WO1995002657A1 - Festschmierstoffzusatz für harzgebundene reibbelagmischungen - Google Patents
Festschmierstoffzusatz für harzgebundene reibbelagmischungen Download PDFInfo
- Publication number
- WO1995002657A1 WO1995002657A1 PCT/AT1994/000082 AT9400082W WO9502657A1 WO 1995002657 A1 WO1995002657 A1 WO 1995002657A1 AT 9400082 W AT9400082 W AT 9400082W WO 9502657 A1 WO9502657 A1 WO 9502657A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- friction
- solid lubricant
- lubricant additive
- resin
- coefficient
- 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.)
- Ceased
Links
Classifications
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- 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
- F16D69/025—Compositions based on an organic binder
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- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
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- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/02—Carbon; Graphite
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/1003—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds used as base material
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/0403—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds used as base material
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/041—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving a condensation reaction
- C10M2217/0415—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving a condensation reaction used as base material
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
- C10M2217/0425—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone used as base material
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/043—Mannich bases
- C10M2217/0435—Mannich bases used as base material
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/044—Polyamides
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/044—Polyamides
- C10M2217/0443—Polyamides used as base material
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/045—Polyureas; Polyurethanes
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/045—Polyureas; Polyurethanes
- C10M2217/0453—Polyureas; Polyurethanes used as base material
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
- C10M2217/0465—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers used as base material
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- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
Definitions
- the invention relates to an additive for friction lining mixtures with which the coefficient of friction and wear can be set in a targeted manner and vibrations can be reduced.
- This additive can be used to advantage in asbestos-free and lead-free friction lining mixtures for highly loaded friction pairs such as those found in brakes, clutches, synchronized gearboxes, etc.
- the friction materials in the automotive industry must have the following properties: The coefficient of friction must be adapted to the specific task and be stable over a wide range of speeds and temperatures regardless of the shape and age of the material. It is particularly important that the coefficient of friction almost returns to its original value even after extreme temperature loads in the cold. This value should be above 0.30 for disc brake pads.
- the friction material may only wear out a little, but on the other hand it must not attack the brake disc strongly. To ensure good comfort properties, no noise may occur.
- the sensitivity to moisture must be as low as possible.
- such friction linings must be able to be manufactured industrially at a reasonable cost.
- Ceramic friction linings have been known for some time, but have so far not been able to establish themselves. However, more recent work in this area makes it appear possible to use ceramic-based car friction linings in the long term.
- Sintered metals are another basis for friction materials. On On this basis, various types of brake and clutch pads are manufactured; Various additives from the field of metal 1 deformation have proven themselves as auxiliary substances.
- Asbestos is hardly used anymore for the reinforcing and filling substances.
- inorganic or organic fibers e.g. Carbon or aramid fibers or metals in powder, chip or fiber form.
- Different mineral fibers and different forms of mica are also used.
- Barium sulfate, MgO or various types of clay are mainly used as fillers.
- the friction-active fillers are divided into friction and lubricants. They should influence the level of the coefficient of friction, ensure that this coefficient of friction remains largely the same at different temperatures and prevent the friction lining and the counter material from wearing out too quickly. In addition, they should have a positive effect on the noise generated during braking.
- PbS lead sulfide
- a problem that cannot be solved with lead sulfide is the required constant constancy of the coefficient of friction when the temperature rises (no fading) and the associated best possible resetting of the coefficient of friction after temperature exposure (recovery).
- the wear of the brake discs e must not be too high.
- the sulfides of copper are also known as components of friction lining mixtures.
- EP-A 0 497 751 proposes to use manganese II sulfide together with the sulfides of copper and / or other metals.
- the use of CuS is preferred over Cu "S, since Cu ⁇ S causes 78 times brake disk abrasion and instability during pad recovery (recovery) over CuS.
- S manganese sulfide, zinc sulfide or barium sulfide, 2 to 20% by weight of a metal oxide, preferably magnesium oxide or calcium oxide, optionally 1 to 5% by weight of a dye and 5 to 10% by weight of a filler, preferably ground rubber or Bloated iculit, contains.
- a metal oxide preferably magnesium oxide or calcium oxide
- a dye optionally 1 to 5% by weight of a dye and 5 to 10% by weight of a filler, preferably ground rubber or Bloated iculit, contains.
- DE-0S 23 54 848 relates to an anti-friction composite material based on polytetrafluoroethylene, a resin and a fiber component which contains glass fibers, graphite / carbon fibers or metal fibers as a fiber component, alone or in combination.
- the composite material can contain Cu 2 S in an amount of up to 50% by weight, based on polytetrafluoroethylene.
