EP0675192B1 - Verwendung von organischen Bismuthverbindungen in Hochdruckschmierfettzusammensetzungen für Wälzlager mit erhöhter Lebensdauer - Google Patents

Verwendung von organischen Bismuthverbindungen in Hochdruckschmierfettzusammensetzungen für Wälzlager mit erhöhter Lebensdauer Download PDF

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EP0675192B1
EP0675192B1 EP95200782A EP95200782A EP0675192B1 EP 0675192 B1 EP0675192 B1 EP 0675192B1 EP 95200782 A EP95200782 A EP 95200782A EP 95200782 A EP95200782 A EP 95200782A EP 0675192 B1 EP0675192 B1 EP 0675192B1
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Prior art keywords
bismuth
grease
bismuth compounds
organic bismuth
compounds according
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French (fr)
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EP0675192A1 (de
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George Tin Yau Wan
Dick Meijer
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SKF Engineering and Research Centre BV
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SKF Engineering and Research Centre BV
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    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/28Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
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    • C10M129/48Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
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    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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    • C10M2207/128Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
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    • C10M2207/10Carboxylix acids; Neutral salts thereof
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    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/14Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
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    • C10N2040/02Bearings

Definitions

  • the invention relates to the use of organic bismuth-compounds in extreme pressure grease lubricant compositions for application in rolling bearings.
  • extreme pressure grease lubricants are applied in order to make sure that an appropriate amount of lubricant film is always available within the bearing, in particular on the raceways and rolling elements thereof.
  • Such extreme pressure lubricant compositions generally contain an oil, a soap thickener, one or more EP additives and optionally further additives.
  • the EP additives form a friction-reducing film on the metal surfaces of the bearing, usually due to a chemical reaction of the additives with the surface metals.
  • the function of the supplied lubricant extreme-pressure additives is to minimize wear and to prevent scuffing and welding between contacting surfaces.
  • lead/sulfur-containing additives can be used.
  • Extreme pressure lubricant compositions also contain a soap thickener, such as lithium 12-hydroxy stearate, which provides the grease with the desired physical and chemical structure.
  • a soap thickener such as lithium 12-hydroxy stearate
  • the grease should be able to maintain this structure in the bearing as long as possible under high temperature, vibratory and mechanical shearing action.
  • the grease In cases where the soap structure is damaged the grease is no longer able to hold the oil in place, which will then drain away out of the bearing. As a consequence the lubricating properties of the grease are lost and the bearing service life is reduced considerably if the grease is not replenished at short intervals. Furthermore, the grease should be chemically non-aggressive with respect to the metal parts of the bearing, in particular with the above environment with high temperatures and vibration.
  • a bismuth containing additive and especially an EP additive, a bismuth containing soap, or both can be used.
  • a grease containing a bismuth additive is known from NLGI SPOKESMAN, Vol. 57, Nr. 2, May 1993, 0. ROHR "Bismuth, a new metallic but non-toxic replacement for lead as EP additive in greases", pages 6.50 - 13.57.
  • a bismuth additive promotes the formation of a film on the rolling bearing metal surfaces and therefore could serve as a replacement for lead as extreme pressure additive in grease.
  • the bismuth additive indeed appears to offer even better lubricating properties than a lead additive, in particular under high load, high temperature and high sliding speed conditions.
  • the organo-bismuth compound functions as a corrosion inhibitor and as an antioxidant.
  • the bismuth compound used according to the invention does not necessarily have to be an EP additive, i.e.:
  • the invention therefore relates to the use of bismuth compounds in an extreme pressure lubricant for rolling bearing applications as an additive for extending the useful service life of rolling bearings.
  • the invention relates to the use of a bismuth containing soap in an extreme pressure lubricant for rolling bearing applications for extending the useful service life of rolling bearings.
  • a bismuth containing soap can be mixed with an oil and optionally one or more EP- or other additives. When a bismuth containing soap is used it is not strictly necessary to use Bi-containing or other EP-additives.
  • these compounds are in general bismuth carboxylates of the formula (R-CO 2 ) 3 Bi, in which R is a branched, straight or cyclic alkyl group with 1-30 carbon atoms or an aryl, alkaryl or aralkyl group with 5-20 carbon atoms.
  • Paraffinic bismuth carboxylates with 6-10 carbon atoms or naphthenic bismuth carboxylates are preferred, such as bismuth naphthenate and bismuth octoate.
  • bismuth compounds as EP additives according to the invention is not limited to the bismuth compounds mentioned above, and other organo bismuth compounds can be used, such as the bismuth containing additives known from the above prior art, or compounds analogous to known lead/sulfur-EP additives, in which the lead is replaced by bismuth.
  • the bismuth containing EP additives are used to partly or
  • EP additives such as lead/sulfur additives or sulfur/phosphorous additives in extreme pressure lubricant compositions.
