EP0308759B1 - Lubrifiant métallique résistant aux chocs et à l'usure présentant un effet de rénovation, ainsi que procédé de fabrication de ce produit - Google Patents
Lubrifiant métallique résistant aux chocs et à l'usure présentant un effet de rénovation, ainsi que procédé de fabrication de ce produit Download PDFInfo
- Publication number
- EP0308759B1 EP0308759B1 EP88114875A EP88114875A EP0308759B1 EP 0308759 B1 EP0308759 B1 EP 0308759B1 EP 88114875 A EP88114875 A EP 88114875A EP 88114875 A EP88114875 A EP 88114875A EP 0308759 B1 EP0308759 B1 EP 0308759B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricant
- weight
- metal
- fact
- respect
- 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.)
- Expired - Lifetime
Links
- 239000000314 lubricant Substances 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 230000009471 action Effects 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910002059 quaternary alloy Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 239000004005 microsphere Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000011133 lead Substances 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011135 tin Substances 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012188 paraffin wax Substances 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 239000007970 homogeneous dispersion Substances 0.000 claims abstract description 3
- 239000002480 mineral oil Substances 0.000 claims abstract 3
- 239000000654 additive Substances 0.000 claims abstract 2
- 239000003921 oil Substances 0.000 claims description 11
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000010687 lubricating oil Substances 0.000 claims description 4
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 2
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 239000013008 thixotropic agent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000000956 alloy Substances 0.000 description 17
- 238000005461 lubrication Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XMUVWGSHBGHBDH-UHFFFAOYSA-J molybdenum(4+);sulfanide Chemical compound [SH-].[SH-].[SH-].[SH-].[Mo+4] XMUVWGSHBGHBDH-UHFFFAOYSA-J 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- SGHWILJCQCTGGE-UHFFFAOYSA-N 2-dodecyl-2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)(C(O)=O)CCCCCCCCCCCC SGHWILJCQCTGGE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M5/00—Solid or semi-solid compositions containing as the essential lubricating ingredient mineral lubricating oils or fatty oils and their use
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/08—Alloys based on copper with lead as the next major constituent
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B1/00—Engines characterised by fuel-air mixture compression
- F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
- F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
Definitions
- This invention refers to a shockproof, wearproof metal lubricant with restoring action of worn metal surfaces and the relative production process.
- the task of lubrication is to increase the mechanical efficiency of the machines, through a reduction of the friction between moving surfaces rubbing against each other, and to prevent or reduce wear on said moving parts, increasing their lifespan, by placing between them a veil of greasy substances more or less viscous than the lubricants, and help to maintain a suitable thermic state, subtracting continuous heat from the machine.
- liquid or semisolid lubricants like oil or lubricating grease
- solid lubricants comprise graphite, talc, bentanite and molybdenum bisulphide, all substances with a lamellar structure, almost always used in suspension of liquids, e.g. graphitic oils.
- metal powders which act as support to the liquid or semisolid lubricants to improve their poor shockproof and wearproof qualities. The interest in attempting to use metal products is based on the necessity to form a permanent protective layer on the mechanical moving parts submitted to friction.
- the metal powders serve, in fact, to fill the natural pores and flaws, invisible to the naked eye, of the metal surfaces of the moving mechanical parts subject to wear.
- the results obtained with the use of metal powders are a reduction of friction, an increase in flowability, a lowering of the operating temperature and rate of wear, an improvement in lubrication, a restoration of the clearances and coupling provided by the constructor and consequently a reduction also in energy consumptions.
- lead which offers excellent lubricating and anti-seizing qualities.
- due to its too low melting point (327.5°C) it has never been possible to use this metal as auxiliary for traditional lubricants.
- the metal used for this purpose is copper, which has a melting point of 1083°C.
- the object of this invention is to optimize the copper and lead alloy so that it may be used for the formulation of lubricating products free from the above problems.
- Another object of this invention is to provide a copper and lead alloy which can be dispersed in traditional liquid or semisolid lubricants and solves all problems linked with different types of friction, wear and lubrication of the various mechanical systems.
- these objects are obtained by adding to the copper-lead alloy other metals with function of activators.
- the object of this invention is therefore a shockproof, wearproof lubricant with restoring action of the worn metal surfaces, consisting of a stable, homogeneous dispersion of microspheres of a quaternary alloy of copper, lead, tin and silver in a mixture of naphthene and paraffin oils.
- the microspheres of the alloy can be obtained by means of melting and subsequent process of atomization in a micronized spheric powder in various measures. Its spheric structure, with respect to the lamellar one, offers the advantage of a greater flowability on the surface to be treated, and, in the case of unsuitable thicknesses, ejection or non-reception.
