AU603927B2 - Creación de Inventos y Patentes con Inteligencia Artificial

AU603927B2 – A lubricant comprising an oil-in water emulsion, a process for the preparation thereof and the use of the lubricant
– Google Patents

AU603927B2 – A lubricant comprising an oil-in water emulsion, a process for the preparation thereof and the use of the lubricant
– Google Patents
A lubricant comprising an oil-in water emulsion, a process for the preparation thereof and the use of the lubricant

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Publication number
AU603927B2

AU603927B2
AU22386/88A
AU2238688A
AU603927B2
AU 603927 B2
AU603927 B2
AU 603927B2
AU 22386/88 A
AU22386/88 A
AU 22386/88A
AU 2238688 A
AU2238688 A
AU 2238688A
AU 603927 B2
AU603927 B2
AU 603927B2
Authority
AU
Australia
Prior art keywords
lubricant
oil
emulsion
lubricant according
silica
Prior art date
1987-09-21
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

Application number
AU22386/88A
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AU2238688A
(en

Inventor
Michael Joseph Garvey
Ian Charles Griffiths
Ian Thompson
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.)

Unilever PLC

Original Assignee
Unilever PLC
Priority date (The priority date 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 date listed.)
1987-09-21
Filing date
1988-09-19
Publication date
1990-11-29

1988-09-19
Application filed by Unilever PLC
filed
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Unilever PLC

1989-03-23
Publication of AU2238688A
publication
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patent/AU2238688A/en

1990-11-29
Application granted
granted
Critical

1990-11-29
Publication of AU603927B2
publication
Critical
patent/AU603927B2/en

2008-09-19
Anticipated expiration
legal-status
Critical

Status
Ceased
legal-status
Critical
Current

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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

C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes

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

C10M125/26—Compounds containing silicon or boron, e.g. silica, sand

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

C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 – C10M137/00

C10M139/04—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 – C10M137/00 having a silicon-to-carbon bond, e.g. silanes

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

C10M173/00—Lubricating compositions containing more than 10% water

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

C10M2201/02—Water

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

C10M2201/087—Boron oxides, acids or salts

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

C10M2201/10—Compounds containing silicon

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

C10M2201/10—Compounds containing silicon

C10M2201/102—Silicates

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

C10M2201/10—Compounds containing silicon

C10M2201/105—Silica

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

C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic 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

C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions

C10M2207/28—Esters

C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids

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

C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions

C10M2207/28—Esters

C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids

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

C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions

C10M2207/28—Esters

C10M2207/283—Esters of polyhydroxy 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

C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions

C10M2207/28—Esters

C10M2207/286—Esters of polymerised unsaturated acids

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

C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions

C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines

C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms

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

C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions

C10M2215/26—Amines

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

C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions

C10M2227/04—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes

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

C10N2040/00—Specified use or application for which the lubricating composition is intended

C10N2040/08—Hydraulic fluids, e.g. brake-fluids

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

C10N2040/00—Specified use or application for which the lubricating composition is intended

C10N2040/20—Metal working

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

C10N2040/00—Specified use or application for which the lubricating composition is intended

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

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

C10N2040/00—Specified use or application for which the lubricating composition is intended

C10N2040/20—Metal working

C10N2040/241—Manufacturing joint-less pipes

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

C10N2040/00—Specified use or application for which the lubricating composition is intended

C10N2040/20—Metal working

C10N2040/242—Hot working

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

C10N2040/00—Specified use or application for which the lubricating composition is intended

C10N2040/20—Metal working

C10N2040/243—Cold working

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

C10N2040/00—Specified use or application for which the lubricating composition is intended

C10N2040/20—Metal working

C10N2040/244—Metal working of specific metals

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

C10N2040/00—Specified use or application for which the lubricating composition is intended

C10N2040/20—Metal working

C10N2040/244—Metal working of specific metals

C10N2040/245—Soft metals, e.g. aluminum

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

C10N2040/00—Specified use or application for which the lubricating composition is intended

C10N2040/20—Metal working

C10N2040/244—Metal working of specific metals

C10N2040/246—Iron or steel

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

C10N2040/00—Specified use or application for which the lubricating composition is intended

C10N2040/20—Metal working

C10N2040/244—Metal working of specific metals

C10N2040/247—Stainless steel

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

C10N2050/01—Emulsions, colloids, or micelles

Abstract

A lubricant comprising an oil-in-water emulsion and solid particles, in which the oil is a lubricating material and the oil droplets are stabilized by a surface coating of partially hydrophobic silica particles of a size less than 1 micrometer. This lubricant is to be used as a hydraulic fluid and as a metal-working or metal-rolling fluid.