- EP-A 0 108 892 relates to construction materials with good sliding properties for sliding bearings and sliding contacts, which consist of 20 to 80% by weight of metal sulfide, the rest being carbon. Fe, Co, Ni, Cu, Mo, Sn or Sb are mentioned as the metal of the sulfide. Sulfide combinations are not disclosed. Cu "S is preferred as the Cu sulfide. According to the invention, a solid lubricant additive for resin-bonded friction lining mixtures is proposed, which is characterized in that it is a combination of copper-I-sulfide (Cu "S) with at least one further sulfide of molybdenum, zinc, antimony, tungsten, tin and / or the titanium contains.
- Cu "S copper-I-sulfide
- Copper I-sulfide (Cu ? S) can be made synthetically from the elements.
- the solid lubricant additive according to the invention can additionally contain a phosphate, pyrophosphate or polyphosphate of sodium, potassium, magnesium, calcium, boron, aluminum, copper, zinc and / or iron.
- graphite can additionally be contained.
- the solid lubricant additive can additionally contain one or more of the oxides of aluminum, iron, chromium, zinc, manganese, antimony, titanium, molybdenum, silicon and / or zirconium.
- Soft metals can also be used if necessary.
- the insoluble or sparingly soluble phosphates are preferably used.
- the additives according to the invention are tested on entire brake pads in order to create conditions that are as practical as possible.
- the raw materials are mixed in a Lödige batch mixer FM 50 for 17 minutes. From this mixture the covering size
- the pads After the pads have cooled down, they are ground flat on the surface using a cylinder head grinding machine to ensure that they are fully supported on the brake disc during the test.
- the raw coverings prepared in this way are cured in a Heraeus circulating air drying cabinet at temperatures up to 280 * C.
- the test is carried out with an RWS 75 friction test bench from Krauss, whereby the friction value and the wear behavior of the pads and the brake disc are checked.
- a running-in phase with 100 braking operations of 5 seconds each ensures good contact between the brake pad surface and the brake disc.
- the following tests are carried out at the base temperatures 100 ° C, 200 ° C, 400 ° C and 500 * C.
- the base temperature is first reached and then braked from this for 5 seconds and the brake disc is cooled again until the respective base temperature is reached again.
- This cycle is carried out 200 times in succession per base temperature. After these 200 brake applications, the brake pads are removed and the weight loss is measured for both the pads and the disc. The wear can be calculated from this.
- the contact pressure of the brake pads is 100 N / cm 2 , the normal force registered during braking is the basis for the calculation of the coefficient of friction.
- the evaluation unit of the coefficient of friction test stand is designed so that the coefficient of friction can be determined using a. Clerk can be recorded.
- the fading, the coefficient of friction difference between 100 and 500 * C and the recovery, the difference between a coefficient of friction measured at the end at 100 ° C. and the value initially measured at 100 ° C., are then determined from this.
- the pad wear values are the average of the values of the two individual pads used in a brake.
- Examples 1 to 9 describe the characteristics of the solid lubricant combinations according to the invention in a modern, steel-free formulation.
- the recipe is designed for a coefficient of friction of around 0.3 to 0.35 and experience has shown that it is particularly well suited to show the characteristics of solid lubricant additives.
- TCP means tri-calcium phosphate **): KPP means potassium pyrophosphate
- GNB total wear of the surface
- GNS total wear of the disc fading: difference in coefficient of friction between 100 and 500 ° recovery: difference in coefficient of friction at 100 ° before and after thermal stress
- MylOO coefficient of friction at 100 °
- Examples 10 to 18 are based on a typical low-steel recipe, as used in modern car disc brakes. It is characterized by a higher coefficient of friction, higher load capacity and lower wear values than the one previously described.
- Example 10 shows the properties of a solid lubricant combination without oxidic components as a comparison.
- Examples 11 to 14 illustrate the coefficient of friction-supporting effect of the addition of Al, O 3 into various combinations of Ci S according to the invention with other sulfides and with phosphates.
- Examples 15 to 18 show the possibility of variation by means of other oxides and the resultant possibility of influencing the coefficient of friction level while maintaining the favorable wear values and the coefficient of friction constancy.
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Abstract
Vorgeschlagen wird ein Festschmierstoffzusatz für harzgebundene Reibbelagmischungen, mit dem Kennzeichen, dass er eine Kombination aus Kupfer-I-Sulfid (Cu2S) mit zumindest einem weiteren Sulfid des Molybdäns, des Zinks, des Antimons, des Wolframs, des Zinns und/oder des Titans enthält.
