture of the friction material prior to its intended use.
- the lubricating phase will typically be formed in the surface region of the friction material.
- Tin sulphides are typically formed at the braking interface at temperature of from 600 to 900° C., more typically from 700 to 800° C.
- the present invention provides a friction material for a brake pad, brake shoe, brake lining or clutch lining, wherein said friction material includes a sulphur source and a tin source, wherein said sulphur source is selected from one or both of sulphur and/or a metal sulphide selected from one or more of iron, copper, zinc, titanium and bismuth, and wherein said tin source is selected from one or more of tin, a tin-containing compound and a tin-containing alloy, said friction material optionally further comprising a carbon source, and wherein, in use, said sulphur source and said tin source react in-situ to form a lubricating phase having the general formula Sn x S y , where x is form 0.5 to 5 and y is from 1 to 10, said reaction being initiated or effected by heat resulting from the generation of friction.
- the lubricating phase preferably has the general formula Sn x S y , where x is form 0.5 to 2 and y is from 1 to 3. More preferably, x is form 0.8 to 1.2 and y is from 1.5 to 2.5. Still more preferably, x is approximately 1 and y is approximately 2.
- the sulphur source and the tin source are typically be present in the friction material in a combined total amount of up to 15% by weight.
- the sulphur source and the tin source are present in a combined total amount of from 0.5 to 10% by weight, more preferably from 2 to 8% by weight, still more preferably from 4 to 6% by weight.
- the sulphur source will typically be present in the friction material in an amount of up to 10% weight.
- the tin source will typically be present in the friction material in an amount of up to 5% weight.
- the ratio of the metal sulphide to tin (or a compound containing tin or an alloy containing tin) is preferably in the range of from 1:1 to 5:1. More preferably, there is at least two times the stoichiometric quantity of metal sulphide to tin (or a compound containing tin or an alloy containing tin).
- the sulphur source and/or the tin source will typically be provided in the form of fine powders for blending in the friction material formulation. It should be appreciated that the efficacy of the conversion from the precursors to the active tin-sulphide species will depend on the particle size and surface area of the precursor particles. In the case of tin metal, powders with a mean particle size of 50 ⁇ m, and in the case of tin oxides, of less than 2 ⁇ m, are preferred.
- the sulphur source and/or the tin source is/are encapsulated in a carbon source, for example a polymer such as polyisobutylene.
- the friction material may further comprises one or both of a reducing agent and/or a catalyst.
- Graphite if present, may function as both a lubricant and a reducing agent.
- the sulphur source may advantageously be coated with the tin source by, for example, a sol-gel technique.
- sulphur source particles may be coated with tin oxide using a sol-gel technique.
- a suitable process for doing this is described in, for example, International (PCT) Application No. PCT/GB03/001561), which relates to processes for coating inorganic particulate materials with colloidal tin species.
- colloidal SnO 2 is coated on, for example, FeS 2 particles.
- the friction material according to the present invention will typically also include one or more of metal fibres (e.g. steel wool), metal powders, organic and mineral fibres, organic components and binders, fillers and frictional materials.
- the present invention also provides a brake pad, brake shoe, brake lining or clutch lining comprising a friction material as herein described.
- the sulphur source comprises Sn and the sulphur source comprises FeS 2 , then the in-situ reaction to form SnS 2 is: Sn+FeS 2 -->SnS 2 +Fe.
- the in-situ reaction to form SnS 2 is: Sn+FeS 2 -->SnS 2 +Fe.
- the inventors have found that an excess of the metal sulphide above the stoichiometric level is often required to convert all of the tin to the desired sulphide. In particular, at least twice the stoichiometric amount and sometimes as much as five times the stoichiometric amount is required. Thus, for example, on the basis of 2:1 stoichiometry, the weight percentages in the friction material formulation would be 6.56% by weight FeS 2 to 3.25% by weight Sn.
- a high degree of dispersion of the precursors in the friction material and the interfacial nature of the friction surface reaction can lead to a significant enhancement of the chemical interactions compared to bulk chemistries.
- Reaction products using the in-situ principle according to the present invention have different properties from those produced by conventional pre-formulation reactions.
- coating particles with tin oxide using a sol-gel technique is used to further facilitate the dispersion of the precursor components and improve reactivity.
- the present invention further provides a method of manufacturing a friction material for a friction element, wherein the method comprises incorporating a sulphur source and a tin source into a friction element, and wherein reaction of said sulphur source and said tin source results in the formation of a lubricating phase, said reaction being initiated or effected by heat resulting, from the generation of friction, wherein said sulphur source is selected from one or both of sulphur and/or a metal sulphide selected from one or more of iron, copper, zinc, titanium and bismuth, and wherein said tin source is selected from one or more of tin, a tin-containing compound and/or a tin-containing alloy.
- the present invention further provides for the use of a tin source and a sulphur source for manufacturing a friction material, wherein reaction of said tin source and said sulphur source results in the formation of a lubricating phase, said reaction being initiated or effected by heat resulting from the generation of friction, wherein said sulphur source is selected from one or both of sulphur and/or a metal sulphide selected from one or more of iron, copper, zinc, titanium and bismuth, and wherein said tin source is selected from one or more of tin, a tin-containing compound and/or a tin-containing alloy.
