CN1013382B - Method for producing composite coating based on chromium - Google Patents
Method for producing composite coating based on chromiumInfo
- Publication number
- CN1013382B CN1013382B CN89101996.0A CN89101996A CN1013382B CN 1013382 B CN1013382 B CN 1013382B CN 89101996 A CN89101996 A CN 89101996A CN 1013382 B CN1013382 B CN 1013382B
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- coating
- electrolytic solution
- chromium
- diamond particle
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Saccharide Compounds (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
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- Electroplating Methods And Accessories (AREA)
- Polishing Bodies And Polishing Tools (AREA)
Abstract
A method of obtaining composite chromium-based coatings consists in the electrochemical deposition from a chromizing electrolyte containing colloidal cluster diamond particles measuring 0.001-0.01 microns at a concentration of 5-40 g/l.
Description
The present invention relates to the electroplating technology field, or rather, relate to prepare the method for composite coating based on chromium.
Chromium base coating is widely used in various technical fields, for example be used to improve pressing mold, drawing-die, the life-span of cylinder jacket of diesel engine and compression ring and reliability, and improve in friction, the life-span and the reliability of the miscellaneous part of in big load-up condition, working under abrasive wear and the cavitation corrosion situation.
In these cases, composite deposite is to be made of chromium, and contains disperse phase, particularly contains the metal matrix of superabrasive particle.Such coating has the physical-mechanical property and the wear resistance of raising.This coating has obtained to promote the most widely, in these coating, mainly decides above-mentioned those performances by disperse phase, and metal only is the particulate of these disperses to be interconnected and it is attached on the piece surface.
(E.M.C о к о л о в с к а я as everyone knows, " Ф и з и к о-х и м и я к о м п о з и п и о н н ы х м а т e р и а л о в; 1976; и з д. м г у; 230 pages); the content in disperse phase is the 5-10%(volume), and when the particle size of this phase was reduced to the 0.5-0.01 micron, the physical-mechanical property and the wear resistance of composite deposite reached maximum value.Think that traditionally the size that further reduces particulate will cause the reduction of their content in coating, its result makes the debase of coating.In view of the above, in practical application, be not recommended in particle size in the composite deposite less than 0.01 micron disperse phase.
Usually, but preparation has the electrolytic solution that the method for composite deposite of disperse particulate is to use the salt that contains metal refining and contains disperse phase electroplates.The composition of electrolytic solution, and the performance of disperse phase comprise the size of particulate, and character and to the stability of settlement action and cohesion has determined the quality of the coating that obtains.
To the essential requirement that the disperse particulate proposes, be their chemical stabilities in adopted electrolytic solution equally.For (strong acid) plating chromic electrolyte of severe corrosive, diamond particle is the most desirable.
People have implemented a series of methods that prepare composite coating based on chromium.Known have a kind of method for preparing this coating, it comprises that adding particle size in the electrolytic solution that is dissolved with chromic salts is disperse silicon-dioxide (the C а й Ф у л л и H P.C. " K о м б и-н и р о в н н ы e з л e к т р о х и м и ч e с к и e п о к р ы т и я и м а т e р и а л ы " of 0.01-0.1 micron, х и м и я, (М о с к в а), 1971,101 pages), in the electrolytic solution that is heated to working temperature, insert anode and part then, feed electric current and make the current density that reaches necessary, plated part as negative electrode, the result has obtained to be made of chromium, contains the coating of silicon dioxide microparticle during it is formed.The wear resistance of the coating that obtains, solidity to corrosion and all higher with the bonding strength of piece surface.But under the situation of temperature fluctuation, for example when causing metal contracts or extending, this coating has rapid destructive tendency.
Another kind of known method is that diamond powder is followed metal, particularly follow nickel electroplate together (Е. Л. П р у д н и к о в, " и н с т р у м e н т с а л м а з н о г а л ъ в а н и ч e с к и м п о к р ы т и e м ", 1985, м а щ и н о с т р о e н и e, (М о с к в а), 91 pages).Above-mentioned coating only is used as the coating of abrasive material, and if just can not be used as antifriction (а н т и Ф и к д и о н н ы e) and anti abrasive coating without special processing, this special processing just is the edge rust that makes diamond particle sharp-pointed, so that on the working-surface of coating, set up the plane, doing like this needs arduous work and needs to use adamantine machining tool, promptly needs additional technological operation.