Description
Festschmierstoffzusatz für harzgebundene Reibbelagmischungen
Die Erfindung betrifft einen Zusatz für Reibbelagmischungen, mit dem Reibungskoeffizient und Verschleiß gezielt eingestellt und Vibrationen reduziert werden können. Dieser Zusatz kann vorteilhaft in asbestfreien und bleifreien Reibbelagmischungen für hochbelastete Reibpaare wie sie in Bremsen, Kupplungen, Synchrongetrieben etc. vorkommen, eingesetzt werden. Im allgemeinen müssen die Reibmaterialien in der Automobi 1 industrie folgende Eigenschaften besitzen: Der Reibungskoeffizient muß der speziellen Aufgabe angepaßt und über einen großen Bereich von Geschwindigkeiten und Temperaturen unabhängig von der Form und dem Alter des Materials stabil sein. Besonders wichtig ist es, daß der Reibwert auch nach extremen Temperaturbelastungen in der Kälte annähernd wieder seinen ursprünglichen Wert annimmt. Dieser Wert soll bei Scheibenbremsbelägen über 0,30 liegen. Das Reibmaterial darf sich nur wenig abnützen, darf aber andererseits die Bremsscheibe nicht stark angreifen. Um gute Komforteigenschaften zu gewährleisten dürfen keine Geräusche auftreten. Die Empfindlichkeit gegenüber Feuchtigkeit muß möglichst gering sein. Darüberhinaus müssen sich solche Reibbeläge mit vertretbaren Kosten industriell herstellen lassen.
Es ist äußerst schwierig, alle an ein Reibmaterial gestellten Anforderungen zu erfüllen. Aus diesem Grund haben sich verschiedene ReibmaterialSysteme entwickelt, die dann für jeweils bestimmte Anwendungsgebiete optimal sind.
Reibbeläge aus reinem Kohlenstoff (oft kohlefaserverstärkt) sind von der Zusammensetzung her einfach und werden häufig für Flugzeugbremsen eingesetzt. Erste Versuche, dieses System für PKW- Scheibenbremsen einzusetzten, zeigten jedoch fundamentale Schwächen auf.
Keramische Reibbeläge sind schon einige Zeit bekannt, konnten sich aber, bisher nicht durchsetzen. Neuere Arbeiten auf diesem Gebiet lassen es jedoch möglich erscheinen, längerfristig PKW- Reibbeläge auf Keramik-Basis zum Einsatz zu bringen.
Sintermetalle sind eine weitere Basis für Reibmaterialien. Auf
dieser Basis werden verschiedene Arten von Brems- und Kupplungsbelägen hergestellt; verschiedene Zusätze aus dem Bereich der Metal 1Verformung haben sich als Hilfsstoffe bewährt.
Die kostengünstigste Art, Reibmaterialien herzustellen, ist auf Basis von Phenol- oder Kresolharzen. Der Großteil der PKW- und LKW-Bääge wird heute so produziert. Es werden hauptsächlich solche Harze auf Phenol und Kresolbasis eingesetzt, 'die je nach Anwendung Thermoplast- oder Kautschuk-modifiziert sein können. Um solche Rei materialien den verschiedenen Anforderungen der Praxis anzupassen, müssen jedoch eine ganze Reihe anorganischer Zusätze wie Metalle, mineralische Fasern und verschiedene weitere anorganische Füllstoffe und Additive zugesetzt werden.
Bei den verstärkend und füllend wirkenden Stoffen wird heute kaum mehr Asbest verwendet. An dessen Stelle treten anorganische oder organische Fasern, wie z.B. Kohlenstoff- oder Aramidfasern bzw. Metalle in Pulver-, Span- oder Faserform. Auch verschiedene Mineralfasern und verschiedene Formen von Glimmer kommen zur Anwendung. Als Füllstoff wird hauptsächlich Bariumsulfat, MgO oder verschiedene Tonerden verwendet.
Die reibwertaktiven Füllstoffe teilen sich in Reibmittel und Gleitmittel. Sie sollen die Höhe des Reibwertes beeinflussen, für ein weitgehendes Gleichbleiben dieses Reibwertes bei verschiedenen Temperaturen sorgen und einen zu raschen Verschleiß des Reibbelags und des Gegenmaterials verhindern. Darüberhinaus sollen sie positiv auf die Geräuschentwicklung beim Bremsvorgang einwirken.
In diesem Zusammenhang wird auf "Friction Materials", Chemical Tecnnology Review No. 100 Noyes Data Corporation, USA 1978 als relevanter Stand der Technik und als relevante Offenbarung Bezug genommen.
Eines der wichtigsten praktisch verwendeten Gleitmittel ist Bleisulfid (PbS). Obwohl PbS heute auch in v-ielen-auch nicht asoesthältigen-Belägen eingesetzt wird, versucht man bei Neuentwicklungen Bleisulfid durch andere Gleitmittel zu ersetzen.