- the friction element may be, for example, a brake pad, brake shoe, brake lining or clutch lining.
- the present invention describes the novel principle of utilising friction energy to produce the functional species from cheaper precursors.
- the present invention relies on thermal energy generated during normal driving and braking to form friction modifiers in-situ in the friction material.
- Cheaper basic tin and sulphur compounds may be used in the blends, whose reaction products are capable of significant effects on friction material performance.
- cheaper basic precursor additives such as elemental tin, tin oxide, sulphur and metal sulphides may be used.
- the normal temperature and pressure at the friction interface results in reaction of these precursors to form the active compounds at the surface of the friction material.
- Table 1 shows simultaneous thermogravimetric analysis and differential scanning calorimetry analysis for samples of tin and iron disulphide, and mixtures thereof. The samples were heated in air from ambient temperature to 1000° C. at a heating rate of 10° C./minute.
- a lubricating phase when a tin source and a sulphur source are incorporated into a friction material, the tin source and the sulphur source were encapsulated in an organic polymer (PIB) for further testing.
- PIB organic polymer
- Table 2 shows various blends of the tin and sulphur sources with the organic polymer.
- the PIB polymer is incorporated in a typical quantity of ⁇ 5% by weight.
- Table 3 shows X-ray powder diffraction data for blends 1, 2, 3 and 4 (whose composition is described in Table 2) after being heated at 500° C. for 2 hours.
- the data shows that blends 1 and 2 (comprising mixtures of tin metal powder with iron disulphide) both show evidence of thermal reaction to form tin-sulphur species.
- blends 3 and 4 comprising mixtures of tin (IV) oxide with iron disulphide
- Sn (IV) species need to be reduced to Sn (II) before formation of the lubricating phase, which is not possible at the reaction temperature.
- Table 4 details the general composition of the trial brake pad formulations.
- Table 5 details various lubricating phases/precursors added to the general composition described in Table 4 (all in 5% by volume).
- Table 5 details the results of wear tests on the various brake pad formulations. The results clearly show the effectiveness of blends 1 to 4 in reducing the wear rate of the brake pad formulations compared to the composition C1 in which no lubricating phase is added; in addition, the results show that the performance of blends 1 to 4 is comparable or better than the performance of the conventional lubricating phases Sb 2 S 3 or PbS (in comparative examples C2 and C3) or the commercial lubricating phases (in comparative examples C4 and C5).
- Table 5 also details the friction of coefficient measured for the various brake pad formulations. These show little variation between the different samples.
- Table 6 shows a X-Ray Diffraction (XRD) study on the powdered surfaces of the prototype brake pads formulated using blends 2 and 4 (whose compositions are given in Table 2), carried out at 500° C. In both cases reaction to form tin sulphide (SnS) as the major product is evident. Overall, the phase analyses for the two powdered surfaces were almost identical, although the pad containing blend 4 did show some unreacted SnO 2 . This result for blend 4 is in contrast to the results in Table 3 where no tin sulphide was formed in compositions containing SnO 2 . This therefore emphasises the importance of heat produced by friction in the production of the lubricating phase, as no reaction was evident in the absence of friction.
- XRD X-Ray Diffraction
- Table 7 illustrates various ways in which the sol-gel technique can be used to prepare novel products comprising an intimate blend of inorganic tin species with iron disulphide.
- Table 8 details a series of calculation to establish weight ratios of the components required to produce 5% SnS 2 in brake pad formulations.
- **‘Ultimate C’ is a proprietary antimony trisulphide replacement marketed by Itaprochim and known to contain MoS 2 and FeS 2 .
- ***‘CPG2’ is a proprietary friction stabilising additive marketed by Chemetall and claimed to contain 90% SnS 2 .
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Abstract
Description
- The present invention relates to a friction material and a process for the production of a friction material. In particular, the present invention relates to a friction material that relies on a lubricating phase of a compound containing tin and sulphur.
- Friction materials are used in brake pads, brake shoes, brake linings and clutch linings for automobiles, heavy goods vehicles, trains and the like. The resistance to sliding motion between, for example, a brake pad and a brake disc results in the generation of heat. Thus, at least some of the energy of motion is converted to heat as the vehicle brakes.
- Friction materials are complicated multi-component materials and may comprise, for example, metal fibres, metal powders, organic or mineral fibres, binders, fillers and frictional components. Friction materials also often contain solid lubricants (also known as friction modifiers or stabilisers). The purpose of the lubricant is to improve the braking and wear characteristics of the friction material. For example, NVH (Noise, Vibration and Hardness) is an important parameter in many applications. The lubricant helps prevent wear, squeal and other undesirable effects.
- Known solid lubricants for use in friction material formulations include graphite and sulphides of molybdenum, lead, antimony and tin.
- Lead and antimony sulphides have been widely used as friction stabilisers in friction materials. However, lead and antimony sulphides are increasingly considered to be harmful to the environment.