The method (GB, B, 1391001) that also has a kind of known preparation metal matrix, particularly composite coating based on chromium.This method obtains coating by electroplating, and electroplating bath components is as follows:
CrO
3250 grams per liters
H
2SO
41.25-2.5 grams per liter
Cathode current density is a 6.4-10.7 peace/decimetre
2Use natural or the synthetical diamond as disperse phase, its particle size is the 0.01-30.0 micron, consumption is a 10-30 grams per liter electrolytic solution.The diamond disperse particulate that uses in this method has sharp-pointed edge, and is the abrasive material type therefore.For obtaining to have the performance of antifriction, the sharp edges of diamond particle in coating is orientated inwardly, and makes the flat surfaces orientation outwardly, the result makes complex technical processization.In addition, be the stable not sedimentation of the suspensoid of security deposit's hard rock in electrolytic solution, in advance will be with diamond particle successively at the mixture of hydrochloric acid, caustic soda, sulfuric acid and tonka bean camphor, handle in the cationic surfactant, then through super-dry, and place dense metal salt solution or the continuation of insurance of sour relaying to deposit, and perhaps joining in the electrolytic solution immediately and use, this makes complex technical processization equally.In addition, only obtain little cathode current density when implementing this method, the result has reduced the productivity of this technology.
Task of the present invention is to set up a kind of like this method for preparing composite coating based on chromium, uses this method can obtain to have high rigidity, strong wear resistance, and the coating of good antifriction performance, and adamantine consumption also can be used common technology less simultaneously.
This task is to solve like this, a kind of like this method for preparing composite coating based on chromium is provided, this method is to carry out electrochemical deposition with the plating chromic electrolyte that contains the diamond particle suspended substance, according to the present invention, use colloidal particle group as diamond particle in the method, particle size is the 0.001-0.01 micron, and content is the 5-40 grams per liter.
Use chromed hardened or self-regulating (buffered) electrolytic solution as plating chromic electrolyte.
The diamond particle group that uses in this method is that shape approaches spherical or oval-shaped particulate, does not have sharp-pointed edge (non-abrasive material type).This diamond or under the concentration that improves (in the enriched material at electrolytic solution), can both form stable system and sedimentation and cohesion not take place no matter under the working concentration of composition in electrolytic solution.
As mentioned above, it is generally acknowledged that the particle size of disperse phase is reduced to and will causes coating performance to degenerate below 0.01 micron.
But when using particle size to roll into a ball less than 0.01 micron diamond particle, the hardness of gained coating has all obtained significant raising with part bonded intensity and wear resistance.This be because, selected size diamond particle group has little inertia, thus disperse phase can be under best condition by electrolytic solution to the coating surface mass transfer, this just allows at high current density deposit coating.Through finding out, when electrochemistry chromium plating (equally at chemistry or other metals of electrochemical deposition, copper for example, nickel is during silver), diamond particle group is owing to have very high physical and chemical activity, thereby forms nucleus of crystal (nucleus), and the crystallization of metal is promptly begun by them.Owing in this process, have a large amount of particulates, so crystallization has the characteristics of common polycrystalline nuclear.Formed coating is organized tiny, and is long-range unordered in crystal structure.The size of chromium crystal grain approaches the size of diamond particle, and this point is confirmed by the data that X ray facies analysis and electron microscope record.In addition, the disperse phase particulate is actually mertialess mass transfer and chromium produces general crystallization, and the combination of these two kinds of effects has guaranteed that coating deposits on the equipotential surface equably.
With containing particle size is that the diamond of 0.01-0.5 micron is compared as the coating of disperse phase, undersized chromium crystal grain (highly trickle tissue) guaranteed coating microhardness obvious raising (for the former 1.5-2.5 doubly) wear resistance of coating also brings up to the former 2.5-3.0 doubly.
In addition, test shows, adds diamond particle group and reduced Cr in plating chromic electrolyte
6+→ Cr
3+The reductive energy barrier, this just can save to form Cr in electrolytic solution
3+Ion and on any negative electrode flower electrolytic solution initial " check " (the п р о р а б о т к и) operation of being carried out in 4-6 hour.