Description

AUSTRALIA
PATENTS ACT 1952 COMPLETE SPECIFICATION Form
(ORIGINAL)
FOR OFFICE USE 03,27 Short Title: Int. Cl: Application Number: Lodged: 0 *0f 00 0 o 0e o o 0 0 *00 00 0 0 0 0 00 0 0 9 00 O Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: TO BE COMPLETED BY APPLICANT 0o 0 0 S 0 00 0 00 00 9000 0 so **00 0 0 0 S0 0 00 0 0 0000 0 oo o 0 ii Name of Applicant: Address of Applicant: UNILEVER PLC UNILEVER HOUSE
BLACKFRIARS
LONDON EC4
ENGLAND
Actual Inventor: Address for Service: GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.
Complete Specification for the invention entitled: A LUBRICANT COMPRISING AN OIL-IN-WATER EMULSION, A PROCESS FOR THE PREPARATION THEREOF AND THE USE OF THE UBRICANT The following statement is a full description of this invention including the best method of performing it known to me:r
A
-I-
C a I1 0 06 r 0 I0 0 00 £0e 0 04 O 00 S00 00 0@ 0 00 06 a 0 o so o oe o oo 0 0 0 e oa o9e0 o a o a 6 0 00006 a Title: A lubricant comprising preparation thereof and the use an oil-in-water emulsion, a process for the of the lubricant.
The invention relates to a lubricant comprising an oil-in-water 5 emulsion in which the oil is a lutricating material. More in particular the invention relates to such emulsions with droplets having a controlled degree of instability, and to a process for the preparation of such a lubricant and to the use of the lubricant or the oil-in-water emulsion as a hydraulic fluid, a metal working, or metal-rolling fluid.
10 Lubricating formulations containing an oil, solid particles and water are known from European patent application 33,170. In this patent application a hydraulic fluid has been disclosed being an oil-in-water emclsion that comprises 90-99 weight of water, from 0.5-5 weight of a lubricating oil and an emulsifier. In the description it has been indicated that the viscosity can be increased by adding a thickener which might be a water-soluble polymer, fumed silicas and aluminas. In the claims and in the examples no attention has been given to the use of the inorganic thickeners, but when the thickeners are used their purpose is to thicken the aqueous phase.
-2- From U.S. patent 2,722,515t U.S. patent 2,628,197 and British patent 858,863 emulsions are known in ‘which the oil component is emulsified in water with the aid of a soap or surfactant (emulsifier). The solid particles are present either dispersed throughout the bulk of the emulsified oil droplets or dispe–rsed in the aqueous phase. In the former case the solid particles act as a thickener or filler for the oil or as an abrasive (see U.S. patent 2,112,632). In U.S. patent 31454,495 a lubricant composition has been disclosed for use in the cold forming of metals, which composition comprises a liquid phase and a solid phase, the solid phase being dispersed in the liquid phase. The porous solid can consist of finely 4 C V divided aluminum hydroxide impregnated with molten polyolef in which is quite different from the composition according to the invention.
:0 ‘:In British patents 952,351 and 952,352 emulsions have been disclosed which can be used as a medium in which the polymerization of Q e 15 ethylenically unsaturated polymers can be polymerized, 0 0 aThe lubricant according to the invention, comprises an oil-in-water emulsion and solid particles, in which the oil is a 000 0 a lubricating material, is characterized in that the oil droplets are 0:0: 20stabilized by a surface coating of partially hydrophobic silica particles 0 0 of a size less than 1. micrometer. Lubricating compositions containing ~o~o silica particles which act as an emulsifier and which are located at the surface of oil droplets are novel.
There has been a need for fire resistant fluids with lubricating properties especially for applications where there is a possible risk from fire. it proved to be difficult to obtain emulsions with a controlled degree of instability permitting the droplets to be stable in the bulk of the dispersion and yet with a triggered instability on contacting a surface so as to form a lubricating oil film thereon..
The pra~sent invention provides an oil-in-water emulsion with silica particle coated droplets wherein the droplets comprise lubricating material. For a suitable degree of stability of the emulsion, partial hydrophobing of the silica particles may be recommendable so that the silica particles are rendered sufficiently hydrophobic to hold them at the oil-water interface.