  • the bismuth compound when used as an EP additive it can be added to the soap, the oil or to the already formed mixture of the oil and the soap thickener. Usually and preferably the additive is admixed with the oil.
  • the bismuth containing EP additives are used in the usual amounts, in general the amount of bismuth will be 0,1-5 % by weight of the total lubricant composition. Mixtures of one or more bismuth compounds can be used, optionally in admixture with one or more other EP additives. Further conventional additives for lubricant compositions can be used in usual amounts, if desired.
  • the bismuth containing EP additives can be soluble or non-soluble in the oil component of the lubricant composition.
  • the bismuth containing EP additives can also be used in extreme pressure lubricant compositions, which contain for instance non-soap thickeners, such as polyurea-based compounds, polytetrafluorethylene or silicone as a thickener instead of a soap.
  • non-soap thickeners such as polyurea-based compounds, polytetrafluorethylene or silicone as a thickener instead of a soap.
  • this soap is usually a bismuth-salt of a fatty acid with 10-30 carbon atoms or a derivative thereof.
  • the bismuth analogues of known soap-thickeners are used, in which the bismuth replaces the metal, i.e. barium, aluminium, calcium, lithium, sodium, strontium etc. Examples are bismuth stearate, bismuth tristearate, bismuth tripalmetate, bismuth trioleate and derivatives thereof, such as bismuth 12-hydroxy stearate.
  • the bismuth soap can contain the same or different fatty acid groups. Also mixtures of bismuth containing soaps can be used.
  • the bismuth containing soap is used in the usual amounts, depending upon the desired properties of the final lubricant composition. In general, this amount will vary between 5-14 % by weight of the total composition for a "soft" grease to 15-25 % by weight of the total composition for a "stiff" grease.
  • the bismuth containing soap can also be used in combination with known soaps containing other metals, such as lithium-soaps or calcium-soaps in a grease formulation. This will reduce the costs of the final extreme pressure lubricant composition.
  • the invention furthermore relates to a method for preparing an extreme pressure lubricant composition in which a bismuth containing soap or thickener is mixed with an oil and optionally one or more EP- or other additives.
  • a bismuth containing soap or thickener is mixed with an oil and optionally one or more EP- or other additives.
  • the mixing of the soap, the oil and the thickener can be carried out in a manner known per se for the preparation of EP greases from the prior art.
  • a bismuth containing EP additive as mentioned above is used.
  • the bismuth containing soap, the oil and the EP additives and other additives are used in the usual amounts.
  • the bearing service life is further increased by the favourable influence of the bismuth additive on stress corrosion and fatigue life.
  • Non-limiting example 2 illustrates the preparation of a bismuth-containing soap of the invention.
  • the grease samples 1, 2 and 4 are further described in Table 2.
  • Grease samples 1, 2 and 4 above were subsequently applied for bearing life tests under high load and high temperature conditions as listed below in Table 1: Bearing type Deep groove ball bearing (DGBB 6206 2RS1) Speed 2500 rpm Radial load 6000 N Test temperature 120 ⁇ 2°C (outer ring) Grease filling 2,4 g Strategy sudden death factor group of 2, in which sets of two bearings are run simultaneously until one of the bearings fails. Type of failure Bearing noise (fatigue related) Temperature rise (grease failure) C/P 3,25 Kappa 0,75 (calculated on the base oil rheology and assuming fully flooded conditions). Grease Relubrication none
  • Table 3 shows the bearing life test results of SKF LGEP2 (sample 4) and the two Bi-greases (samples 1 and 2). It shows that the observed L10 life of both bismuth greases is about 2 times longer than the reference grease LGEP2. Based on the statistical hypothesis test procedures, the comparison of L10 life between LGEP2 and the bismuth greases is classed as weakly significant i.e. the probability of significance is greater than 80%, but less than 90%. The test comparison of the L50 life between LGEP2 and sample 3 is statistically significant (i.e. >90% probability).
  • Figure 2 shows the spectrum plot of a test bearing (#22). It can be seen that the frequency at 205 Hz is due to a ball defect, outer ring defect frequency is at 157 Hz, and the 230 Hz frequency is attributed to inner ring defect. Post investigation of the failed bearing confirmed the spectrum data. In general, all the failed bearings due to rolling contact fatigue were detected and recorded by the SKF CoMo monitoring system.
  • Figure 3 shows a time trend versus the overall spectrum energy value plot for a bearing (#23). This was the criterion used to terminate the test automatically when the overall value increase to a set alarm level (A2) as shown.
  • Figure 4 illustrates a plot of temperature recorded versus time. The machine of a test group bearings (#3 and #4) stopped due to a sudden increase in temperature of bearing #3 after approximately 680 hours of running.
  • Grease samples 1 and 2 have also been shown to give better shear stability than grease sample 4 containing S/P additive.
  • the poor results for sample 4 are due to the softening of grease structure, resulting an excessive oil leakage from the grease.
  • sample 3 prolonges the roller bearing life of flange-roller bearings and avoids the possible adverse effect of an S/P EP additive on fatigue life.
  • the bismuth soap is prepared as other metal soaps such as lead soap. This preparation can be carried out in either an open vessel or an autoclave.
  • Normal bismuth base grease can be prepared by:
  • the mixed complex bismuth base lubricating greases can also be prepared according to the preparation technology of other metal soaps such as lead or lithium.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Rolling Contact Bearings (AREA)