Like this, for obtaining chromium based electrochemical composite deposite, use diamond particle group to cause coating to form the change of mechanism, and obviously improved the performance of coating, that is:
-diamond particle group forms stable disperse in plating chromic electrolyte;
-diamond particle group can quicken Cr
6+Be reduced into Cr
3+, the result has alleviated the preparation work of process, and the ongoing energy consumption of the process that reduced;
The little quality (little inertia) of-diamond particle group has guaranteed the effective mass transfer of diamond particle to coating surface, makes and can work under high current density;
-because diamond particle group has high physical-chemical activity, and they have guaranteed the general crystallization of chromium, and the result forms the tissue of the super disperse of coating, this coating has high microhardness and wear resistance;
-undersized diamond particle group and undersized chromium crystal grain have guaranteed the microfluctuation of replicated surfaces exactly, and the result has increased institute's bonded total surface, so just makes to cause coating to be improved from the critical load numerical value that matrix metal breaks away from;
-diamond content little (0.3-1.0%(weight) in coating) under the situation, improved the quality of coating, this makes this technology comparatively economical;
-be that the composite deposite of base has higher solidity to corrosion with chromium and diamond particle group;
-reduced the energy barrier when reducing chromium, the general crystallization of chromium in diamond particle group, diamond is to effective mass transfer of part coating surface, and these effects have guaranteed the uniform deposition of coating on the equi-potential surface;
In plating chromic electrolyte, the diamond particle mass contg is the 5-40 grams per liter.The diamond particle mass contg is brought up to the strong retrogradation that will cause electrolytic solution more than 40 grams per liters and coalescent, and the result can hinder gas and separate out convection current with electrolytic solution, and hinders passing through of electric current.The diamond particle mass contg is reduced to 5 grams per liters when following in electrolytic solution, can significantly reduce the quality of coating.Will be by the content of correspondingly being determined diamond particle group in the electrolytic solution by the size and dimension of plating part.For example for the small size part with sharp-pointed sharp edges, the diamond particle mass contg is the electrolytic solution better effects if of 15-40 grams per liter.Bao cutter for example, dental drill, microsurgery instrument are all recognized with being such part.The diamond particle group of electrolytic solution middle and high concentration has guaranteed the reduction of strength of electric field on the part sharp edges, and has reduced to form the probability of dendrite.Diamond particle group's concentration is can harden the effectively surface of large-scale part of the electrolytic solution of 5-15 grams per liter, and these large-scale parts have: the part of the piston rod of punch die, pressing mold, hydro-cylinder, cylinder of internal combustion engine, speed reduction unit guide gear and transmission change-box and other machines and machinery.The viscosity of electrolytic solution is also not very high in the case, and this process is effective under the situation of electrolytic solution thermal natural convection.
When deposition was the coating of base with chromium and diamond particle group, the temperature of electrolytic solution depended on the purposes of coating.For example for friction means, bearing, liner, hydro-cylinder and gear, need have low-friction coefficient, high-wearing feature has simultaneously than soft, and this moment, the temperature of electrolytic solution can be determined in 35-50 ℃ scope.For the compression ring and the maneuvering shaft of cutter, punch die and pressing mold, oil engine, promptly for such situation: when coating was worked under the condition of big load (pressure+shearing force), the temperature of electrolytic solution was defined as 50-70 ℃.
For plating chromium and diamond particle group during for the coating of base, cathode current density in the electrolytic solution can change in the scope of broad, it depends on the desired structure of coating, for example stratiform or columnar structure, the optical property (opal or shinny) that also depends on required coating also depends on the hydromechanics fluid situation of technological process simultaneously.
For example, when electrolytic solution natural convection, current density is decided to be 40-60 peace/decimetre
2, and when the zone of plating coating forces to infeed electrolytic solution, and when using mechanical activation by the coating of plating, then current density can be decided to be 200-600 peace/decimetre
2
Because the net effect of coating performance that aforesaid method obtains, and because the simplification of this technology, make this method compare and have competitive capacity with the method for known plating coating, these known methods such as gas phase and plasma deposition, ion and detonation flame spraying, welding, and use elements such as nitrogen, boron, carbon to carry out surface diffusion to make surface hardening.