In a preferred embodiment of the invention the solid partiqles comprise colloidal silica, which has been rendered partially hydrophobic by treatment of the silica particles with a silating agent e.g. trimethyl chlorosilane or an organic cationic compound. The use of quarternary ammonium compounds, such as e.g. cetyl trimethyl ammonium bromide for this purpose ia particularly recommended.
The use of an amount of solid particles in the emulsion in the range bct–en 0.01 and 25, preferably between 0.02 and 10% was found useful. Also the size of the solid particles I’a O was found to be important and the use of solid particles having a in at least one direction a size between 0.003 and 1, preferably i o between 0.005 and 0.5 micrometer was found beneficial. Ideally the 0 concentration of particles in the emulsion should be low enough to be substantially depleted from the aqueous phase onto the droplets of the emulsion.
One convenient way of preparing a suitable colloidal silica sol S is by mixing a colloidal silica with a cationic surfactant solution at a S concentration of the surfactant low enough to prevent visible aggregation Sof the silica. In the surface active silica sol ao obtained subsequently a i ’20 suitable lubricating oil is homogenized.
l The lubricating oil phase comprises a molecule having at least carbon and/or silicon atoms and compounds of the class consisting of mineral oil, ester, ether, polyalpha-olefin, silicone oil, derivatives and i mixtures thereof are very suitable. Organic esters, in particular esters derived from a polyol with a tertiary alpha carbon atom such as trimethylolpropane, trimethylolethane, pentaerythritol are preferred, especially if the carbocylic acid constituent is a C6-C22 (mainly straight chain) monocarboxylic acid. The amount of oil phase (droplets) in the emulsion normally ranges between 0.1 and 70%, preferably between 0.5 and of the emulsion. The emulsion may also contain conventional additives that are used in hydraulic and other water based functional fluids. These other additives include corrosion inhibitors, shear stabilizing agents, thickeners, bactericides, dyes, water softening agents, odour masking agents, surfactants, anti-wear additives, de-foamers, extreme-pressure additives and the like. Such additives are readily available and their use is well known to those skilled in the art.
The silica particles forming the coating of the oil droplets, in particular when suitably hydrophobic, have a tendency to condense or polymerize at the oil-water interface to form a permanent, but brittle two dimensional aggregated interfacial sKin. For Qatisfactory perfurmunce as a lubricating material it is desirable that the coated droplets of the emulsion, when subjected to distortion or to asymmetric pressure, undergo an irreversible rupturing and thereby form a lubricating film of droplet material on the neighbouring surfaces.
Under certain circumstances it is preferable that the aqueous phase also includes an amount of hydrophobing agent in the range of 0.1 to 100 mg per gram of solid particle. The concentration of hydrophobing agent S 0necessary to render the particle sufficiently hydrophobic to adsorb at the ‘Ii a oil water interface is less than that required for monolayer coverage of the particles which is given by the expression 0i °C 3 moles g- 1 where r is the effective particle radius, prAN p is the particle density, A is the area of the surface occupied by the hydrophobing agent and N is Avogadro’s number. re expression approximates to 0.006/r(nm) moles of agent per gram of par.icles. The a amount of agent is, therefore, less than 0,006/r moles of agent per gram of particles where r is the effective particle radius. In practice a fev percent of the above amount is used, for example, 0.003 g per gram of silica a Q C 4 particles. The present invention also provides a process for preparing an oil-in-water emulsion with silica particle coated droplets with a lubricating material in which a lubricating oil is emulsified in an aqueous phase containing suitable hydrophobic silica particles so as to form an emulsion of droplets coated with a skin of solid particles.
In another embodiment the inventicn comprises the use of an oil-in-water emulsion as described above as a hydraulic fluid, as a lubricant or as a metal-working fluid.