Claims (13)

  1. Verwendung von organischen Bismuthverbindungen in einer Hochdruckschmierfettzusammensetzung für Wälzlagerverwendungen zum Erhöhen der Lebensdauer von Wälzlagern.
  2. Verwendung von organischen Bismuthverbindungen nach Anspruch 1 zum Erhöhen der Dauerhaltbarkeit von Wälzlagern.
  3. Verwendung von organischen Bismuthverbindungen nach Anspruch 1 zum Erhöhen der Oxidationsdauer von Wälzlagern bei erhöhten Temperaturen.
  4. Verwendung von organischen Bismuthverbindungen nach Anspruch 1 zum Erhöhen der Verschleißdauer von Walzen und Flanschen von Axiallagern unter axialer Belastung.
  5. Verwendung von organischen Bismuthverbindungen nach Anspruch 1 zum Schützen von Wälzlagermetallkomponenten gegen Spannungskorrosion.
  6. Verwendung von organischen Bismuthverbindungen nach Anspruch 1 zum Schützen von Wälzlagermetalloberflächen gegen chemischen Angriff.
  7. Verwendung von organischen Bismuthverbindungen nach Anspruch 1 zum Erhöhen der Lebensdauer einer Hochdruckschmiermittelzusammensetzung für Wälzlagerverwendungen.
  8. Verwendung von organischen Bismuthverbindungen nach Anspruch 1 und/oder 7 zum Verbessern der Hochdruckeigenschaften des Seifen- oder Verdickungsmittelbestandteils in der Hochdruckschmiermittelzusammensetzung.
  9. Verwendung von organischen Bismuthverbindungen nach Anspruch 1, 7 und/oder 8 zum Steigern der Scherstabilität des Seifen- oder Verdickungsmittelbestandteils in dem Schmierfett.
  10. Verwendung von organischen Bismuthverbindungen nach den Ansprüchen 1 bis 9, wobei die Bismuthverbindung als ein Additiv, bevorzugt als ein EP-Additiv, verwendet wird.
  11. Verwendung von organischen Bismuthverbindungen nach den Ansprüchen 1 bis 9, wobei die Bismuthverbindung als eine Seife oder Verdickungsmittel verwendet wird.
  12. Verwendung nach einem der Ansprüche 1 bis 11, wobei das Bismuthadditiv im wesentlichen frei von "aktivem Schwefel" ist.
  13. Verwendung nach Anspruch 12, wobei die Schmierfettzusammensetzung im wesentlichen frei von "aktivem Schwefel" enthaltenden Additiven/Komponenten ist.
EP95200782A 1994-03-28 1995-03-28 Verwendung von organischen Bismuthverbindungen in Hochdruckschmierfettzusammensetzungen für Wälzlager mit erhöhter Lebensdauer Expired - Lifetime EP0675192B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL9400493 1994-03-28
NL9400493A NL9400493A (nl) 1994-03-28 1994-03-28 Gebruik van bismut-verbindingen in vet-smeermiddel-samenstellingen voor hoge drukken voor wentellager-toepassingen met lange levensduur.