With chromium and the little material of diamond group is the part time job surface hardening that the coating of base can be used to make numerous kinds, these parts comprise cutter: Si Cone, expanding drill, milling cutter, steel Saw bar, file, needle file, dental drill, the operated pressing tool of the metal-powder that is used to cold pressing, and are used for the pressing mold and the punch die of deep cooling draw metal; Machine and mechanical component, for example axle of the cylinder of oil engine, piston ring, air distributing device, hydro-cylinder, medical instrument, slasher, scraper, drawing-die etc.
Table 1 has listed that to have with chromium and diamond particle group be that the part of the coating of base is compared the multiple that prolong its work-ing life with come the part on curing surface with currently known methods.
Table 1
By coating that the present invention obtains
The known method for curing of part kind with compare with known method
The prolongation in work-ing life
The pressing unit cyaniding 15-90 of-metal-powder of colding pressing doubly
（карбонитрация）
The drawing-die of-deep cooling draw metal and punch die chromium plating 2.5-4 are doubly
-steel Saw bar quenching 4.0-8.0 doubly
-Si Cone quenching 4.0-5.0 doubly
-Si Cone nitrogen TA 1.3-1.5 doubly
-drill bit (being used for glass reinforced plastic) quenching 10-30 doubly
-expanding drill (being used for glass reinforced plastic) quenches 50 times
Skull operation quenches 11 times with milling cutter
-oral cavity dental burr chromium plating 5-12 doubly
-IC engine gas distribution axle chromium plating 2-2.5 doubly
-motion motorcycle IC engine cylinder chromium plating 2-3 doubly
The hard of-the high-strength steel that is used to stretch
Alloy pressing mold and punch die-0.9-1.0 are doubly
-file, needle file quenching 2.5-4.0 are doubly
Preparation is that the method for the composite deposite of base is easy to realize in industry with chromium and diamond particle group, and can implement in the following manner.
The diamond particle group that adds 4-6% in the plating chromic electrolyte for preparing by known method contains hydro-colloid.The content of diamond particle group is the 5.0-40.0 grams per liter in the electrolytic solution.Part to be plated as negative electrode is loaded in the plating tank that fills the electrolytic solution that is heated to specified temperature in advance.Anode is made by lead or by stibiated lead alloy.Use electrolyte resistance corrosive material to make plating tank, for example Shi Yong TA, glass, pottery or plastics.Before starting working, with mechanical stirring or bubbling, for example the method with blowing compressed air stirs electrolytic solution.Just needn't force later on to stir, the stability of diamond particle group's suspensoid in electrolytic solution is by the character of itself, simultaneously by the separating out of gas on anode and the negative electrode, and leans on the thermal convection of electrolytic solution and is guaranteed.
The purposes of determining to depend on part of the thickness of coating of being plated.For example for slasher, its thickness is the 0.02-0.06 micron, is the 0.5-5.0 micron for cutter, is the 10.0-50 micron for die arrangement, for cylinder of internal-combustion engine is the 80.0-200.0 micron, for recoverable machine and mechanical component then greater than 200.0 microns.
The most desirable method of preparation electrolytic solution is to prepare a kind of like this enriched material.It promptly forms the electrolytic solution of working concentration behind dilute with water.This enriched material can be simplified the transportation and the preservation of the electrolytic solution that contains diamond particle group.
During the plating tank work that fills diamond particle group, its composition is analyzed and necessary adjustment.In order on the part of complicated shape, to plate coating, adopt anode and shielding slab with the known method preparation.Before plating coating to the preparation of part, promptly mechanical treatment, deoil, pickling, the removal of oxide film is all finished with known method equally.
In order to understand the present invention better, be listed below embodiment.The following bath composition of quoting is not got rid of to the possibility that wherein adds various additives, for example evaporates and the adding additive for the surface tension or the minimizing that reduce electrolytic solution.But should be noted that these additives may and form some independent particulate groups with the interaction of diamond particle group and cause adamantine cohesion and sedimentation, can reduce the efficient of technological process and the quality of coating like this.
Embodiment 1
With 250.0 grams per liter chromic anhydrides, 2.5 grams per liter sulfuric acid are dissolved in the distilled water successively, and add 6%(weight) diamond particle group contain hydro-colloid, diamond particle is of a size of the 0.001-0.01 micron.The content of diamond particle group is 5 grams per liters in the electrolytic solution.The electrolytic solution that is obtained is packed in the plating tank with steam, hot water or electric heater heating.Electrolytic solution is heated to 35 ℃.Anode is hung into plating tank, and part to be plated is as negative electrode.When the part of deal with complex shapes, use special-purpose anode and shielding slab.