The invention is illustrated by the following examples Example 1 A partially hydrophobed silica dispersion was prepared by adding 25 g of 0.037 cetyl trimethyl anonium bromide solution to an equal weight of a 10% w/w silica dispersion (Ludox HS40 ex. E.I. De Pont de Nemours Co.; average silica particle size of approximately 13nm (0.013 um)) with rapid stirring. The dispersion contained no visible aggregates and had a pH of 9.9, To 45 g of this dispersion were added 5 g ester
(C
7 -carboxylic ester of tr.methylolpropane) and the mixture was homogenised using a Silverson high shear mixer (1.6 cm diameter head, maximum power) for 2 minutes.
S; The emulsion was examined by optical microscopy which showed c .o the presence of spherical and spheroidal droplets up to 30 micrometer SC 0 S diameter. The emulsion creamed on standing but there was an S 15 insignificant amount of coalescence after two days.
C0 0 c
G
Example 2 The silica dispersion obtained according to example I was Sdiluted fifty fold with distilled water then mixed as in example 1 with I c the ester to form a 10% w/w oil in wate’ dispersion.
cc 20 The resulting emulsion creamed rapidly with coalescence to S give a layer of oil on the surface of the emulsion Microscopic e xamination showed the presence of emulsion droplets, in the aqueous phase, up to approximately 1000 micrometer’.
SExample 3 S 25 Example 2 was repeated with high shear mixing (using a SSilverson high shear mixer) for 20 minutes. The emulsion creamed without coalescence and from optical microscopy was found to contain droplets up to 200 micrometer.
In order to demonstrate and visualise the phenomena of controlled emulsion stability, the following experiment was performed.
A few drops of the above emulsion were placed on a glass microscope slide, and covered with a glass cover slip. On applying vertical pressutre to the microscope slide cover slip, it was observed that deformation of the droplets readily occurred which led to coalescence and rupturing against the glass surfaces.
Example 4 g of 0.012% w/w cetyl trimethyl ammoniumn bromide (CTAB) solution was added with rapid stirring to an equal weight of 2% w/w silica dispersion (Ludox SM ex Du Pont de Nemours colloidal silica having an average particle size of approximately 7 nanometers). 5 g of this mixture were then diluted by addition of 45 g distilled water.
io qn g or tnls alspersion (O.1 aiu 2 o.oo LI’TAB) were added 5 g of the above ester followed by homogenisation using a Silverson blender as described in example 1.
Microscopic examination showed the emulsion to contain mainly spherical droplets of size up to 50 micrometer. There was no visible coalescence, but the droplets were observed to rupture when pressure was S- s applied to the microscope cover slip as described above.
c 0 i! G c lp e o0 !j o o 8m l S 15 45 g of an aqueous partially hydrophobed, silica dispersion a were prepared by addition of 22.5 g of 0.0024% w/w cetyl trimethyl ammonium bromide to 22.5 g of 0.8% w/w silica dispersion ‘(diluted Ludox HS40 40% silica) with rapid stirring on a magnetic C C C a 0 f0 stirrer for one minute followed by a pH adjustment to pH 7 with C 000 20 concentrated hydrochloric acid. There was no visible aggregation of the silica, o To the above silica dispersion was added 5 g of the ester in example 1 and the mixture homogenised in a 100 cm 3 (tall form) beaker using a Silverson mixer, fitted with a 1,6 cm diameter head, on 00 25 maximum power for 20 minutes.
oooc i sThe emulsion was examined by optical microscopy, which showed droplets up to 50 micrometer in diameter with no visible coalescence.
Coalescence of emulsion droplets and rupture against the glass surface could be observed on application of pressure to the microscope slide as described above, The emulsion was added to an equal weight of a 5% aqueous solution of Blanose Refind CMC X8200 (Hercules, D.s. 2.1 MW 50,000) and stirred for 30 minutes using a Heidolph stirrer (PTFE blade) at 300 rpm.
Examination by microscopy showed no deterioration of the emulsion.