Ein durch Bleisulfid nicht zu lösendes Problem ist die verlangte weitgehende Konstanz des Reibwertes bei Temperaturerhöhung (kein Fading) und die damit zusammenhängende möglichst gute Rückstellung des Reibwertes nach Temperaturbelastung (Recovery). Auf der Bremsscheibe soll sich
kein Belag bilden, wobei der Verschleiß der Bremsschei e nicht zu hoch werden darf.
Auf der anderen Seite sind auch die Sulfide des Kupfers als Bestandteile von Reibbelagmischungen bekannt. Z.B. schlägt die EP-A 0 497 751 vor, Mangan- II-sulfid zusammen mit den Sulfiden des Kupfers und/oder anderer Metalle zu verwenden. In der US-PS 3 477 983 wird der Einsatz von CuS gegenüber Cu„S bevorzugt, da Cu~S gegenüber CuS den 78-fachen Bremsscheibenabrieb und Instabilität bei der Belagerholung (Recovery) hervorruft.
Im Derwent-Abstract 91-342 504 [47] werden Reibmaterialien vorgeschlagen, die 5-15 Gew.-% Fasermaterialien, hauptsächlich auf Zellulosebasis, enthal¬ ten. Die Fasermaterialien sind mit 0,5 bis 10 Gew.-% einer Dispersion impräg¬ niert, die eine Polymerlösung oder einen Latex (20 bis 50 Gew.-% Feststoffe), 1 bis 5 Gew.-% Graphit, 2 bis 10 Gew.-% eines Metallsulfids zur Vermeidung von Blockieren, vorzugsweise MoS„, Cu?S, Mangansulfid, Zinksulfid oder Ba¬ riumsulfid, 2 bis 20 Gew.-% eines Metalloxids, vorzugsweise Magnesiumoxid oder Calciumoxid, gegebenenfalls 1 bis 5 Gew.-% eines Farbstoffs sowie 5 bis 10 Gew.-% eines Füllstoffs, vorzugsweise gemahlenen Gummi oder Bläh- ver iculit, enthält.
Auf der anderen Seite ist der Einsatz von Cu?S in Antifriktionsverbundwerk- stoffen, also z.B. Gleitlagern oder Büchsen und Schleifkontakte, die defi¬ nitionsgemäß möglichst geringe Reibung aufweisen sollen, vorgeschlagen worden. So betrifft die DE-0S 23 54 848 einen Antifriktionsverbundwerkstoff auf Basis von Polytetrafluoräthylen, einem Harz und einer Faserkomponente, der als Faserkomponente Glasfasern, Graphit/Kohlefasern oder Metallfasern alleine oder in Kombination enthält. Dabei kann der Verbundwerkstoff zur Erhöhung seiner Leistung, insbesondere Verschleißfestigkeit bei erhöhter Temperatur, Cu2S in einer Menge von bis zu 50 Gew.-%, bezogen auf Polytetrafluoräthylen, enthalten.
Die EP-A 0 108 892 betrifft Konstruktionswerkstoffe mit guten Gleiteigen¬ schaften für Gleitlager und Schleifkontakte, die aus 20 bis 80 Gew.-% Metall- sulfid, Rest Kohlenstoff, bestehen. Als Metall des Sulfids sind Fe, Co, Ni, Cu, Mo, Sn oder Sb genannt. Sulfidkombinationen sind nicht geoffenbart. Als Cu-sulfid wird Cu„S bevorzugt.
Erfindungsgemäß vorgeschlagen wird ein Festschmierstoffzusatz für harz¬ gebundene Reibbelagmischungen, der dadurch gekennzeichnet ist, daß er eine Kombination aus Kupfer-I-Sulfid (Cu„S) mit zumindest einem weiteren Sulfid des Molybdäns, des Zinks, des Antimons, des Wolframs, des Zinns und/oder des Titans enthält.
Kupfer-I-Sulfid (Cu?S) kann synthetisch aus den Elementen hergestellt werden.
Der erfindungsgemäße Festschmierstoffzusatz kann zusätzlich ein Phosphat, Pyrophosphat oder Polyphosphat des Natriums, Kaliums, Magnesiums, Calciums, Bors, Aluminiums, Kupfers, Zinks und/oder Eisens enthalten.
Nach einem weiteren Kennzeichen der Erfindung kann zusätzlich Graphit enthalten sein.
Endlich kann der Festschmierstoffzusatz zusätzlich eines oder mehrere der Oxide des Aluminiums, Eisens, Chroms, Zinks, Mangans, Antimons, Titans, Molybdäns, Siliciums und/oder Zirkons enthalten.
Auch weiche Metalle können gegebenenfalls zusätzlich eingesetzt werden.
Unter den Phosphaten werden bevorzugt die unlöslichen bzw. schwer löslichen Phosphate eingesetzt.