In advance part is carefully cleared up, known chemistry and/or electrochemical bath in deoil rinsing and being connected on the electric current bus rod of negative electrode then.
Use can be along with the change of current polarity the standard constant current power supply of regulating voltage and electric current.
Part is placed electrolytic solution, be heated to the temperature of electrolytic solution, in 30 seconds of turn-on reversal electric current, current density is 30 peace/decimetres
2, connect 15 seconds of forward current then, current density is 60 peace/decimetres
2, connect forward current then, current density is 30 peace/decimetres
2The sedimentation velocity of coating be the 1.0-1.1 micron/minute.
It is the method that 108.9 degree De Jiao Cone bodies are pressed into that use is made De ， Cone angle with the carbon containing natural diamond, and the coating microhardness that records is 650 kilograms/millimeter
2
Embodiment 2-5
Method according to embodiment 1 prepares coating.The content of diamond particle group is respectively 10,20,30,40 grams per liters in electrolytic solution.The average microhardness of gained coating is corresponding at this moment equals 840,1130,1206,1030 kilograms/millimeter
2
Embodiment 6-8
Method according to embodiment 1 prepares coating.The content of diamond particle group is 15 grams per liters in the electrolytic solution.Electrolyte temperature is respectively 45,55,75 ℃.The average microhardness of the coating that obtains is corresponding to 1020,1410,1280 kilograms/millimeter at this moment
2
Embodiment 9
Dissolving 250 grams per liter chromic anhydrides in distilled water, 0.5 grams per liter sulfuric acid adds 6 grams per liter barium sulfate, 20 grams per liter silicon fluoro acid potassiums and 4%(weight) diamond particle group contain hydro-colloid.The content of diamond particle group is 15 grams per liters.
Gained electrolytic solution is heated to 55 ± 2 ℃, and stirred 15 minutes, partly be transferred in the solution so that the microsolubility composition is silicofluoric acid Potassium and barium sulfate with known method.All subsequent handling is finished by embodiment 1 described method.Cathode current density is 60 peace/decimetres
2, the current density of forward current is 90 peace/decimetres
2The sedimentary speed of coating be the 1.1-1.3 micron/minute.The performance of coating is listed in table 2.
Embodiment 10-14
According to embodiment 9 preparation coating.The content of diamond particle group is respectively 2,4,10,20,40 grams per liters in the electrolytic solution.Coating performance is listed in table 2.
The cut resistance test of coating is to finish on the frictional testing machines of " brake shoe-rotating shaft " mode, drips a small amount of low viscosity oil during test.
Friction surface is 1 centimetre
2, the load of friction surface is 100 kilograms of seconds (к г с).
Test period is 100 hours, and the sliding velocity in the contact is 0.8 meter per second.
Brake shoe and rotating shaft are by containing chromium 4%(weight) steel make.Coating is plated on the brake shoe, and rotating shaft is as the opposite object.
When using diamond particle group, reduced the grinding loss of opposite object, reduced the temperature of frictional coefficient and frictional belt according to the foregoing description.
Embodiment 15
Dissolving 225 grams per liter chromic anhydrides add 6 grams per liter Strontium Sulphates in distilled water, 20 grams per liter silicon fluoro acid potassiums, and the method adding diamond particle group of pressing embodiment 9.Each processing parameter is determined according to embodiment 9 equally.Above-mentioned electrolytic solution is compared with 9 with embodiment 1 has less corrosive nature.For part, and, have the part of sharp edges for undersize part by aluminium and aluminium alloy system, for example blade, pin, jig drill head, dental drill, should preferably use above-mentioned electrolytic solution.The numerical value that the microhardness of its coating and wear resistance and embodiment 9 are obtained is suitable.