The emulsion was allowed to stand for 48 hours with no visible creaming but a small number of coalesced oil droplets were observed on the surface, Example 6 Equal weights of a 0.8% w/w silica dispersion (as used in exmunple 1) and 0.0024% w/w cetyl trimethyl ammonium bromide (OTAB) solution were mixed by adding CTAB solution to the silica dispersion with rapid, non turbulent stirring. The pH of this dispersion was reduced by the addition of concentrated HCl1 to pH g of ester (example 1) were emulsified in 45 g of the above dispersion usiniig a Silverson mixer (max power 20 mins) and the resulting emulsion was added to 50 g 1.2% aqueous Guar gum solution (Meypro Guar %0 CSA 200/50 ex. Meyhall Chemical) and stirred for 5 minutes.
This thickened emulsion showed no signs of creaming over a period of 24 hours and on microscopic examination droplets of up to c um were observed that coalesced under pressure.
S00 Example 7 I 1 5 A sample of partially hydrophobic silica was prepared by slowly adding a 400 g aqueous solution of 0.15% cetyl trimethyl amnonium bromide to 400 g of a 10% silica sol (Ludox HS40 ex. Du n Pont) whilst subjecting the latter to sonication at full power using a V^ Dawe 7530A Soniprobe.
An emulsion concentrate was prepared by adding 25 g of hindered ester (branched C018 ester of pentaerythritol) to 50 g of the partially hydrophobic silica prepared as above. The mixture was subjected to sonication for five minutes at full power using a Dawe ®0QO 7530A Sonipobe.
*S TO 1 25 The above concentrate was mixed with 425 g of suspending agent, prepared by making up a solution containing 0.1% Carbopol |l 940 (ex. Goodrich) and 0.2% formaldehyde in water, made mildly alkaline I (0.04% sodium hydroxide).
I Thus an emulsion was produced containing droplets of the ester I 30 coated by a solid skin, of diameter 0.1-100 um. Over a period of several months no noticable creaming occurred.
Eaile 8 An emulsion was prepared by adding ester to hydrophobic silica in the same proportions as in Example 7. The ester used was a dimer ester, neopentyl glycol 2-ethyl hexyl dimerate, giving the same result as obtained in Example 7.
-8- Example 9 An emulsion concentrate was prepared as in example 8. This was diluted with glycerol to form a 5% ester emulsion. This was tested for its film forming abilities as follows; The ability of the emulsion to deposit an elastohydrodynamic (EHD) lubrication film was evaluated using a rolling point contact apparatus. Such apparatus has been used in the study of lubrication, to determine the thicknesses of lubrication films produced by water based fluids. A description of the apparatus used is provided in the literature being G.T. Wan, P. Kenny and H.A. Spikes «Elastohydrodynamic Properties of Water-based Fire-resistant Hydraulic Fluids». Tribology International 17(6), (1984), 309-315 and H. Hamaguchi, H.A. Spikes and A. Camerron ‘Elastohydrodynamic Properties of Water-in-Oil Emulsions».
Wear 43, (1977), 17-24. Briefly, the method relies on the destructive interference produced when coherrent light is reflected from the top and bottom surfaces of a lubricant film. The film is formed between a steel ball bearing and a glass disc which has been coated with a reflective layer of chromium. The contact point is observed using a top-lit microscope, and interference colours in the contact zone identify the presence of an EM- film. Each interference colour corresponds to a specific film thickness; the technique can be used to identify EHD films from 0.1 to 2 um thick.
A sample of the emulsion wa. placed on the underside of the chromium-plated glass disc. A 1″ (2.54 cm) diameter steel ball bearing 5 was placed in contact with the fluid and a load of 29,4N was applied.
The disc was then rotated, causing the ball bearing to rotate, and the contact zone was observed under a microscope. The speed required to achieve the first yellow interference colour, which corresponds to a film thickness of 0.14 urn, was noted. The results of the film forming abilities are given in table A.
-7 -9- Table A emulsion of example 9 pure ester glycerol hydraulic fluid Standard fully formulated high-water based hydraulic fluid.
‘Jollint oPood ico Rorm Pin fMM i.M 1 3.4 x 10″ 3 3.86 x 10 3 7.74 x l0 1 no film formed c c e c tc c GC GC C C C 0C 0 0 0 C0 0 o t 0 C 00 C CC C C C 00 C CC CC 0 C 00 C CO o o CC0 0 0000 0 0 0 00 0 0 C C As can be seen from table A, the solid stabilised emulsion showed the ability to deposit an EHD film at the same rolling speed as 15 the base ester, This implied that the lubricating film deposited frcsr the emulsion consisted of the base ester.
