EP0453565B1 - Schmiermittelzubereitung für heizwalzen von stahl - Google Patents

Schmiermittelzubereitung für heizwalzen von stahl Download PDF

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Publication number
EP0453565B1
EP0453565B1 EP89907268A EP89907268A EP0453565B1 EP 0453565 B1 EP0453565 B1 EP 0453565B1 EP 89907268 A EP89907268 A EP 89907268A EP 89907268 A EP89907268 A EP 89907268A EP 0453565 B1 EP0453565 B1 EP 0453565B1
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Prior art keywords
heat
oil
grease
hot
group
Prior art date
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Expired - Lifetime
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EP89907268A
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English (en)
French (fr)
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EP0453565A4 (en
EP0453565A1 (de
Inventor
R. C/O Nippon Steel Corp. Muroran Works Kurahashi
T. C/O Nippon Steel Corp. Muroran Works Kouga
Masataka Shirata
Masayoshi Sakakibara
Hiroshi Kamiyashiki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyodo Yushi Co Ltd
Nippon Steel Corp
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Kyodo Yushi Co Ltd
Nippon Steel Corp
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Priority claimed from JP1134323A external-priority patent/JPH0813980B2/ja
Application filed by Kyodo Yushi Co Ltd, Nippon Steel Corp filed Critical Kyodo Yushi Co Ltd
Publication of EP0453565A1 publication Critical patent/EP0453565A1/de
Publication of EP0453565A4 publication Critical patent/EP0453565A4/en
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Publication of EP0453565B1 publication Critical patent/EP0453565B1/de
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    • C10M2213/06—Perfluoro polymers
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
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    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
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    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
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    • C10M2229/02—Unspecified siloxanes; Silicones
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    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
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    • C10N2010/04—Groups 2 or 12
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
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    • C10N2040/241—Manufacturing joint-less pipes
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    • C10N2040/245—Soft metals, e.g. aluminum
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
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    • C10N2040/247—Stainless steel

