DE1621206B2 - PROCESS FOR COATING WITH SLIDING FRICTION ON WORKPIECES STRESSED BY WEAR - Google Patents
PROCESS FOR COATING WITH SLIDING FRICTION ON WORKPIECES STRESSED BY WEARInfo
- Publication number
- DE1621206B2 DE1621206B2 DE19671621206 DE1621206A DE1621206B2 DE 1621206 B2 DE1621206 B2 DE 1621206B2 DE 19671621206 DE19671621206 DE 19671621206 DE 1621206 A DE1621206 A DE 1621206A DE 1621206 B2 DE1621206 B2 DE 1621206B2
- Authority
- DE
- Germany
- Prior art keywords
- electroless
- bath
- wear
- workpieces
- coating
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/1266—O, S, or organic compound in metal component
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
Es ist seit längerem bekannt, daß man metallische oder nicht metallische Feststoffe verschiedensten Elektrolyten, z. B. elektrolytischen Nickelbädern, zusetzen kann und daß diese während der Elektrolyse in den Niederschlag mit eingelagert werden können.It has long been known that metallic or non-metallic solids of various electrolytes, z. B. electrolytic nickel baths, and that this during the electrolysis in the Precipitation can be stored with.
Durch die Inkorporation von Feststoffteilchen können die physikalischen, chemischen und elektrochemischen Eigenschaften des abgeschiedenen Metalls erheblich beeinflußt werden, beispielsweise Härte, Verschleißfestigkeit, Reibungskoeffizient, Temperaturbeständigkeit, Oxydationsbeständigkeit, Korrosionsbeständigkeit, Reflexionseigenschaften, Glanz.Through the incorporation of solid particles, the physical, chemical and electrochemical Properties of the deposited metal are significantly influenced, for example Hardness, wear resistance, coefficient of friction, temperature resistance, oxidation resistance, corrosion resistance, Reflective properties, gloss.
Nach diesem Verfahren hergestellte Metallüberzüge haben jedoch den Nachteil, daß bei dickeren Schichten, wie sie für technische Zwecke angewendet werden, selbst nach Anwendung von gerichteten Innenanoden aufwendige Nachbearbeitungsprozesse, wie Schleifoperationen, erforderlich sind.Metal coatings produced by this method, however, have the disadvantage that when thicker Layers as used for technical purposes, even after the use of directional internal anodes complex post-processing processes, such as grinding operations, are required.
Ebenfalls bekannt sind Bäder oder Verfahren zur stromlosen Abscheidung von Metallniederschlägen.Also known are baths or processes for the electroless deposition of metal precipitates.
In der Literatur wird ausdrücklich darauf hingewiesen, daß die stromlosen Bäder von allen Verunreinigungen durch Feststoffteilchen freizuhalten seien, da sie sich anderenfalls infolge Keimbildung zersetzen würden.In the literature it is expressly pointed out that the electroless baths are free from all impurities must be kept free by solid particles, otherwise they will decompose as a result of nucleation would.
Es hat sich nun überraschenderweise gezeigt, daß stromlosen Bädern eine Reihe von unlöslichen bzw. schwerlöslichen Teilchen entsprechender Reinheit und beträchtlicher Teilchengröße zugesetzt werden können, die in den Niederschlag eingebaut werden. Diese Teilchen können im Bad z. B. durch Rühren, Umpumpen, Einleiten von Gasen (z. B. Luft, Stickstoff) oder Warenbewegung in Suspensionen gehalten werden. It has now been shown, surprisingly, that electroless baths contain a number of insoluble or sparingly soluble particles of appropriate purity and considerable particle size can be added, which are built into the precipitation. These particles can be in the bathroom, for. B. by stirring, pumping, Introducing gases (e.g. air, nitrogen) or moving goods are kept in suspensions.
Inzwischen ist ein stromloser Nickel-Elektrolyt in der Literatur bekanntgeworden, dem kleine Feststoffpartikelchen zugesetzt werden sollen zwecks Abscheidung einer dünnen Nickelschicht. Nach einer Verchromung soll eine mikroporöse Chromschicht' erzielt werden, um eine gesteigerte Korrosionsschutzwirkung des Niederschlages zu erreichen. DL-Patentschrift DDR 41 406).In the meantime, an electroless nickel electrolyte has become known in the literature, to which small solid particles are to be added for the purpose of separation a thin layer of nickel. After chrome plating, a microporous chrome layer should be achieved in order to achieve an increased anti-corrosion effect of the precipitate. DL patent GDR 41 406).
Die vorliegende Erfindung bezieht sich auf die »stromlose« Abscheidung verhältnismäßig dicker »dispersionsgehärteter« Metallüberzüge. Der Ausdruck »stromlose Abscheidung«, wie er hier verwendet wird, bezieht sich auf die Abscheidung von Metallüberzügen ohne äußere Stromquelle, vorzugsweise durch chemische Reduktion.The present invention relates to the "electroless" deposition of relatively thick "dispersion hardened" Metal coatings. The term "electroless deposition" as used here refers to the deposition of metal coatings without an external power source, preferably by chemical means Reduction.
Als »dispersionsgehärtet« bezeichnen wir Metall-. überzüge, in die bei der Abscheidung inerte Feststoffteilchen eingebettet wurden. Dabei können diese Teilchen vom Metall teilweise oder vollkommen eingeschlossen sein.We refer to metal as »dispersion hardened«. coatings in which solid particles are inert during deposition were embedded. These particles can be partially or completely enclosed by the metal be.