- While tin sulphides offer good performance and are considered less harmful than lead and antimony sulphides, these materials have a limited supply. The manufacturing process to form a friction formulation comprising a tin sulphide lubricating phase is also relatively expensive. Typically tin sulphide costs approximately three to four times the cost of antimony and lead sulphides. This has limited the uptake of tin sulphide technology.
- The friction material according to the present invention is more environmentally friendly than conventional friction materials. It also represents the development of a commercially advantageous tin-based product.
- Accordingly, in a first aspect, the present invention provides a process for the in-situ formation of a lubricating phase comprising sulphur and tin in a friction material, wherein reaction of a sulphur source with a tin source in said friction material results in the formation of said lubricating phase, and wherein said reaction is initiated or effected by heat resulting, in use, from the generation of friction, wherein said sulphur source is selected from one or both of sulphur and/or a metal sulphide selected from one or more of iron, copper, zinc, titanium and bismuth, and wherein said tin source is selected from one or more of tin, a tin-containing compound and/or a tin-containing alloy.
- Preferably, the lubricating phase is or includes a sulphide of tin. The sulphide of tin will typically have the general formula SnxSy, where x is form 0.5 to 5 and y is from 1 to 10. Preferably, x is form 1 to 5. Preferably, y is from 5 to 10. Suitable examples include one or more of SnS, SnS2 and Sn2Ss. SnS2 is the preferred lubricating phase, although it will be appreciated that a complex combination of sulphides may be present.
- SnS2 will typically be formed if there is an excess of sulphur over tin at the reaction site. If there is insufficient sulphur, then a lower sulphide may be formed such as, for example, SnS or Sn2S3. As will be appreciated, in order to form SnS2 the minimum (mole) ratio of sulphur to tin is 2:1. An excess above this stoichiometric ratio is, however, preferred so as to account for non-ideal solid state mixing.
- In a preferred embodiment of the present invention there is an excess of said sulphur source above the stoichiometric level required to form a lubricating phase comprising a sulphide of tin. In a particularly preferred embodiment, an excess of said first precursor, for example FeS2, is provided so as to convert all of the tin to SnS2. For example, mixtures containing a two-fold ratio of FeS2 to Sn may be used.
- It will be appreciated that two or more different sulphur sources and/or two or more different tin sources may be included. In order to simplify the process, however, it is often desirable to have just two precursors, for example one sulphur source and one tin source.
- The sulphur source may be one or both of sulphur and/or a metal sulphide. Examples of metal sulphides include one or more of iron, copper, zinc, titanium and bismuth, including combinations of two or more thereof. The preferred metal sulphides are one or more of FeS, FeS2, Cu2S, ZnS, TiS2 and Bi2S3.
- The use of a metal sulphide, preferably FeS2, is preferred to the use of free sulphur. The metal sulphide may be provided in the form of a fine (for example micron-sized) powder. The metal sulphide may be encapsulated with a carbon source (for example a polymer) during blending.
- Even though the use of metal sulphides is preferred, the addition of free sulphur to the formulations may be desirable for certain applications.
- The tin source may be selected from one or more of tin, a compound containing tin and an alloy containing tin. Suitable examples include one or more of SnO, SnO2 and a Cu—Sn bronze. The tin source may also be provided in the form of a fine (for example micron-sized) powder. The tin source may also be encapsulated with a carbon source (for example a polymer) during blending.
- The friction material preferably further comprises a carbon source. Preferably, the carbon source, if present, may be selected from one or both of graphite and/or a polymer. Examples of suitable polymers include polyisobutylene (PIB) and phenolic resins. While not wishing to be restricted by theory it is considered that the presence of carbon prevents or restricts the burn-off of sulphur to, for example, SO2. Also, in the case of tin oxide, for example SnO2, the carbon source may reduce the tin oxide to metallic tin, which makes it more reactive with the sulphur source to form, for example, SnS2.
- Advantageously, the sulphur source and/or the tin source(s) is/are encapsulated in a carbon source, for example a polymer such as polyisobutylene (PIB). Preferably, the carbon source (preferably a polymer, more preferably PIB) should be included in the friction material in a proportion of less than or equal to 5 wt. % of the combined weight of the carbon, sulphur and tin sources.
- The friction material may further comprises one or both of a reducing agent and/or a catalyst.
- Graphite, if present, may function as both a lubricant and a reducing agent.
- The formation of sulphides of tin can be accelerated in a reducing environment. For example, the reaction of tin or tin oxide and sulphur or FeS2 is accelerated in a reducing environment. The underlying mechanisms are believed to involve complex intermediates, redox and disproportionation.
- The presence of reducing agents such as graphite, for example, may affect the chemistry by controlling the extent and reversibility of oxidation reactions. For example, tin oxide will reduce to tin metal in the presence of carbon, while tin metal will combine with sulphur under pressure and appropriate conditions to produce mixed complex sulphides.
- The sulphur source and the tin source will typically be present in the friction material in a combined total amount of up to 15% by weight and preferably in an amount of from 0.5 to 10% by weight, more preferably from 2 to 8% by weight, still more preferably from 4 to 6% by weight. Approximately 5% by weight is the optimum amount.