Mit dem erfindungsgemäßen Festschmierstoffzusätz können asbestfreie Brems¬ beläge mit sehr guten Gebrauchseigenschaften hergestellt werden, die blei- sulfidhältigen Belägen durchaus ebenbürtig, wenn nicht sogar überlegen sind:
Beispiele:
Die Prüfung der erfindungsgemäßen Additive erfolgt an ganzen Bremsbelägen, um möglichst praxisnahe Verhältnisse zu schaffen.
A. Herstellung der Beläge
Die Rohstoffe werden in einem Lödige-Chargenmischer FM 50 17 Minuten lang gemischt. Von dieser Mischung werden der Belaggröße
- ά -
entsprechend ausgewogene Anteile in die Preßform einer Leinweber- Bremsbelag-Laborpresse eingefüllt und dort bei Temperaturen um 150* C gepreßt. Die Belagmasse wird dabei auf die vorher in die Form eingelegte eiserne Rückenplatte des Bremsbelags gepreßt und gleichzeitig mit dieser verklebt.
Nach dem Auskühlen der Beläge werden diese mit einer Zylinderkopfschleifmaschine oberflächlich plan geschliffen, um eine volle Auflage auf die Bremsscheibe beim Test zu gewährleisten. Die so vorbereiteten Rohbeläge werden in einem Heraeus Umlufttrockenschrank bei Temperaturen bis 280* C ausgehärtet.
B. Prüfung der Beläge
Die Prüfung erfolgt mit einem Reibwertprüfstand RWS 75 der Firma Krauss, wobei -Reibwert und das Verschleißverhalten der Beläge und der Bremsscheibe geprüft wird. Durch eine Einlaufphase mit 100 Bremsungen ä 5 Sekunden wird ein guter Kontakt zwischen Bremsbelagoberfläche und Bremsscheibe gewährleistet. Die folgenden Tests werden bei den Basistemperaturen 100° C, 200° C, 400° C und 500* C durchgeführt. Dabei wird durch Aktivierung der Bremse zuerst die Basistemperatur erreicht und dann von dieser ausgehend 5 Sekunden gebremst und solange die Bremsscheibe wieder gekühlt, bis die jeweilige Basistemperatur wieder erreicht ist. Dieser Zyklus wird pro Basistemperatur 200 mal hintereinander durchgeführt. Nach diesen jeweils 200 Bremsungen werden die Bremsbeläge entnommen und sowohl bei den Belägen als auch bei der Scheibe der Gewichtsverlust gemessen. Daraus kann der Verschleiß errechnet werden. Der Anpreßdruck der Bremsbeläge ist 100 N/cm2, die während der Bremsung registrierte Normalkraft ist die Grundlage für die Berechnung des Reibwertes. Die Auswerteeinhei des ReibwertprüfStands ist so konzipiert, daß der Reibwert mit Hilfe eines. Schreibers aufgezeichnet werden kann. Daraus wird dann auch das Fading, die Reibwertdifferenz zwischen 100 und 500* C sowie die Recovery, die Differenz eines am Schluß bei 100' C gemessenen Reibwerts und dem anfänglich bei 100° C gemessenen Wert, bestimmt.
Die Belagverschleißwerte sind der Durchschnitt aus den Werten der beiden in einer Bremse eingesetzten Einzelbeläge.
Beispiele 1-9:
Die Beispiele 1 bis 9 beschreiben in einer modernen, stahlfreien Rezeptur die Charakteristik der erfindungsgemäßen Festschmierstoffkombinationen. Die Rezeptur ist auf ein Reibwertniveau von etwa 0.3 bis 0.35 ausgelegt und erweist sich erfahrungsgemäß als besonders gut geeignet, die Charakteristik von Festschmierstoffzusätzen aufzuzeigen.