Glycerol, the suspending agent Used in example 9, did not form an EHD film until a speed two orders of magnitude higher than required for example 9 were reached.
A standard fully formulated water-based hydraulic fluid, did not show any EHD film formaztion, although the rolling speed was increased to 3 ms- 1 Similar experiments on surfactant stabilised oil-in-water emulsion based hydraulic fluids have been reported in the above mentioned lite-ature. Thay show that EHD films are not formed from 25 these fluids.
Example Emulsions were prepared in accordance with examples 1, 7 and 8. They were 4 -ted for their lubricating ability using the Falex test.
For comparison purposes standard fluids as detailed in table B were also testedt The lubricating properties of a fluid can be conveniently assessed by means of the Falex Method («Measuring Wear Properties of Fluid Lubricants (Falex method)» ASTMD 2670-67). The test measures the wear between a rotated shaft and two vee-blocks after a specified period of time.
60-70 cm 3 of the test fluid was placed in the cup of the Falex lubricant testing machine (ex, Favlle-LeVally Corp., Bellwood, Illinois) equipped with a new test shaft and vee-blocks. The shaft was of diameter 6 mm and constructed from SAE 3135 steel of hardness R
B
87-91 and surface roughness 10 RMS. The vee-blocks (960 block angle) were made from AISI 1137 steel of hardness RC 20-24 and surface roughness 10 RMS, The vee-blocks were clamped to the shaft by means of two levers, to the ends of which a force was applied using a notched load wheel. This force could be measured using a load gauge.
0 10 The vee-blodks were clamped together with a force of 250 lbs, o’e and the surfaces were run-in by rotating the shaft at 290 rpm for five 00 00 0 o0 minutes. The test load was then increased to 700 lbs force and the o°°o position of the notched wheel noted. The shaft was then rotated for a 0″o 0 further fifteen minutes, any wear being taken up by rotating the load 0 00 15 wheel, After this time, the load was temporarily reduced to 600 lbs force, then increased to 700 lbs force. The test was then stopped and 0 110 o0 o’ the number of notches that the wheel had been advanced was noted? this 0o0 0 was the Falex wear index. Should the vee-blocks sieze the shaft during the test, a shear pin breaks and the fluid is judged to have «failed».
0000 °oo° 20 Th results as obtained are shown in table B. a low wear index implies good lubrication.
0000 0oo o Table B o o 00 0 Sample Falex Wear Index 0.1% aqueous carbopol 940 (registered name of Goodrich) failed mineral oil 200SN failed pure ester from example 1 54 example 1 emulsion 14 pure ester from example 7 69 exa:ple 7 emulsion 4 pure ester from example 8 61 example 8 -emulsion Standard fully formulated High Water 3 Based hydraulic fluid
-U,
-11- As can be seen from the above table B, both E!queou Carbopol (the thickening agent used in examples 7 and 8) and mnirn without additives proved ineffective lubricants on this test, and the apparatus siezed, By contrast, the pure esters prevented siezure or severe wear, but more effective still were the solid stabilised emulsions prepared from these esters, Indeed, the wear protection approached that given by a fully formulated hydraulic fluid a product which includes anti-wear and extreme-pressure additives, No such additives were included in the ‘0 emulsions tested Example 11 j The procedure in example 6 was repeated using equal weights of il i a 0.8% w/W silica dispersion and 0,005% w/w tetradecyl trimethyl !i ammonium bromide, The resulting emulsion containing droplets of up to micrometer was observed to coalesce under pressure on a microscope I slide.
Example 12 g of 0.012% w/w hexadecyl trimethyl ammonium chloride (CTAC) solution was added with rapid stirring to an equal weight of 2% 20 w/w silica dis;ersion (LUdox SM ex Du Pont de Nemours colloidal silica S° d having an average particle size of approximately 7 nanometers), 5 g of i this mixture were then diluted by addition of 45 g distilled water, To 45 g of this dispersion SiO 2 0.006% CTAC) were added 5 g of the ester describod in example 1 followed ty 25 homogenisation using a Silverson blender as described in Example 1,.
}Microscopic examination showed the emulsion to contain mainly spherical droplets of size up to 50 micrometer. There was no visible applied to the microscope cover slip as described above,