- As will be appreciated by those skilled in the art, the friction material may comprise, in addition to the lubricating phase, one or more of metal fibres, metal powders, organic or mineral fibres, binders, fillers and frictional components.
- As will also be appreciated, the lubricating phase may act as a friction stabiliser and/or modifier. Thus, the term lubricating phases is intended to encompass these terms as well.
- The friction material may be or may be comprised in a brake pad, a brake shoe, a brake lining or a clutch lining.
- In the present invention, the lubricating phase is formed in the friction material in-situ during the friction-generating process, for example the braking process. This is in contrast to conventional methods where the lubricating phase is formed during the manufacture of the friction material prior to its intended use. The lubricating phase will typically be formed in the surface region of the friction material. Tin sulphides are typically formed at the braking interface at temperature of from 600 to 900° C., more typically from 700 to 800° C.
- In a second aspect, the present invention provides a friction material for a brake pad, brake shoe, brake lining or clutch lining, wherein said friction material includes a sulphur source and a tin source, wherein said sulphur source is selected from one or both of sulphur and/or a metal sulphide selected from one or more of iron, copper, zinc, titanium and bismuth, and wherein said tin source is selected from one or more of tin, a tin-containing compound and a tin-containing alloy, said friction material optionally further comprising a carbon source, and wherein, in use, said sulphur source and said tin source react in-situ to form a lubricating phase having the general formula SnxSy, where x is form 0.5 to 5 and y is from 1 to 10, said reaction being initiated or effected by heat resulting from the generation of friction.
- All features herein described with reference to the first aspect are equally applicable either singularly or in combination with the invention according to the second aspect.
- The lubricating phase preferably has the general formula SnxSy, where x is form 0.5 to 2 and y is from 1 to 3. More preferably, x is form 0.8 to 1.2 and y is from 1.5 to 2.5. Still more preferably, x is approximately 1 and y is approximately 2.
- The sulphur source and the tin source are typically be present in the friction material in a combined total amount of up to 15% by weight. Preferably, the sulphur source and the tin source are present in a combined total amount of from 0.5 to 10% by weight, more preferably from 2 to 8% by weight, still more preferably from 4 to 6% by weight.
- The sulphur source will typically be present in the friction material in an amount of up to 10% weight.
- The tin source will typically be present in the friction material in an amount of up to 5% weight.
- In stoichiometric terms, the ratio of the metal sulphide to tin (or a compound containing tin or an alloy containing tin) is preferably in the range of from 1:1 to 5:1. More preferably, there is at least two times the stoichiometric quantity of metal sulphide to tin (or a compound containing tin or an alloy containing tin).
- The sulphur source and/or the tin source will typically be provided in the form of fine powders for blending in the friction material formulation. It should be appreciated that the efficacy of the conversion from the precursors to the active tin-sulphide species will depend on the particle size and surface area of the precursor particles. In the case of tin metal, powders with a mean particle size of 50 □m, and in the case of tin oxides, of less than 2 □m, are preferred.
- Advantageously, the sulphur source and/or the tin source is/are encapsulated in a carbon source, for example a polymer such as polyisobutylene.
- The friction material may further comprises one or both of a reducing agent and/or a catalyst.
- Graphite, if present, may function as both a lubricant and a reducing agent.
- The sulphur source may advantageously be coated with the tin source by, for example, a sol-gel technique. For example, sulphur source particles may be coated with tin oxide using a sol-gel technique. A suitable process for doing this is described in, for example, International (PCT) Application No. PCT/GB03/001561), which relates to processes for coating inorganic particulate materials with colloidal tin species. In a preferred embodiment of the present invention, colloidal SnO2 is coated on, for example, FeS2 particles.
- As will be appreciated, the friction material according to the present invention will typically also include one or more of metal fibres (e.g. steel wool), metal powders, organic and mineral fibres, organic components and binders, fillers and frictional materials.
- The present invention also provides a brake pad, brake shoe, brake lining or clutch lining comprising a friction material as herein described.
- As mentioned above, there is preferably an excess of the sulphur source above the stoichiometric level required to form the lubricating phase. This feature will be described further by way of the following example. If the tin source comprises Sn and the sulphur source comprises FeS2, then the in-situ reaction to form SnS2 is: Sn+FeS2-->SnS2+Fe. On a stoichiometric basis, to produce for example 5% by weight SnS2 in the friction material, one would use 3.28% by weight FeS2 and 3.25% by weight Sn in the formulation. However, the inventors have found that an excess of the metal sulphide above the stoichiometric level is often required to convert all of the tin to the desired sulphide. In particular, at least twice the stoichiometric amount and sometimes as much as five times the stoichiometric amount is required. Thus, for example, on the basis of 2:1 stoichiometry, the weight percentages in the friction material formulation would be 6.56% by weight FeS2 to 3.25% by weight Sn. As will be appreciated, the calculation will be different for other metal sulphides such as FeS or Cu2S, but the principle remains the same: an excess of the metal sulphide above the stoichiometric level is often required to convert all of the tin to the desired sulphide. In all formulations, 3.25% be weight of Sn should result in 5% by weight SnS2, provided that complete conversion takes place.