Basismischung:
Vol-%
Kupferwolle 10
Talcum 20
Baryt 13
Polyarylamidfasern 10
Gummimehl 5
Friction Dust 10
Phenolharz 25
Folgende Additive wurden der Basismischung zugesetzt
Beispiel Cu,S PbS ZnS Sb,S3 MoS, TCP*' KPP"> Graphit
1 7
2 7
3 7
4 4 3
5 4 3
6 4 3
7 2.5 1 3.5
8 2.5 1 3.5
9 3 2 2
*): TCP bedeutet Tri-Calcium-Phosphat **): KPP bedeutet Kalium-Pyrophosphat
it der zuvor beschriebenen Prüfprozedur wurden folgende Resultate erhalten:
Beispiel GNB GNS Fading Recovery Myl00"">
1 35.9 3.5 0.05 0.10 0.32
2 85.9 7.6 0.08 0.09 0.32
3 47.2 2.0 0.07 0.05 0.34
4 38.1 2.7 0.05 0.06 0.33
5 30.7 6.5 0.05 0.03 0.35
6 25.1 2.0 0.03 0.05 0.30
7 34.3 3.5 0.02 0.02 0.33
8 32.8 3.4 0.00 0.01 0.33
9 26.2 2.5 0.06 0.05 0.31
***): GNB: Gesamtverschleiß des Belages GNS: Gesamtverschleiß der Scheibe Fading: Reibwertdifferenz zwischen 100 und 500° Recovery: Reibwertdifferenz bei 100° vor und nach Temperaturbelastung MylOO: Reibwert bei 100°
Man erkennt, daß durch einzelne Additive (Beispiele 1-3) keine optimalen Eigenschaften erzielt werden können. Durch die erfindungsgemäße Kombination von Cu2S mit verschiedenen anderen Sulfiden (Beispiele 4-6) und von Graphit (Beispiel 9) lassen sich die Nerschleißwerte deutlich verbessern. Die Reibwertstabilität wird durch Zusatz von Phosphaten (Beipiele 7 und 8) verbessert, ohne die günstigen Verschleißwerte wesentlich zu beeinflussen.
Beispiele 10- 18:
Grundlage für die Beispiele 10 bis 18 ist eine typische Low-Steel Rezeptur, wie sie in modernen PKW-Scheibenbremsen eingesetzt wird. Sie zeichnet sich durch höheren Reibwert, höhere Belastbarkeit und geringere Verschleißwerte als die zuvor beschriebene aus.
Basisrezeptur:
Gew.-%
Stahlwolle 20
Glasfasern 8
Messingspäne 15
Polyarylamidfasern 2
Phenolharz 10
Baryt 10
Friction Dust 5
Graphit 7
Koks 9
Dieser Basisrezeptur wurden folgende Zusätze beigefügt:
Beispiel Cu,S ZnS Sb,S3 TCP 12 -'3
10 6 3 2
11 6 3 2 3
12 6 3 2 3
13 6 3 3
14 6 3 3
15 6 3 2
16 6 3 2
17 6 3 2
18 6 3 2
Anmerkung: die in den Beispielen 10, 12 und 13 auf 100% fehlenden Anteile wurden durch Baryt ergänzt.
Entsprechend oben beschriebener Versuchsführung wurden folgende Resultate erhalten:
Beispiel GVB GVS Fading Recovery Myl
10 18.3 2.0 0.08 0.07 0.35
11 14.9 3.7 0.04 0.02 0.41
12 22.7 5.3 0.03 0.02 0.38
13 16.9 3.9 0.04 0.02 0.40
14 24.7 5.5 0.03 0.02 0.38
15 16.1 2.5 0.03 0.04 0.36
16 14.2 2.5 0.04 0.03 0.36
17 15.3 3.0 0.04 0.04 0.38
18 15.7 3.1 0.03 0.02 0.39
Beispiel 10 zeigt als Vergleich die Eigenschaften einer Festschmierstofϊkombination ohne oxidische Anteile. Die Beispiele 11 bis 14 verdeutlichen den reibwertstützenden Effekt der erfindungsgemäßen Zugabe von Al,O3 in verschiedene erfindungsgemäße Kombinationen von Ci S mit anderen Sulfiden und mit Phosphaten. Beispiele 15 bis 18 zeigen die Variationsmöglichkeit durch andere Oxide und die daraus ergebende Möglichkeit der Beeinflussung des Reibwertniveaus unter Beibehaltung der günstigen Verschleißwerte und der Reibwertkonstanz.
Claims
1. Festschmierstoffzusatz für harzgebundene Reibbelagmischungen, da¬ durch gekennzeichnet, daß er eine Kombination aus Kupfer-I-Sulfid (Cu^S) mit zumindest einem weiteren Sulfid des Molybdäns, des Zinks, des Antimons, des Wolframs, des Zinns und/oder des Titans enthält.
2. Festschmierstoffzusatz nach Anspruch 1, dadurch gekennzeichnet, daß er ein Phosphat, Pyrophosphat oder Polyphosphat des Natriums, Kaliums, Magne¬ siums, Calziums, Bors, Aluminiums, Kupfers, Zinks und/oder Eisens enthält.