Publications (2)

Publication Number Publication Date
EP0675192A1 EP0675192A1 (de) 1995-10-04
EP0675192B1 true EP0675192B1 (de) 2002-09-11

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* Cited by examiner, † Cited by third party
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NL1002587C2 (nl) * 1996-03-12 1997-09-15 Skf Ind Trading & Dev Geleidende polymeer-verdikte smeervetsamenstellingen.
US6090755A (en) * 1994-03-28 2000-07-18 Skf Industrial Trading & Development Company, B.V. Use of bismuth compounds in extreme pressure grease lubricant compositions for rolling bearing applications with extended service life
KR100363758B1 (ko) * 1994-09-09 2003-03-15 에스케이에프 엔지니어링 앤 리서치 센터 비.브이. 중합체성농조화제및이를함유한윤활그리스조성물
NL1002586C2 (nl) * 1996-03-12 1997-09-15 Skf Ind Trading & Dev Polymeer-verdikte smeermiddelen voor hoge werktemperaturen.
DE19634733A1 (de) * 1996-08-28 1998-03-05 Henkel Kgaa Verwendung von Wismutverbindungen in Kühlschmiermitteln
US20030036485A1 (en) * 2001-07-18 2003-02-20 Sanborn Robert H. Motor oil fortifier
US7491683B2 (en) 2003-07-04 2009-02-17 Jtekt Corporation Grease composition for rolling bearing and rolling bearing using the same
JP4262668B2 (ja) * 2004-02-09 2009-05-13 Ntn株式会社 グリース組成物および転がり軸受
JP4262630B2 (ja) * 2004-04-08 2009-05-13 Ntn株式会社 鉄道車両用軸受
EP1719812B1 (de) 2004-02-09 2018-04-04 NTN Corporation Schmierfett
JP4754818B2 (ja) * 2004-12-28 2011-08-24 Jfeスチール株式会社 継目無鋼管熱間圧延用潤滑剤
US20090003742A1 (en) * 2005-01-24 2009-01-01 Nsk Ltd. Grease Composition For Hub Unit Bearing, And Hub Unit Bearing For Vehicle
DE112006000987T5 (de) 2005-04-20 2008-03-06 Ntn Corp. Schmierfettzusammensetzung, Lager mit eingeschlossenem Schmierfett und Rotationsübertragungsvorrichtung mit eingebauter Einwegkupplung
JP4838549B2 (ja) * 2005-08-04 2011-12-14 Ntn株式会社 グリース組成物および該グリース封入転がり軸受
CN103403138A (zh) 2010-12-09 2013-11-20 Skf公司 具有改进的低摩擦性能的聚合物增稠的润滑脂组合物
CN105925360B (zh) * 2016-05-04 2019-04-09 金陵科技学院 一种添加自修复剂锂基润滑脂的制备方法

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Also Published As

Publication number Publication date
JP3727683B2 (ja) 2005-12-14
DE69528100D1 (de) 2002-10-17
NL9400493A (nl) 1995-11-01
EP0675192A1 (de) 1995-10-04
JPH0841478A (ja) 1996-02-13
DE69528100T2 (de) 2003-01-02

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