Claims (1)
1, prepare the method for composite coating based on chromium by the plating chromic electrolyte that contains the diamond particle suspended substance by electrochemical deposition, it is characterized in that, use the colloidal particle group of particle size as the 0.001-0.01 micron as diamond particle, its amount is the 5-40 grams per liter.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU4382417 | 1988-02-11 | ||
| SU4382417 | 1988-02-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1036607A CN1036607A (en) | 1989-10-25 |
| CN1013382B true CN1013382B (en) | 1991-07-31 |
Family
ID=21357255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89101996.0A Expired CN1013382B (en) | 1988-02-11 | 1989-02-10 | Method for producing composite coating based on chromium |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0386245B1 (en) |
| JP (1) | JPH02503095A (en) |
| CN (1) | CN1013382B (en) |
| AT (1) | ATE103019T1 (en) |
| AU (1) | AU3057489A (en) |
| DE (1) | DE3888539D1 (en) |
| DK (1) | DK501189D0 (en) |
| FI (1) | FI894781A0 (en) |
| HU (1) | HU202291B (en) |
| NO (1) | NO894029L (en) |
| NZ (1) | NZ227949A (en) |
| PL (1) | PL277676A1 (en) |
| WO (1) | WO1989007668A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT408352B (en) * | 1999-03-26 | 2001-11-26 | Miba Gleitlager Ag | GALVANICALLY DEPOSIT ALLOY LAYER, ESPECIALLY A RUNNING LAYER OF A SLIDING BEARING |
| RU2147524C1 (en) * | 1999-06-29 | 2000-04-20 | Князев Евгений Владимирович | Method of manufacturing objects |
| DE19931829A1 (en) | 1999-07-08 | 2001-01-18 | Federal Mogul Burscheid Gmbh | Galvanic hard chrome layer |
| CN101255592B (en) * | 2007-12-07 | 2010-07-07 | 华南理工大学 | Chromium/diamond composite deposite and preparation method thereof |
| RU2699699C1 (en) * | 2018-11-15 | 2019-09-09 | Сергей Константинович Есаулов | Composite metal-diamond coating, method of its production, diamond-containing additive of electrolyte and method of its production |
| CN114525568A (en) * | 2022-02-21 | 2022-05-24 | 重庆大学 | Cr-modified nano diamond wear-resistant coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4369098A (en) * | 1980-08-12 | 1983-01-18 | Barristo, Ltd. | Method of manufacturing abrasive articles |
-
1988
- 1988-11-21 JP JP89502222A patent/JPH02503095A/en active Pending
- 1988-11-21 HU HU891276A patent/HU202291B/en not_active IP Right Cessation
- 1988-11-21 DE DE89902349T patent/DE3888539D1/en not_active Expired - Lifetime
- 1988-11-21 WO PCT/SU1988/000230 patent/WO1989007668A1/en not_active Application Discontinuation
- 1988-11-21 AU AU30574/89A patent/AU3057489A/en not_active Abandoned
-
1989
- 1989-02-10 PL PL27767689A patent/PL277676A1/en unknown
- 1989-02-10 NZ NZ227949A patent/NZ227949A/en unknown
- 1989-02-10 CN CN89101996.0A patent/CN1013382B/en not_active Expired
- 1989-08-29 AT AT89902349T patent/ATE103019T1/en active
- 1989-08-29 EP EP89902349A patent/EP0386245B1/en not_active Expired - Lifetime
- 1989-10-09 FI FI894781A patent/FI894781A0/en not_active Application Discontinuation
- 1989-10-09 NO NO89894029A patent/NO894029L/en unknown
- 1989-10-10 DK DK501189A patent/DK501189D0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3888539D1 (en) | 1994-04-21 |
| EP0386245A4 (en) | 1991-07-03 |
| ATE103019T1 (en) | 1994-04-15 |
| JPH02503095A (en) | 1990-09-27 |
| NZ227949A (en) | 1990-12-21 |
| WO1989007668A1 (en) | 1989-08-24 |
| DK501189A (en) | 1989-10-10 |
| HU891276D0 (en) | 1990-03-28 |
| EP0386245B1 (en) | 1994-03-16 |
| CN1036607A (en) | 1989-10-25 |
| NO894029D0 (en) | 1989-10-09 |
| EP0386245A1 (en) | 1990-09-12 |
| NO894029L (en) | 1989-10-09 |
| AU3057489A (en) | 1989-09-06 |
| HUT52181A (en) | 1990-06-28 |
| PL277676A1 (en) | 1989-09-04 |
| FI894781A0 (en) | 1989-10-09 |
| DK501189D0 (en) | 1989-10-10 |
| HU202291B (en) | 1991-02-28 |
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