- the new formulates, specific for lubricants for the lines Industry, Car Drive in general and Navigation are also characterized by the fact of comprising also special auxiliary substances which must stabilize, standardize and often all keep in suspension, in the mixture of paraffin and naphthene oils, the microspheres of quaternary alloy to guarantee complete homogeneity and stability of said formulates.
- the alloy used in the manufacture of the lubricants of this invention can be obtained by means of melting and subsequent atomization process of the metals in the following preferred quantities: COPPER, between 40 and 60%, preferably 56%, with respect to the weight of the alloy; LEAD, between 30 and 50%, preferably 40%, with respect to the weight of the alloy; TIN, between 1 and 5%, preferably 3%, with respect to the weight of the alloy; SILVER, between 0.1 and 2%, preferably 1%, with respect to the weight of the alloy.
- the quaternary alloy is present in the various types of lubricants in quantities of between 12 and 16% in weight and preferably 14% in weight of the total lubricant composition.
- microspheres are therefore separated in various fractions, generally four, with different diameter intervals, usable for the formulation of four main types of metal lubricants in the following sectors: Diameter in microns Sector Use/Destination 0.1 to 40 Car drive (and motor cycling) 2 and 4-stroke diesel and petrol engines 40 to 60 Car drive Transmissions, gear-shifts, differential gears); Industry compressors, pumps, small reduction gears; Navigation transmissions, gear-shifts, U-drive,V-drive etc.; 60 to 90 Industry Pinions for lamination trains, pumps, hoisting reduction gears, convertors, cog-wheels, helical gears, etc.; 90 to 115 Industry Any type of industrial plant where excessive clearances and wear are found, e.g. in old and neglected plants.
- composition of the four main formulates prepared with the four grain size fractions of quaternary alloy previously indicated is shown in table A, where the raw materials and relative percentages, the characteristics and function of each of them are specified.
- the products obtained are compatible and perfectly mixable with any lubricating oil for either engines or transmissions, but are not compatible with oils additivated with graphite or molybdenum bisulphide and with other solid lubricants. They are suitable for each type of lubrication of any metal surface, both sliding and rolling, with circulation of the lubrication or with fixed chamber. For example, for rapid engines with internal combustion, tests carried out by the applicant have established that, in any type of lubrication, a quantity of metal lubricant not exceeding 4% in weight is recommended.
- This protective film protects, through time, the actual piece, withstanding its loads and future wear and improving, according to the shockproof properties of the mixture, its operation.
- the diameter interval within which said metal lubricant can be used without undergoing substantial modifications of quality and characteristics is very wide and varies from -200° to +800°C.
- the properties of the metal microspheres of being naturally self-lubricating makes it possible to create, within the diameter limits indicated, a self-lubrication process of the treated parts, even when faults or temporary breaks in lubrication take place, with consequent overheating of said parts, guaranteeing, when temperatures do not exceed 830°, the prevention of seizing.
- the colloidal mixture with suspending action formed by the metal lithium and dodecylhydroxystearic acid components is inserted, continuing stirring for the time necessary for its complete dispersion, at any rate until, with a dripping test, there are no lumps or deposits of said mixture. Said dripping test will then be repeated after the insertion of each other component.
- the following are then loaded in this order, the thixotropic agent uncompressed silica gel, the greasy, absorbent agent trioleate glyceryl, the mixture with wearproof, rustproof, detergent action, formed by components metal zinc, metal magnesium and phosphor and the alloy in copper, lead, tin and silver powder (56%-40%-3%-1%).
- the preparation tank must not be submitted to agitation or vibrations of any type (ultrasounds included), to avoid damaging the product.
- the tank is contained in thermostat bath.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
- Materials For Medical Uses (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Powder Metallurgy (AREA)
Claims (8)
- Métal resistant aux chocs, lubrifiant contre l'usure, avec une action de restauration des surfaces du métal usé, consistant en une dispersion stable et homogène de microsphères d'un alliage quaternaire de cuivre, plomb, étain et argent dans un mélange de naphthène et huile de paraffine.
- Métal lubrifiant selon la revendication 1, caractérisé par le fait que le dit quaternaire alliage comprend:
40-60% en poids de cuivre, de préférance 56%; 30-50% en poids de plombe, de préférence 40%; 1-5% en poids d'étain, de préférance 3%; et 0,1-2% en poids d'argent, de préférance 1%. - Métal lubrifiant selon les revendications 1 et 2, caractérisé par le fait que les microsphères du dit alliage métallique ont un diamètre compris entre 0,1 e 115 microns.
- Métal lubrifiant selon n'importe quelle précédente revendication, caracterisé par le fait que le dit quaternaire alliage est présent en quantités comprises entre 12% et 16%, de préférence 14% en poids du lubrifiant.