Definitions

  • the present invention relates to a lubricating composition for hot-rolling steel. More particularly, the present invention relates to a lubricating composition by which a transfer of heat to a work roll from a material to be rolled is prevented and the effect of reducing the thermal crown of the work roll is attained by incorporating a specific heat-insulating agent into a base oil or base grease.
  • the main object of the conventional lubricant for hot rolling is to reduce wear of a work roll and improve the roll surface, because the requirement for the quality of a rolled product is relatively moderate and the thermal crown of the work roll is not regarded as important. Nevertheless, recently, an increased of the quality of the product has been demanded, and the effect of reducing the thermal crown of the work roll, which has an direct adverse influence on the quality of the product, has become important.
  • EP-A-135,932 discloses a lubrication composition for metal forming, which comprises a condensed phosphoric acid; a sulfur- or chlorine-containing organic compound as extreme pressure additive; and a solid lubricant such as boron nitride as an additive when the mold temperature is 300 ° C or higher.
  • US-A-4,107,058 discloses a composition containing a lithium soap grease and an insoluble phosphorus composition such a tricalcium phosphate.
  • the present invention relates to a lubricant composition for hot-rolling steel, which is characterized in that a heat-insulating agent is incorporated into a base oil or base grease. More specifically, it was found that if two specific kinds of heat-insulating agents, i.e., (A) an inorganic compound which is melted by an absorption of heat at a temperature lower than 1200°C, and (B) an inorganic powder, selected from silicon dioxide or silicon nitride, or powder of amorphous carbon, which is not melted or decomposed at a temperature lower than 1200 ° C and has a heat conductivity lower than 0.01 cal/cm.s.
  • A an inorganic compound which is melted by an absorption of heat at a temperature lower than 1200°C
  • B an inorganic powder, selected from silicon dioxide or silicon nitride, or powder of amorphous carbon
  • a lubricating composition for hot-rolling steel which consists essentially of a base oil or base grease; a combination of heat-insulating agents (A) and (B), the heat-insulating agent (A) being an inorganic compound which is melted by an adsorption of heat at a temperature lower than 1200 ° C, the heat-insulating agent (B) being an inorganic powder, selected from silicon dioxide or silicon nitride, or powder of amorphous carbon, which is not melted or decomposed at a temperature lower than 1200 ° C and has a heat conductivity lower than 0.01 cal/cm. s.
  • heat-insulating agents (A) and (B) being selected from the group consisting of a condensed phosphoric acid salt and silicon nitride; a condensed phosphoric acid salt and amorphous carbon; a condensed phosphoric acid salt and silicon dioxide; sodium chloride and silicon nitride; and sodium silicate and silicon nitride
  • said extreme pressure additive being selected from the group consisting of zinc dialkyldithiophosphate, tricresyl phosphate and sulfurized lard
  • said solid lubricant being selected from the group consisting of graphite, molybdenum disulfide, mica and MCA
  • said heat-insulating agents (A) and (B) being contained at a weight ratio of from 49/1 to 1/49 and in a total amount of 5 to 50% by weight of the composition.
  • the lubricating property of the base oil or grease can be further improved, and the lubricating property, heat-insulating property, storage stability, working property, and water washing resistance of the base grease can be further improved.
  • Fig. 1 is a diagram illustrating the method of measuring the contact heat transfer ratio between metals.
  • the surface temperature of a work roll is elevated to about 800 ° C by contact with a material to be rolled.
  • Most of the conventional lubricants for hot rolling comprise a mineral oil, an oiliness agent, an extreme pressure additive, and a solid lubricating agent, in combination, and although the lubricating property is taken into consideration, an insulation of heat (prevention of transfer of heat to the work roll from the material to be rolled) is not considered.
  • Japanese Unexamined Patent Publication No. 60-6211 teaches that a roll can be protected by adding a fine powder of an inorganic compound having a melting point lower than 1200 ° C under atmospheric pressure, an average particle size smaller than 1 ⁇ m, and no corrosive action on iron and steel including cast iron and cast steel and other metals, and acting as a substance having a poor heat conductivity to a commercially available hot-rolling oil (liquid).
  • the base oil disclosed in this patent publication is a commercially available hot-rolling oil (liquid) and is different from the base grease used in the second embodiment of the present invention.
  • the powder used in the invention of the above-mentioned patent publication is a powder of an inorganic compound which melts at a temperature lower than 1200 ° C, and the heat transfer-preventing effect is drastically reduced after melting.
  • an inorganic compound melting at a temperature lower than 1200 ° C and an inorganic powder not melting or decomposing at a temperature lower than 1200°C are used in combination,
  • the heat-insulating agent used in the present invention includes (A) an inorganic compound which is melted by an absorption of heat at a temperature lower than 1200°C and (B) an inorganic powder which is not melted or decomposed at a temperature lower than 1200°C, is stable against oxidation and has a heat conductivity lower than 0.01 cal/cm •s• ° C at room temperature (20 °C) and a friction coefficient smaller than 0.7.
  • the inorganic compound (A) which is melted by an absorption of heat at a temperature lower than 1200 ° C is at least one of condensed phosphoric acid salts such as (KP0 3 ) n , (NaP0 3 ) n and K 4 P 2 0 7 , sodium silicate, chromic acid salts such as K 2 Cr 2 0 7 -, and halides such as NaCI, KCI, KF, KBr and KI.
  • Condensed phosphoric acid salts and sodium silicate which have no corrosive action on a rolling mill or a material to be rolled, are especially preferable.
  • the friction coefficient referred to herein is determined by the pin-on-disk method (a rod having a diameter of 3 mm and a flat top end is pressed under a load of 1 kgf against a disk having a diameter of 11 mm, and the disk is slid at a speed of 0.01 m/s).