3. Festschmierstoffzusatz nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß er Graphit enthält.
4. Festschmierstoffzusatz nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß er eines oder mehrere der Oxide des Aluminiums, Eisens, Chroms, Zinks, Mangans, Antimons, Titans, Molybdäns, Siliciums und/oder Zirkons enthält.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0138893A AT399162B (de) | 1993-07-14 | 1993-07-14 | Festschmierstoffzusatz für harzgebundene reibbelagmischungen |
| ATA1388/93 | 1993-07-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1995002657A1 true WO1995002657A1 (de) | 1995-01-26 |
Family
ID=3512803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/AT1994/000082 Ceased WO1995002657A1 (de) | 1993-07-14 | 1994-06-22 | Festschmierstoffzusatz für harzgebundene reibbelagmischungen |
Country Status (3)
| Country | Link |
|---|---|
| AT (1) | AT399162B (de) |
| WO (1) | WO1995002657A1 (de) |
| ZA (1) | ZA944604B (de) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996022477A1 (en) * | 1995-01-16 | 1996-07-25 | Antonio Carmine Bellicoso | Mixture composition for friction material |
| WO1996036681A1 (de) * | 1995-05-17 | 1996-11-21 | Chemetall Ges. Mbh | Festschmierstoff, insbesondere für reibbeläge, reibbelagmischungen und reibbeläge |
| AT402907B (de) * | 1995-10-16 | 1997-09-25 | Chemetall Gmbh | Zwei- und dreimetallsulfide als aktive füllstoffe für schleifkörper, sowie zwei- und/oder dreimetallsulfide enthaltende schleifkörper |
| DE19815992A1 (de) * | 1998-04-09 | 1999-10-14 | Chemetall Gmbh | Festschmierstoffe auf Basis von Zinnsulfid und Kohlenstoff |
| WO2001001010A1 (en) * | 1999-06-29 | 2001-01-04 | Alliedsignal Inc. | Solid lubricants containing bismuth sulfide for use in friction linings |
| WO2020189649A1 (ja) * | 2019-03-20 | 2020-09-24 | 曙ブレーキ工業株式会社 | 摩擦材 |
| WO2020227496A1 (en) * | 2019-05-08 | 2020-11-12 | Dow Silicones Corporation | Antifriction coating formulation compositions |
| WO2021079831A1 (ja) * | 2019-10-25 | 2021-04-29 | 曙ブレーキ工業株式会社 | 摩擦材 |
| CN113508244A (zh) * | 2019-03-13 | 2021-10-15 | 米巴摩擦技术有限公司 | 摩擦结构组件 |
| CN114630887A (zh) * | 2019-10-30 | 2022-06-14 | Gkn动力传动国际有限公司 | 用于等速万向节的包含硫化锌和硫化铜以及二硫化钼和/或二硫化钨的润滑脂组合物 |
| JP2022548662A (ja) * | 2019-09-18 | 2022-11-21 | ゲーカーエン ドライブライン インターナショナル ゲゼルシャフト ミト ベシュレンクテル ハフツング | 硫化銅を含む等速ジョイント用グリース組成物 |
| US11725158B2 (en) | 2019-09-18 | 2023-08-15 | Gkn Driveline International Gmbh | Grease composition for constant velocity joints |
| US12025198B2 (en) | 2021-03-30 | 2024-07-02 | Robert Bosch Gmbh | Antimony free and copper free ceramic friction material composition |
| US12498009B2 (en) | 2019-03-20 | 2025-12-16 | Akebono Brake Industry Co., Ltd. | Friction material |
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| US3477983A (en) * | 1966-06-23 | 1969-11-11 | Abex Corp | Friction elements |
| DE3237163C2 (de) * | 1982-10-07 | 1986-04-30 | Nukem Gmbh, 6450 Hanau | Verfahren zur Herstellung von Formkörpern mit guten Gleiteigenschaften |
| DE3513031C1 (de) * | 1985-04-11 | 1986-02-20 | Dow Corning GmbH, 8000 München | Festschmierstoffkombination und deren Verwendung in Reibbelaegen |
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| DE2354848A1 (de) * | 1973-11-01 | 1975-05-07 | Pawel M Iwanow | Antifriktionsverbundwerkstoff |
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| JPH02180993A (ja) * | 1989-01-06 | 1990-07-13 | Fujikura Ltd | 潤滑処理鉄系部品及びその製造法 |
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| EP0497751A1 (de) * | 1991-01-28 | 1992-08-05 | Chemson Polymer-Additive Gesellschaft M.B.H. | Harzgebundene Reibbelagmischung mit einem Festschmierstoffzusatz |