- A high degree of dispersion of the precursors in the friction material and the interfacial nature of the friction surface reaction can lead to a significant enhancement of the chemical interactions compared to bulk chemistries. Reaction products using the in-situ principle according to the present invention have different properties from those produced by conventional pre-formulation reactions.
- In a preferred embodiment, coating particles with tin oxide using a sol-gel technique is used to further facilitate the dispersion of the precursor components and improve reactivity.
- The present invention further provides a method of manufacturing a friction material for a friction element, wherein the method comprises incorporating a sulphur source and a tin source into a friction element, and wherein reaction of said sulphur source and said tin source results in the formation of a lubricating phase, said reaction being initiated or effected by heat resulting, from the generation of friction, wherein said sulphur source is selected from one or both of sulphur and/or a metal sulphide selected from one or more of iron, copper, zinc, titanium and bismuth, and wherein said tin source is selected from one or more of tin, a tin-containing compound and/or a tin-containing alloy.
- The present invention further provides for the use of a tin source and a sulphur source for manufacturing a friction material, wherein reaction of said tin source and said sulphur source results in the formation of a lubricating phase, said reaction being initiated or effected by heat resulting from the generation of friction, wherein said sulphur source is selected from one or both of sulphur and/or a metal sulphide selected from one or more of iron, copper, zinc, titanium and bismuth, and wherein said tin source is selected from one or more of tin, a tin-containing compound and/or a tin-containing alloy.
- The friction element may be, for example, a brake pad, brake shoe, brake lining or clutch lining.
- The present invention describes the novel principle of utilising friction energy to produce the functional species from cheaper precursors. In particular, the present invention relies on thermal energy generated during normal driving and braking to form friction modifiers in-situ in the friction material. Cheaper basic tin and sulphur compounds may be used in the blends, whose reaction products are capable of significant effects on friction material performance. Thus, instead of adding expensive proprietary tin sulphide compounds into the friction material during manufacture, cheaper basic precursor additives such as elemental tin, tin oxide, sulphur and metal sulphides may be used. The normal temperature and pressure at the friction interface results in reaction of these precursors to form the active compounds at the surface of the friction material.
- The present invention will now be described further with reference to the following Examples.
- Table 1 shows simultaneous thermogravimetric analysis and differential scanning calorimetry analysis for samples of tin and iron disulphide, and mixtures thereof. The samples were heated in air from ambient temperature to 1000° C. at a heating rate of 10° C./minute.
- It can be clearly seen that chemical reactions are occurring in the mixtures of tin and iron disulphide at elevated temperatures, possibly resulting in the formation of tin sulphide species. It would also appear that mixtures containing tin (IV) only result in products containing tin (IV) products, as expected.
- In order to demonstrate the formation of a lubricating phase when a tin source and a sulphur source are incorporated into a friction material, the tin source and the sulphur source were encapsulated in an organic polymer (PIB) for further testing. These blends of materials are not friction materials in themselves; however tests on these blends under the conditions in which a friction material might operate serve to demonstrate the viability of this approach to a lubricating phase for a friction material. Table 2 shows various blends of the tin and sulphur sources with the organic polymer. The PIB polymer is incorporated in a typical quantity of ≦5% by weight.
- Table 3 shows X-ray powder diffraction data for blends 1, 2, 3 and 4 (whose composition is described in Table 2) after being heated at 500° C. for 2 hours. The data shows that blends 1 and 2 (comprising mixtures of tin metal powder with iron disulphide) both show evidence of thermal reaction to form tin-sulphur species. Whereas blends 3 and 4 (comprising mixtures of tin (IV) oxide with iron disulphide) do not show any evidence of reaction products. One possible explanation for this would be that the Sn (IV) species need to be reduced to Sn (II) before formation of the lubricating phase, which is not possible at the reaction temperature.
- Table 4 details the general composition of the trial brake pad formulations.
- Table 5 details various lubricating phases/precursors added to the general composition described in Table 4 (all in 5% by volume). In addition, Table 5 details the results of wear tests on the various brake pad formulations. The results clearly show the effectiveness of blends 1 to 4 in reducing the wear rate of the brake pad formulations compared to the composition C1 in which no lubricating phase is added; in addition, the results show that the performance of blends 1 to 4 is comparable or better than the performance of the conventional lubricating phases Sb2S3 or PbS (in comparative examples C2 and C3) or the commercial lubricating phases (in comparative examples C4 and C5).
- Table 5 also details the friction of coefficient measured for the various brake pad formulations. These show little variation between the different samples.
- Table 6 shows a X-Ray Diffraction (XRD) study on the powdered surfaces of the prototype brake pads formulated using blends 2 and 4 (whose compositions are given in Table 2), carried out at 500° C. In both cases reaction to form tin sulphide (SnS) as the major product is evident. Overall, the phase analyses for the two powdered surfaces were almost identical, although the pad containing blend 4 did show some unreacted SnO2. This result for blend 4 is in contrast to the results in Table 3 where no tin sulphide was formed in compositions containing SnO2. This therefore emphasises the importance of heat produced by friction in the production of the lubricating phase, as no reaction was evident in the absence of friction.