  • a heat-insulating agent having an average particle size smaller than 50 ⁇ m can be used, but in view of the clearance between the roll and the material to be rolled, preferably the average particle size of the heat-insulating agent is smaller than 10 ⁇ m.
  • the heat-insulating agent (A) is promptly melted by absorption of heat and prevents heat from being transferred to the work roll from the material to be rolled. It is known that the heat conductivity of a liquid is, in general, increased more than that of a powder. Accordingly, it is considered that the heat transfer-reducing effect of the heat-insulating agent (A) is abruptly decreased by melting.
  • the heat-insulating agent (B) since the heat-insulating agent (B) is not melted or decomposed even under high-temperature and high-pressure conditions, the heat-insulating agent (B) is present in the form of a powder in the roll bite and prevents the work roll from falling in contact with the material to be rolled, and it is considered that since the powder per se has a lubricating property, a generation of heat by friction in the roll bite is reduced by the powder of the heat-insulating agent (B).
  • the heat-insulating agent (A) has an excellent heat-insulating property
  • the heat-insulating agent (A) is melted at a high temperature
  • the heat-insulating property is drastically reduced.
  • the heat-insulating agent (B) since the heat-insulating agent (B) is not melted or decomposed at a temperature lower than 1200 ° C, the heat-insulating agent (B) has a heat-insulating property over a broad temperature range. Accordingly, if the heat-insulating agent (A) and the heat-insulating agent (B) are made present at a specific ratio, a lubricating agent having the excellent effects of both heat-insulating agents (A) and (B) can be obtained.
  • the heat-insulating agent is added in an amount of 5 to 50% by weight, especially 10 to 40% by weight. If the amount of the heat-insulating agent is smaller than 5% by weight, the heat-insulating effect is too low, and if the amount of the heat-insulating agent is larger than 50% by weight, the viscosity of the lubricant becomes too high and the oil-supplying property is degraded.
  • the ratio of the heat-insulating agent (A) to the heat-insulating agent (B) is in the range of 49/1 to 1/49, especially 19/1 to 1/4.
  • medium and heavy mineral oils such as spindle oil, machine oil, dynamo oil, motor oil, cylinder oil and bright stock
  • animal and vegetable oils such as beef tallow, lard, sperm oil, palm oil, coconuts oil, linseed oil, rice bran oil and soybean oil
  • synthetic oils such as esters of fatty acids having 8 to 22 carbon atoms with monohydric or polyhydric alcohols, a-olefins, polybutene, silicone oils and fluorine oils, and mixtures of these oils.
  • lithium soap grease As the base grease that can be used in the present invention, there can be mentioned lithium soap grease, calcium soap grease, sodium soap grease, aluminum soap grease, calcium complex grease, polyurea grease and organo-clay grease. Lithium soap grease, calcium complex grease, polyurea grease and organo-clay grease, which have an excellent heat resistance, are preferable.
  • inorganic solid lubricants such as graphite (natural graphite and artificial graphite), molybdenum disulfide, mica (natural mica and artificial mica), fluorinated graphite, boron nitride, soft metals (such as gold, silver and copper) and talc, and organic solid lubricants such as PTFE (polytetrafluoroethylene), MCA (melamine/cyanuric acid adduct) and phthalocyanine.
  • inorganic solid lubricants such as graphite (natural graphite and artificial graphite), molybdenum disulfide, mica (natural mica and artificial mica), fluorinated graphite, boron nitride, soft metals (such as gold, silver and copper) and talc
  • organic solid lubricants such as PTFE (polytetrafluoroethylene), MCA (melamine/cyanuric acid adduct) and phthalocyanine.
  • Graphite natural graphite and artificial graphite
  • mica natural mica and artificial mica
  • boron nitride and talc which have an excellent heat resistance and oxidation stability at a high temperature and have no substantial influence on a material to be rolled
  • the amount added of the solid lubricant is 0 to 40% by weight, especially 5 to 15% by weight. If the amount added of the solid lubricant exceeds 40% by weight, the viscosity of the lubricant becomes too high and the oil-supplying property is reduced.
  • the extreme pressure additive that can be used in the present invention there can be mentioned sulfur compounds, phosphorus compounds, chlorine compounds and organic metal compounds.
  • the amount added of the extreme pressure additive is 0 to 20% by weight, especially 0.5 to 10% by weight. If the amount added of the extreme pressure additive exceeds 20% by weight, undesired side effects such as an appearance of a corrosive action and reduction of the stability of the micell structure of the grease occur.
  • a base oil, a base grease, a heat-insulating agent, an extreme pressure additive, and a solid lubricant were mixed at a mixing ratio shown in Table 1, whereby lubricating agents of Examples 1 through 16 and Comparative Examples 1 through 11 were prepared. With respect to each of the so-obtained compositions, the performances were evaluated according to the test methods described below. The results are shown in Table 1.
  • both ends of a test piece were fixed and the test piece induction-heated gripped between rolls while supplying an oil to the test piece, and a slip lubrication effected.
  • the friction coefficient and seizure resistance of each lubricant were examined to evaluate the lubricating property.
  • Friction coefficient u. T/R. W in which T represents a shaft torque, R represents a roll radius, and W represents a load.
  • a high-temperature material 3 was pressed against a low-temperature material 2 coated with a sample 1, and the contact interface temperature of each sample and the heat flow flux were reckoned backward from the change of the temperatures of both materials with a lapse of time after the contact.
  • the cooling law of Newton was applied in an extended manner to determine the heat transfer coefficient between the metals. The obtained coefficient was compared with the coefficient obtained when the sample is not coated, and the heat transfer ratio determined.
  • reference numeral 4 represents a heat-insulating material and reference numeral 5 represents a thermocouple.