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Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996022477A1 (en) * | 1995-01-16 | 1996-07-25 | Antonio Carmine Bellicoso | Mixture composition for friction material |
| WO1996036681A1 (de) * | 1995-05-17 | 1996-11-21 | Chemetall Ges. Mbh | Festschmierstoff, insbesondere für reibbeläge, reibbelagmischungen und reibbeläge |
| US5958846A (en) * | 1995-05-17 | 1999-09-28 | Chemetall Ges. M.B.H. | Solid lubricant, especially for friction linings, friction lining mixtures |
| AT402907B (de) * | 1995-10-16 | 1997-09-25 | Chemetall Gmbh | Zwei- und dreimetallsulfide als aktive füllstoffe für schleifkörper, sowie zwei- und/oder dreimetallsulfide enthaltende schleifkörper |
| EP0768149A3 (de) * | 1995-10-16 | 1998-01-14 | Chemetall Ges.m.b.H. | Verwendung von Zwei- und/oder von Dreimetallsulfiden |
| DE19815992A1 (de) * | 1998-04-09 | 1999-10-14 | Chemetall Gmbh | Festschmierstoffe auf Basis von Zinnsulfid und Kohlenstoff |
| WO1999052997A1 (de) * | 1998-04-09 | 1999-10-21 | Chemetall Ges.Mbh | Festschmierstoffe auf basis von zinnsulfid und kohlenstoff |
| DE19815992C2 (de) * | 1998-04-09 | 2000-09-14 | Chemetall Ges Mbh Wien | Festschmierstoffe auf Basis von Zinnsulfid und Kohlenstoff |
| WO2001001010A1 (en) * | 1999-06-29 | 2001-01-04 | Alliedsignal Inc. | Solid lubricants containing bismuth sulfide for use in friction linings |
| US6228815B1 (en) | 1999-06-29 | 2001-05-08 | Alliedsignal Inc. | Solid lubricants containing bismuth sulfide for use in friction lining |
| CN113508244A (zh) * | 2019-03-13 | 2021-10-15 | 米巴摩擦技术有限公司 | 摩擦结构组件 |
| CN113508244B (zh) * | 2019-03-13 | 2023-09-29 | 米巴摩擦技术有限公司 | 摩擦结构组件 |
| WO2020189649A1 (ja) * | 2019-03-20 | 2020-09-24 | 曙ブレーキ工業株式会社 | 摩擦材 |
| JP2020152848A (ja) * | 2019-03-20 | 2020-09-24 | 曙ブレーキ工業株式会社 | 摩擦材 |
| US12498009B2 (en) | 2019-03-20 | 2025-12-16 | Akebono Brake Industry Co., Ltd. | Friction material |
| JP7522276B2 (ja) | 2019-03-20 | 2024-07-24 | 曙ブレーキ工業株式会社 | 摩擦材 |
| JP2023143948A (ja) * | 2019-03-20 | 2023-10-06 | 曙ブレーキ工業株式会社 | 摩擦材 |
| CN113597460A (zh) * | 2019-03-20 | 2021-11-02 | 曙制动器工业株式会社 | 摩擦材料 |
| JP7323310B2 (ja) | 2019-03-20 | 2023-08-08 | 曙ブレーキ工業株式会社 | 摩擦材 |
| CN113853421B (zh) * | 2019-05-08 | 2023-03-14 | Ddp特种电子材料美国第9有限公司 | 减摩涂层配制组合物 |
| JP2022532146A (ja) * | 2019-05-08 | 2022-07-13 | ディーディーピー スペシャルティ エレクトロニック マテリアルズ ユーエス ナイン,エルエルシー | 減摩コーティング製剤組成物 |
| CN113853421A (zh) * | 2019-05-08 | 2021-12-28 | Ddp特种电子材料美国第9有限公司 | 减摩涂层配制组合物 |
| WO2020227496A1 (en) * | 2019-05-08 | 2020-11-12 | Dow Silicones Corporation | Antifriction coating formulation compositions |
| JP2022548662A (ja) * | 2019-09-18 | 2022-11-21 | ゲーカーエン ドライブライン インターナショナル ゲゼルシャフト ミト ベシュレンクテル ハフツング | 硫化銅を含む等速ジョイント用グリース組成物 |
| US11725158B2 (en) | 2019-09-18 | 2023-08-15 | Gkn Driveline International Gmbh | Grease composition for constant velocity joints |
| JP2021066834A (ja) * | 2019-10-25 | 2021-04-30 | 曙ブレーキ工業株式会社 | 摩擦材 |
| JP7372111B2 (ja) | 2019-10-25 | 2023-10-31 | 曙ブレーキ工業株式会社 | 摩擦材 |
| WO2021079831A1 (ja) * | 2019-10-25 | 2021-04-29 | 曙ブレーキ工業株式会社 | 摩擦材 |
| CN114630887A (zh) * | 2019-10-30 | 2022-06-14 | Gkn动力传动国际有限公司 | 用于等速万向节的包含硫化锌和硫化铜以及二硫化钼和/或二硫化钨的润滑脂组合物 |
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| US12025198B2 (en) | 2021-03-30 | 2024-07-02 | Robert Bosch Gmbh | Antimony free and copper free ceramic friction material composition |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA944604B (en) | 1995-02-17 |
| AT399162B (de) | 1995-03-27 |
| ATA138893A (de) | 1994-08-15 |
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