- Table 7 illustrates various ways in which the sol-gel technique can be used to prepare novel products comprising an intimate blend of inorganic tin species with iron disulphide.
- Table 8 details a series of calculation to establish weight ratios of the components required to produce 5% SnS2 in brake pad formulations.
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TABLE 1 Thermoanalytical data for tin and iron disulphide, and mixtures thereof Residue at 1000° Weight Onset Peak End Peak area Sample C. (%) Stage loss (%) (° C.) (° C.) (° C.) (μVs/mg) FeS2 67.8 1 20.4 414 451 526 +1706 2 6.5 526 — 679 — 3 5.3 679 776 1000 +391 Sn 118.9 1 — 231 248 268 −35 2 (+14.0) 544 585 606 +213 3 (+4.9) 708 887 917 +40 SnO2 101.6 1 (+1.6) 300 — 1000 — Sn + FeS2 98.9 1 — 231 241 256 −16 (1:1) 2 5.2 390 401 426 +21 3 1.1 573 589 605 −12 4 (+2.9) 695 700 717 +99 5 (+2.3) 746 762 765 — Sn + FeS2 90.5 1 — 228 236 251 −8 (1:2) 2 6.8 398 480 530 +296 3 3.8 568 658 680 +141 4 (+1.1) 700 704, 721 +67 720 Sn + FeS2 80.5 1 — 232 238 250 −4 (1:5) 2 17.8 408 485 534 +1242 3 1.7 534 575 617 4 — 704 748 774 +53 SnO2 + 87.2 1 8.7 434 460 487 +670 FeS2 2 3.3 541 — 688 — (1:1) 3 0.8 688 — 815 — SnO2 + 81.9 1 14.1 420 488 516 +920 FeS2 2 2.8 524 — 680 — (1:2) 3 1.2 680 — 867 — SnO2 + 76.2 1 13.7 379 478 509 +1123 FeS2 2 6.8 509 579 593 (1:5) 3 2.1 593 — 701 — 4 1.2 701 — 864 — -
TABLE 2 Compositions and analysis of powder blends Elemental analysis Blend Stoichiometry of Sn analysis (%) Fe analysis (%) Density number components* Calc. Found Calc. Found (g/cm3) 1 Sn + FeS2 44.7 48.1 21.1 18.9 5.99 2 Sn + 2 FeS2 29.8 31.0 28.0 25.1 5.56 3 SnO2 + FeS2 39.4 41.7 18.5 16.8 5.95 4 SnO2 + 2 FeS2 27.3 30.8 25.7 23.4 5.57 5 Colloidal tin — 37.1 — 16.3 Not phosphate** + measured FeS2 (1:1) *In addition, each blend contains ≦5 weight percent PIB. **Colloidal tin phosphate reacted on to solid FeS2. The tin/sulphur product was synthesised using the sol-gel technique, using the pH adjustment method. -
TABLE 3 X-ray powder diffraction data for precursor blends after heat treatment Sample* Semi- Content of (see table 2 for Phase quantitative sulphides of compositions of blends) identified intensity ratio tin Blend 1 SnS 64% 64% Sn + FeS2 FeS 26% SnO2 10% Blend 2 FeS2 35% 29% Sn + 2 FeS2 Fe7S8 25% Sn2S3 14% SnS 11% SnO2 6% Fe2O3 4% Fe2SnS4 4% Blend 3 SnO2 68% — SnO2 + FeS2 FeS2 32% Blend 4 SnO2 51% — SnO2 + 2 FeS2 FeS2 49% *All sample blends were heated in air at 500° C. for 2 hours. -
TABLE 4 General composition of trial brake pad formulations Density Component (g/cm3) Volume (%) Twaron 1099D 1.43 3.0 Graphite 8787 2.15 9.5 Graphite 8849 2.18 6.5 J1506H resin 1.30 18.0 Brass DT4 8.50 2.0 Exfoliated vermiculite 2.60 3.5 Rockwool RB270 2.78 10.5 Coke D22T 2.08 10.0 Copper fibre 8.90 2.0 Sunny steel fibre 191 7.71 4.5 Zeon Nipol TPC3 1.06 8.0 Barytes 4.25 10.5 Micro Bauxilite 500/800 3.90 1.0 6000-7 Friction dust 1.30 6.0 Lubricating phase/precursors * 5.0 TOTAL — 100.0 * density of lubricating phase varies according to its composition -
TABLE 5 Dynamometer and AKM performance test data for trial brake pad compositions Brake pad formulation C1 C2 C3 C4 C5 1 2 3 4 5 Lubricating None Sb2S3 PbS ‘Ultimate C’** ‘CPG2’*** Blend Blend Blend Blend Blend phase/ 1* 2* 3* 4* 5* precursor additive* Density (g/cm3) 2.56 2.58 2.70 2.56 2.54 2.64 2.63 2.66 2.62 2.60 Wear test rate (cm3/MJ) at 150° C. 0.0734 0.0630 0.0598 0.0694 0.0773 0.0647 0.0600 0.0659 0.0643 0.0432 at 300° C. 0.2030 0.1242 0.1022 0.1809 0.1666 0.0948 0.1271 0.1020 0.1267 0.1232 at 400° C. 0.2492 0.1251 0.1178 0.1754 0.1215 0.0824 0.0720 0.0782 0.0919 0.1052 at 500° C. 0.3698 0.3087 0.3412 0.3325 0.2983 0.2746 0.3312 0.2690 0.2945 0.2716 AKM tests mu nominal 0.43 0.45 0.43 0.43 0.43 0.46 0.42 0.44 0.45 Not tested mu minimum 0.17 0.20 0.13 0.19 0.21 0.19 0.19 0.18 0.20 Not tested *All friction stabilisers incorporated at 5% by volume level in formulation- see table 4 for their complete compositions. **‘Ultimate C’ is a proprietary antimony trisulphide replacement marketed by Itaprochim and known to contain MoS2 and FeS2. ***‘CPG2’ is a proprietary friction stabilising additive marketed by Chemetall and claimed to contain 90% SnS2. -