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

Claims (5)

1. Schmiermittelzusammensetzung zum Warmwalzen von Stahl, die im wesentlichen besteht aus: einem Basisöl oder Basisfett; einer Kombination von wärmedämmenden Mitteln (A) und (B), wobei das wärmedämmende Mittel (A) eine anorganische Verbindung ist, die durch Wärmeadsorption bei einer Temperatur von weniger als 1200°C schmilzt, das wärmedämmende Mittel (B) ein anorganisches Pulver ist, das aus Siliciumdioxid oder Siliciumnitrid oder Pulver von amorphem Kohlenstoff ausgewählt ist, das bei einer Temperatur von weniger als 1200 ° C nicht schmilzt oder zersetzt wird und ein Wärmeleitvermögen von weniger als 0,01 caI/crn•s• °C bei Raumtemperatur und einen Reibungskoeffizienten von weniger als 0,7 aufweist; einem EP-Additiv und einem festen Schmiermittel, wobei die Kombination aus wärmedämmenden Mitteln und (A) und (B) aus der Gruppe ausgewählt ist, die aus einem kondensierten Phosphorsäuresalz und Siliciumnitrid; einem kondensierten Phosphorsäuresalz und amorphem Kohlenstoff; einem kondensierten Phosphorsäuresalz und Siliciumdioxid; Natriumchlorid und Siliciumnitrid; und Natriumsilicat und Siliciumnitrid besteht; das EP-Additiv aus der Gruppe ausgewählt ist, die aus Zinkdialkyldithiophosphat, Tricresylphosphat und geschwefeltem Schmalz besteht, das feste Schmiermittel aus der Gruppe ausgewählt ist, die aus Graphit, Molybdändisulfid, Glimmer und MCA (Melamin/Cyanursäure-Addukt) besteht, und die wärmedämmenden Mittel (A) und (B) in einem Gewichtsverhältnis von 49/1 bis 1/49 und in einer Gesamtmenge von 5 bis 50 Gew.-% der Zusammensetzung enthalten sind.
2. Schmiermittelzusammensetzung zum Warmwalzen von Stahl nach Anspruch 1, wobei das Basisöl eine Verbindung ist, die aus der Gruppe ausgewählt ist, die aus Spindelöl, Maschinenöl, Dynamoöl, Motoröl, Zylinderöl, Brightstock, Rindertalg, Schmalz, Spermöl, Palmöl, Kokosnußöl, Leinsamenöl, Reisöl, Sojabohnenöl, Estern von Fettsäuren mit 8 bis 22 Kohlenstoffatomen mit einwertigen und mehrwertigen Alkoholen, a-Olefinen, Polybuten, Siliconölen und Fluorölen besteht.
3. Schmiermittelzusammensetzung zum Warmwalzen von Stahl nach Anspruch 1, wobei das Basisfett eine Verbindung ist, die aus der Gruppe ausgewählt ist, die aus Lithiumseifenfett, Calciumseifenfett, Natriumseifenfett, Aluminiumseifenfett, Calciumkomplexfett, Polyharnstoffett und Organopolysilicatfett besteht.
4. Schmiermittelzusammensetzung zum Warmwalzen von Stahl nach Anspruch 1, wobei das feste Schmiermittel eine Verbindung ist, die aus der Gruppe ausgewählt ist, die aus natürlichem Graphit, künstlichem Graphit, Molybdändisulfid, natürlichem Glimmer, künstlichem Glimmer, Bornitrid, weichen Metallen, Talkum, Polytetrafluorethylen, Melamin/Cyanursäure-Addukten und Phthalocyanin besteht.
5. Schmiermittelzusammensetzung zum Warmwalzen von Stahl nach Anspruch 1, wobei das EP-Additiv eine Verbindung ist, die aus der Gruppe ausgewählt ist, die aus Schwefelverbindungen, Phosphorverbindungen, Chlorverbindungen und Organometallverbindungen besteht.
EP89907268A 1988-06-14 1989-06-13 Schmiermittelzubereitung für heizwalzen von stahl Expired - Lifetime EP0453565B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP144588/88 1988-06-14
JP14458888 1988-06-14
JP134323/89 1989-05-26
JP1134323A JPH0813980B2 (ja) 1988-06-14 1989-05-26 鋼の熱間圧延潤滑剤組成物
PCT/JP1989/000591 WO1989012669A1 (fr) 1988-06-14 1989-06-13 Compose lubrifiant pour le laminage a chaud de l'acier