Claims (13)

1. A lubricant comprising an oil-in-water emulsion and solid particles of partially hydrophobic silica, in which -the oil is a lubricating material, characterized in that -the oil droplets are stabilized by a surface coating of -the partially hydrophobic silica particles having in at least one direction a size not greater than 1 micrometer.

2. The lubricant accor-ding to claim 1, characzterized in -that the size of the particles ranges between 0.003 and 1 micrometer.

3. The lubricant according to claim 2, characterizad in that the size of the particles ranges between 0.0203 an’d 0.1 micrometer. 0-1 0 4e The lubricant according to claims 1-3, characterized 0a in that the silica is present in the form of a brittle, rigid interfacial skin. The lubricant according to claim 4, characterized in that the coated droplets of the emulsion, when subjected -to distortion or asymmetric pressure, undergo an irreversible rupturing and thereby form a film of droplet material on the neighbouring surfaces to be lubricated.

6. The lubricant according to claim 1, characterized in *that the lubricating material comprises molecules containing at least 10 carbon and/or silicon atoms.

7. The lubricant according to claim 6, characterized in ‘that the lubricating oil is an organic ester.

8. The lubricant according to claim 7r characterized in that the organic ester is derived from a polyol comprising a tertiary alpha carbon atom. 4 7 Q -13

9. The lubricant according to claim 7, characterized in that the ester is derived from C 6 to C 22 carboxylic acids. The lubricant according to claim 1, characterized in that the percentages of lubricating material ranges between 0.1 ard 70% preferably between 0.5 and on basis of the total emulsion.

11. The lubricant according to any of the preceding claims, characterized in that the amount of silica particles ranges between 0.01 and 25% preferably between 0.02 and 10% calculated on the weight of *E C oil.

12. The lubricant according to any of the preceding S’ claims, characterized in that the silica particles are modified using a hydrophobing agent in an amount ranging 0″o between 0.1 to 100 mg per gram of silica particles.

13. The lubricant according to claim 12, characterized in that the silica particles are modified using a hydrophobing agent in an amount ranging between 0.1 to 0′ 4* mg per gram of silica particles.

14. The lubricant according to any of the preceding claims, characterized in that it also contains additives used in hydraulic and/or other water-based functional fluide, such as being corrosion inhibitors, shear stablisinq agents, thickeners, bactericides, dyes, water softening agents, odour masking agents, surfactants, anti-wear additives, de-foamers and extreme-pressure additives. 410 N’v^ 14 A process for preparing a lubricant comprising an oil-in-water emulsion having a composition as disclosed in claims 1-14, characterized in that an aqueous dispersion of suitably hydrophobic silica particles and a lubricating materia is emulsified so as to form an emulsion of droplets coated with a rigid silica skin.

16. A lubricant as claimed in any one of claims 1 to when used as a hydraulic fluid.

17. A lubricant as claimed in any one of claims 1 to when used as metal-working or metal-rolling fluid. 0 00 a 0 o oa I 0 00 0 0 DATED THIS 20TH DAY OF JUNE 1990 o o UNILEVER PLC i oo 0 By its Patent Attorneys: 0 00 GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia. oo a o oo 0000 0 Q 00 0 0 00 0 0000 0000 0 0000 00 0 0 0 0 00 /3 1 s I^I y

AU22386/88A
1987-09-21
1988-09-19
A lubricant comprising an oil-in water emulsion, a process for the preparation thereof and the use of the lubricant

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A lubricant comprising an oil-in water emulsion, a process for the preparation thereof and the use of the lubricant

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Families Citing this family (18)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

JPH07119431B2
(en)

1987-12-24
1995-12-20
旭電化工業株式会社

Oil-soluble additive for addition to base oil and method for producing the same

US5213166A
(en)

1989-12-12
1993-05-25
Mitsui-Cyanamid, Ltd.
Pile driving and pile removing method

GB9021061D0
(en)

1990-09-27
1990-11-07
Unilever Plc
Encapsulating method and products containing encapsulated material

DE4116396C2
(en)

1991-05-18
1996-04-25
Grace Gmbh

Modified amorphous silica, process for their preparation and antiblocking agents

EP0773091A3
(en)

1992-03-20
1998-04-01
Unichema Chemie B.V.
Release composition

US5541048A
(en)

1995-05-12
1996-07-30
Eastman Kodak Company
Lubricant particles, method of preparation, and photographic elements

GB2314341A
(en)

1996-05-21
1997-12-24
John Richard Drewe
Multiphase mixture for use in fluid dynamics

DE19805358A1
(en)

1998-02-12
1999-08-19
Grace Gmbh

Integrated additive composition, process for its preparation and its use

DE19852203A1
(en)

1998-11-12
2000-05-18
Henkel Kgaa

Lubricant with solid particles with a particle size below 500 nm

GB9925439D0
(en)

1999-10-27
1999-12-29
Unilever Plc
Hair treatment compositions

WO2006003403A1
(en)