TABLE 6 X-ray powder diffraction data for surfaces of trial brake pad formulations after dynamometer wear tests Chemical Relative Sample* Phase identified formula amount Brake pad Herzenbergite SnS High formulation Cassiterite SnO2 Medium 2** Magnetite Fe3O4 Medium Marcasite FeS2 Low Pyrite FeS2 Low Tin(II) oxide SnO Low Brake pad Herzenbergite SnS High formulation Cassiterite SnO2 High 4** Magnetite Fe3O4 Medium Marcasite FeS2 Low Pyrite FeS2 Low Tin(II) oxide SnO Low *Both brake pads had been subjected to dynamometer wear tests at 500° C. **Details of brake pad formulations are given in Tables 4 and 5. -
TABLE 7 Analytical data for colloidal tin - coated iron disulphide powders Sn Fe P S Sample Method (%) (%) (%) (%) FeS2 (uncoated) — — 38.5 — 47.0 FeS2 + colloidal tin oxide Addition 19.6 29.4 — 34.2 FeS2 + colloidal tin oxide pH adjustment 12.0 22.7 — 25.2 (2:1) FeS2 + colloidal tin oxide pH adjustment 45.6 15.0 — 16.9 (1:1) FeS2 + colloidal tin Addition 8.1 36.1 — 42.2 tartrate FeS2 + colloidal tin pH adjustment 22.3 28.3 — 31.8 tartrate (2:1) FeS2 + colloidal tin pH adjustment 29.3 23.0 — 25.3 tartrate (1:1) FeS2 + colloidal tin Addition 18.2 25.7 3.0 29.7 phosphate FeS2 + colloidal tin pH adjustment 22.4 24.0 4.1 27.4 phosphate (2:1) FeS2 + colloidal tin pH adjustment 32.3 17.5 5.0 19.1 phosphate (1:1) FeS2 + colloidal tin pH adjustment 37.1 16.3 4.5 15.6 phosphate (1:1) - 1 kg sample -
TABLE 8 Calculated weight ratios of sulphur sources to tin sources required to produce 5% SnS2 in brake pad formulations (a) Sulphur Sn + 2S → SnS2 S Sn SnO SnO2 SnS2 Atomic/molecular weight 32.07 118.71 134.71 150.71 182.85 % required 1.75 3.25 3.68 4.12 5.00 (stoichiometric) % required (2 × 3.50 3.25 3.68 4.12 5.00 stoichiometric) % required (5 × 8.75 3.25 3.68 4.12 5.00 stoichiometric) (b) Iron sulphide Sn + 2FeS → SnS2 + 2Fe FeS Sn SnO SnO2 SnS2 Atomic/molecular weight 87.92 118.71 134.71 150.71 182.85 % required 4.81 3.25 3.68 4.12 5.00 (stoichiometric) % required (2 × 9.62 3.25 3.68 4.12 5.00 stoichiometric) % required (5 × 24.05 3.25 3.68 4.12 5.00 stoichiometric) (c) Iron disulphide Sn + FeS2 → SnS2 + Fe FeS2 Sn SnO SnO2 SnS2 Atomic/molecular weight 119.99 118.71 134.71 150.71 182.85 % required 3.28 3.25 3.68 4.12 5.00 (stoichiometric) % required (2 × 6.56 3.25 3.68 4.12 5.00 stoichiometric) % required (5 × 16.40 3.25 3.68 4.12 5.00 stoichiometric) (d) Copper sulphide Sn + 2Cu2S → SnS2 + 4Cu Cu2S Sn SnO SnO2 SnS2 Atomic/molecular weight 159.17 118.71 134.71 150.71 182.85 % required 8.70 3.25 3.68 4.12 5.00 (stoichiometric) % required (2 × 17.40 3.25 3.68 4.12 5.00 stoichiometric) % required (5 × 43.50 3.25 3.68 4.12 5.00 stoichiometric)
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PCT/GB2006/002554 WO2007007082A1 (en) | 2005-07-11 | 2006-07-11 | Friction material and process for the production thereof |
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EP (1) | EP1920168B1 (en) |
AT (1) | ATE508295T1 (en) |
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Cited By (4)
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US20090061559A1 (en) * | 2007-08-30 | 2009-03-05 | Stanley Electric Co., Ltd. | MANUFACTURE METHOD FOR ZnO-CONTAINING COMPOUND SEMICONDUCTOR LAYER |
DE202010003143U1 (en) | 2009-06-30 | 2010-06-02 | Honeywell Bremsbelag Gmbh | Friction lining mixture for a friction material, in particular for brake and clutch linings |
US20150323028A1 (en) * | 2014-05-12 | 2015-11-12 | Itt Manufacturing Enterprises Llc | Friction material |