- Métal lubrifiant selon n'importe quelle revendication précédente, caracterisé par le fait que le mélange des huiles mineraux est composé de 50% de naphthène avec une viscosité de 26 cP à 40°C (2,7 Engler à 50°C) et 50% d'huile de paraffine avec une viscosité de 86 cP à 40°C (8 Engler à 50°C).
- Métal lubrifiant selon n'importe quelle revendication précédente, caracterisé par le fait que le mélange des huiles mineraux est présent en quantités comprise entre 68% et 74% en poids, par rapport au lubrifiant.
- Métal lubrifiant selon n'importe quelle revendication précédente, caracterisé par le fait qu'il contient aussi:- de 1,1 jusqu'à 2% en poids, par rapport au lubrifiant, d'un mélange colloïdal avec une action de suspension;- de 5 jusqu'à 7% en poids, par rapport au lubrifiant, d'un agent tixothrope;- de 2,14 jusqu'à 5,24% en poids, par rapport au lubrifiant, d'un agent avec une action absorbante du gras.- 0,76% en poids, par rapport au lubrifiant, d'additifs avec une action détèrgente et de protection contre l'usure et contre la rouille, et- 3% en poids, par rapport au lubrifiant, d'un agent qui améliore la viscosité et abaisse le point de congélation.
- Métal lubrifiant selon n'importe quelle revendication précédente, caracterisé par le fait que sont ajoutés en quantité pas excédente le 4% en poids des huiles lubrifiants pour moteurs et transmissions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88114875T ATE83268T1 (de) | 1987-09-24 | 1988-09-12 | Schlagbestaendiger und abnutzungsbestaendiger metallischer schmierwerkstoff mit restaurierender wirkung und diesbezuegliches herstellungsverfahren. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT22016/87A IT1223305B (it) | 1987-09-24 | 1987-09-24 | Lubrificante metallico antiattrito, antiusura, ad azione ripristinante e relativo procedimento di fabbricazione |
| IT2201687 | 1987-09-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0308759A1 EP0308759A1 (fr) | 1989-03-29 |
| EP0308759B1 true EP0308759B1 (fr) | 1992-12-09 |
Family
ID=11190242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88114875A Expired - Lifetime EP0308759B1 (fr) | 1987-09-24 | 1988-09-12 | Lubrifiant métallique résistant aux chocs et à l'usure présentant un effet de rénovation, ainsi que procédé de fabrication de ce produit |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0308759B1 (fr) |
| AT (1) | ATE83268T1 (fr) |
| DE (1) | DE3876561T2 (fr) |
| ES (1) | ES2053657T3 (fr) |
| GR (1) | GR3007187T3 (fr) |
| IT (1) | IT1223305B (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2095996C (fr) * | 1993-05-11 | 2002-11-19 | Terry Grinham | Lubrifiant destine a la surface du diametre interieur d'un pneu dans le cas de materiel supporte par des tourillons rotatifs |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB488590A (en) * | 1936-03-23 | 1938-07-11 | Continental Oil Co | Improvements in and relating to bearings and bearing materials |
| GB699097A (en) * | 1950-10-18 | 1953-10-28 | Glacier Co Ltd | Improvements in or relating to plain bearings |
| GB785936A (en) * | 1953-12-24 | 1957-11-06 | Texaco Development Corp | Improvements in or relating to incorporation of solid materials in oil |
| GB823357A (en) * | 1957-08-16 | 1959-11-11 | Exxon Research Engineering Co | Pipe thread lubricant |
-
1987
- 1987-09-24 IT IT22016/87A patent/IT1223305B/it active
-
1988
- 1988-09-12 EP EP88114875A patent/EP0308759B1/fr not_active Expired - Lifetime
- 1988-09-12 DE DE8888114875T patent/DE3876561T2/de not_active Expired - Fee Related
- 1988-09-12 AT AT88114875T patent/ATE83268T1/de not_active IP Right Cessation
- 1988-09-12 ES ES88114875T patent/ES2053657T3/es not_active Expired - Lifetime
-
1993
- 1993-03-02 GR GR930400022T patent/GR3007187T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IT1223305B (it) | 1990-09-19 |
| DE3876561D1 (de) | 1993-01-21 |
| ATE83268T1 (de) | 1992-12-15 |
| ES2053657T3 (es) | 1994-08-01 |
| IT8722016A0 (it) | 1987-09-24 |
| GR3007187T3 (fr) | 1993-07-30 |
| EP0308759A1 (fr) | 1989-03-29 |
| DE3876561T2 (de) | 1993-05-27 |
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