2004-07-02
2006-01-12
The University Court Of The University Of Edinburgh
Fluid-bicontinuos particle-stabilised gels

DE102005012409A1
(en)

2005-03-17
2006-09-21
Wacker Chemie Ag

Aqueous dispersions of partially hydrophobic silicic acids

US20070202603A1
(en)

2006-02-27
2007-08-30
Steven Wayne Counts
Apparatus and method for sampling and correcting fluids

JP2008063411A
(en)

2006-09-06
2008-03-21
Denso Corp
Heat-transporting fluid, heat-transporting structure and method for transporting heat

EP1958687B1
(en)

2007-02-15
2011-11-23
Unilever PLC
Emulsifier system

US8137747B2
(en)

2008-07-30
2012-03-20
Honeywell International Inc.
Components, turbochargers, and methods of forming the components

DE102013011269A1
(en)

2013-07-03
2015-01-22
Fels-Werke Gmbh

Mold or formwork release agent

CN116014453B
(en)

2022-10-27
2023-08-15
电子科技大学
Super-hydrophobic terahertz wave absorber based on MXene and cage-shaped structure three-dimensional foam

Citations (3)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US2628197A
(en)

1950-08-17
1953-02-10

Socony Vacuum Oil Co Inc

Metalworking lubricant

GB858863A
(en)

1957-05-20
1961-01-18

Hoyt Metal Company Of Great Br

Improvements in or relating to processes for lubricating textile fibres

US3454495A
(en)

1965-09-01
1969-07-08

Hooker Chemical Corp

Composition and process for metal forming

Family Cites Families (11)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US2112632A
(en)

1935-12-17
1938-03-29
H A Montgomery Company Inc
Process and composition for plastic deformation of metals

US2722515A
(en)

1951-03-28
1955-11-01
Shell Dev
Metal working lubricating compositions

GB952352A
(en)

1959-05-27
1964-03-18
Dow Chemical Co
Improvements in and relating to emulsifying agents based on silica

JPS4919750B1
(en)

1970-12-21
1974-05-20

US3948784A
(en)

1975-03-24
1976-04-06
Nalco Chemical Company
Treatment of industrial grinding and cutting lubricants

JPS5461380A
(en)

1977-10-24
1979-05-17
Inoue Japax Res Inc
Improved machining liquid

US4148970A
(en)

1977-12-30
1979-04-10
Diamond Shamrock Corporation
Lubricating composition applied over primer coat

US4244742A
(en)

1978-06-27
1981-01-13
Wacker-Chemie Gmbh
Process for the production of aqueous based inner tire release compositions

CA1169847A
(en)

1980-01-24
1984-06-26
Carl A. Eggers
Hydraulic fluid, hydraulic equipment containing this fluid and a concentrate of this fluid

EP0081008A1
(en)

1981-12-04
1983-06-15
Akzo N.V.
Anticaking compositions for hygroscopic or water-soluble material in particulate form

GB8610023D0
(en)

1986-04-24
1986-05-29
Unilever Plc
Silica platelets

1988

1988-09-19
AU
AU22386/88A
patent/AU603927B2/en
not_active
Ceased

1988-09-20
ES
ES88202045T
patent/ES2025281B3/en
not_active
Expired – Lifetime

1988-09-20
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DE8888202045T
patent/DE3864365D1/en
not_active
Expired – Fee Related

1988-09-20
EP
EP88202045A
patent/EP0309054B1/en
not_active
Expired – Lifetime

1988-09-20
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AT88202045T
patent/ATE66488T1/en
active

1988-09-20
US
US07/247,090
patent/US4995995A/en
not_active
Expired – Fee Related

1988-09-21
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JP63237481A
patent/JPH01108299A/en
active
Pending

1991

1991-10-10
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GR91401529T
patent/GR3002881T3/en
unknown

Patent Citations (3)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US2628197A
(en)

1950-08-17
1953-02-10
Socony Vacuum Oil Co Inc
Metalworking lubricant

GB858863A
(en)

1957-05-20
1961-01-18
Hoyt Metal Company Of Great Br
Improvements in or relating to processes for lubricating textile fibres

US3454495A
(en)

1965-09-01
1969-07-08
Hooker Chemical Corp
Composition and process for metal forming

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1991-09-26

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1989-03-23

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1991-02-26

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