Publications (3)

Publication Number Publication Date
EP0453565A1 EP0453565A1 (de) 1991-10-30
EP0453565A4 EP0453565A4 (en) 1992-01-02
EP0453565B1 true EP0453565B1 (de) 1995-08-30

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EP89907268A Expired - Lifetime EP0453565B1 (de) 1988-06-14 1989-06-13 Schmiermittelzubereitung für heizwalzen von stahl

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AU (1) AU625675B2 (de)
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WO (1) WO1989012669A1 (de)

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Publication number Priority date Publication date Assignee Title
JP2799634B2 (ja) * 1991-03-07 1998-09-21 日本石油株式会社 等速ジョイント用グリース組成物
US5569643A (en) * 1991-03-07 1996-10-29 Nippon Oil Co., Ltd. Grease composition for constant velocity joint
US5508321A (en) * 1994-06-15 1996-04-16 Brebner; Keith I. Intumescent silicone rubber composition
DE102006047621A1 (de) * 2006-10-09 2008-04-10 Chemische Fabrik Budenheim Kg Graphithaltiger Hochtemperaturschmierstoff für Edel- und Kohlenstoffstähle
RU2351640C2 (ru) * 2007-05-14 2009-04-10 Общество с Ограниченной Ответственностью "Научно-Производственный Центр "Конверс-Ресурс" Способ получения и состав смазочной композиции для формирования противоизносных и антифрикционных свойств приповерхностных слоев трущихся деталей

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52101363A (en) * 1977-01-27 1977-08-25 Origin Electric Coatng for lubricating
US4107058A (en) * 1977-08-19 1978-08-15 Exxon Research & Engineering Co. Pressure grease composition
JPS572368A (en) * 1980-06-07 1982-01-07 Nippon Steel Corp Material for coating hot steel surface
JPS581796A (ja) * 1981-06-25 1983-01-07 Kobe Steel Ltd 熱間圧延用潤滑剤
JPS5981394A (ja) * 1982-10-30 1984-05-11 Kobe Steel Ltd 金属のプレス加工用潤滑剤
JPS606211A (ja) * 1983-06-27 1985-01-12 Nippon Steel Corp ロ−ルの保護方法
US4612127A (en) * 1983-09-28 1986-09-16 Hitachi, Ltd. Lubricant for metal forming and process for metal forming
SU1204283A1 (ru) * 1983-11-05 1986-01-15 Предприятие П/Я М-5481 Состав дл нанесени на поверхность стальных листов перед гор чей прокаткой

Also Published As

Publication number Publication date
AU625675B2 (en) 1992-07-16
EP0453565A4 (en) 1992-01-02
EP0453565A1 (de) 1991-10-30
WO1989012669A1 (fr) 1989-12-28
DE68924075T2 (de) 1996-01-25
AU3833489A (en) 1990-01-12
DE68924075D1 (de) 1995-10-05

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