CN108916277A (en) * | 2018-07-18 | 2018-11-30 | 滁州欧瑞斯机车部件有限公司 | A kind of preparation method of copper-based brake block friction material |
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CN101602105B (en) * | 2009-07-07 | 2010-12-08 | 吉林大学 | Metal-based powder metallurgy brake lining material and preparation methods thereof |
KR101777423B1 (en) | 2010-04-23 | 2017-09-11 | 닛신보 브레이크 가부시키가이샤 | Disc brake pad |
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US10233988B2 (en) | 2015-09-23 | 2019-03-19 | Akebono Brake Industry Co., Ltd | Friction material |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5894016A (en) * | 1996-05-07 | 1999-04-13 | H.C. Starck, Gmbh & Co. Kg | Method of preparing metal disulfides and the further processing thereof to form dimetal trisulfides |
US6220405B1 (en) * | 1997-07-02 | 2001-04-24 | Alliedsignal Inc. | Friction material for drum-in-hat disc brake assembly |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3237163C2 (en) | 1982-10-07 | 1986-04-30 | Nukem Gmbh, 6450 Hanau | Process for the production of moldings with good sliding properties |
US5061295A (en) * | 1990-10-22 | 1991-10-29 | Norton Company | Grinding wheel abrasive composition |
DE19815992C2 (en) | 1998-04-09 | 2000-09-14 | Chemetall Ges Mbh Wien | Solid lubricants based on tin sulfide and carbon |
JP2002226834A (en) * | 2001-01-30 | 2002-08-14 | Nisshinbo Ind Inc | Nonasbestos friction material |
-
2005
- 2005-07-11 GB GB0514218A patent/GB2431163A/en not_active Withdrawn
-
2006
- 2006-07-07 US US11/995,173 patent/US8197585B2/en active Active
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5894016A (en) * | 1996-05-07 | 1999-04-13 | H.C. Starck, Gmbh & Co. Kg | Method of preparing metal disulfides and the further processing thereof to form dimetal trisulfides |
US6220405B1 (en) * | 1997-07-02 | 2001-04-24 | Alliedsignal Inc. | Friction material for drum-in-hat disc brake assembly |
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---|---|---|---|---|
US20090061559A1 (en) * | 2007-08-30 | 2009-03-05 | Stanley Electric Co., Ltd. | MANUFACTURE METHOD FOR ZnO-CONTAINING COMPOUND SEMICONDUCTOR LAYER |
US7718468B2 (en) * | 2007-08-30 | 2010-05-18 | Stanley Electric Co., Ltd. | Manufacture method for ZnO-containing compound semiconductor layer |
DE202010003143U1 (en) | 2009-06-30 | 2010-06-02 | Honeywell Bremsbelag Gmbh | Friction lining mixture for a friction material, in particular for brake and clutch linings |
US20100331447A1 (en) * | 2009-06-30 | 2010-12-30 | Honeywell Bremsbelag Gmbh | Friction lining mixture for a friction material, in particular for brake and clutch linings |
EP2270353A2 (en) | 2009-06-30 | 2011-01-05 | Honeywell Bremsbelag GmbH | Friction lining mixture for a friction material, in particular for brake and coupling linings |
US8536244B2 (en) | 2009-06-30 | 2013-09-17 | Honeywell Bremsbelag Gmbh | Friction lining mixture for a friction material, in particular for brake and clutch linings |
US20150323028A1 (en) * | 2014-05-12 | 2015-11-12 | Itt Manufacturing Enterprises Llc | Friction material |
JP2016027086A (en) * | 2014-05-12 | 2016-02-18 | アイティーティー マニュファクチャリング エンタープライジーズ エルエルシー | Friction material |
US9897157B2 (en) * | 2014-05-12 | 2018-02-20 | Itt Italia S.R.L. | Friction material |
US11181159B2 (en) | 2014-05-12 | 2021-11-23 | Itt Italia S.R.L. | Friction material |
CN108916277A (en) * | 2018-07-18 | 2018-11-30 | 滁州欧瑞斯机车部件有限公司 | A kind of preparation method of copper-based brake block friction material |
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ATE508295T1 (en) | 2011-05-15 |
GB0514218D0 (en) | 2005-08-17 |
EP1920168B1 (en) | 2011-05-04 |
US8197585B2 (en) | 2012-06-12 |
EP1920168A1 (en) | 2008-05-14 |
DE602006021756D1 (en) | 2011-06-16 |
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WO2007007082A1 (en) | 2007-01-18 |
US20100011988A9 (en) | 2010-01-21 |
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