Nach dem erfindungsgemäßen Verfahren ist es möglich, auch relativ große Partikelchen (0,01 bis 100 Mikron) stromlos arbeitenden Bädern zuzusetzen und die entsprechenden Abscheidungen auch im kontinuierlichen Betrieb zu erhalten, so daß z. B. Niederschläge zwischen 5 und 200 Mikron erhalten werden können. Diese dispersionsgehärteten Metallüberzüge haben gegenüber den elektrolytisch hergestellten den Vorteil, daß die Maßhaltigkeit bis zur vollen Schichtstärke erhalten bleibt und eine Bearbeitung der Schichten nach der Abscheidung gänzlich entfallen bzw. auf ein Minimum beschränkt werden kann.According to the method according to the invention, it is also possible to use relatively large particles (0.01 to 100 micron) to add electroless baths and the corresponding deposits also in continuous To obtain operation, so that z. B. Precipitates between 5 and 200 microns can be obtained can. These dispersion-hardened metal coatings have the opposite to the electrolytically produced Advantage that the dimensional accuracy is maintained up to the full layer thickness and processing of the Layers after the deposition can be dispensed with entirely or restricted to a minimum.
Ein weiterer Vorteil der stromlos abgeschiedenen, dispersionsgehärteten Metallüberzüge ist der, daß die Schichten, die durch die Einlagerung der Feststoffteilchen in den meisten Fällen schon eine Härtesteigerung erfahren haben, durch Temperatureinwirkung noch weiter gehärtet werden können (1000 bis 1100 HV). Solche Härten können bei elektrolytisch abgeschiedenen Schichten nicht erreicht werden.Another advantage of the electrolessly deposited, dispersion-hardened metal coatings is that the Layers that in most cases already have an increase in hardness due to the inclusion of solid particles have experienced, can be hardened even further by the action of temperature (1000 to 1100 HV). Such hardnesses cannot be achieved with electrodeposited layers.
Nach dem erfindungsgemäßen Verfahren können vorteilhaft alle Teile behandelt werden, die in der Praxis gleitend beansprucht werden, z. B. Gleitlager, ίο Motorengehäuse, Wellen.According to the method according to the invention, all parts can advantageously be treated that are in the Practice sliding stress, z. B. plain bearings, ίο engine housings, shafts.
Als Matrix kann beispielsweise verwendet werden:The following can be used as a matrix, for example:
Abgeschieden aus1) I. NickelDeposited from 1 ) I. Nickel
a) 30 g/l Nickelchlorid 15 g/l Natriumacetat 10 g/l Natriumhypophosphit pH 4a) 30 g / l nickel chloride 15 g / l sodium acetate 10 g / l sodium hypophosphite pH 4
95°C95 ° C
b) 30 g/l Nickelsulfat 100 g/l Natriumcitrat 50 g/l Ammoniumchloridb) 30 g / l nickel sulfate 100 g / l sodium citrate 50 g / l ammonium chloride
10 g/l Natriumhypophosphit pH 8 bis 10
95° C10 g / l sodium hypophosphite pH 8 to 10
95 ° C
c) 30 g/l Nickelchlorid 10 g/l Natriumcitrat 20 g/l Natriumacetat 20 g/l Natriumsuccinat 3 ml/1 N-Diäthylborazan 0,01 g/l Bleichlorid pH 50 ml/1 Methanol 65° Cc) 30 g / l nickel chloride 10 g / l sodium citrate 20 g / l sodium acetate 20 g / l sodium succinate 3 ml / 1 N-diethylborazane 0.01 g / l lead chloride pH 50 ml / 1 methanol 65 ° C
II. KupferII. Copper
a) 20 g/l Kupfersulfat 100 g/l Triäthanolamina) 20 g / l copper sulfate 100 g / l triethanolamine
(oder Seignettesalz bzw. EDTA als Komplexbildner) 20 ml/1 Formaldehyd
pH 12,5
25° C(or Seignette salt or EDTA as a complexing agent) 20 ml / 1 formaldehyde pH 12.5
25 ° C
III. KobaltIII. cobalt
a) 35 g/l Kobaltchlorid 20 g/l Natriumacetat 10 g/l Natriumhypophosphit pH 4,5a) 35 g / l cobalt chloride 20 g / l sodium acetate 10 g / l sodium hypophosphite pH 4.5
95°C95 ° C
b) 30 g/l Kobaltsulfat . ' 110 g/l Natriumcitrat 45 g/l Ammoniumchloridb) 30 g / l cobalt sulphate. '110 g / l sodium citrate 45 g / l ammonium chloride
12 g/l Natriumhypophosphit pH 9
950C12 g / l sodium hypophosphite pH 9
95 0 C
IV. Nickel/KobaltIV. Nickel / Cobalt
a) 20 g/l Nickelchlorid 10 g/l Kobaltchlorid 20 g/l Natriumcitrat 10 g/l Natriumhypophosphit
pH 4,2
95°Ca) 20 g / l nickel chloride 10 g / l cobalt chloride 20 g / l sodium citrate 10 g / l sodium hypophosphite pH 4.2
95 ° C
') In diesen Grundlösungen sind Feststoffe nach Tabelle II suspendiert. Außerdem können Glanzbildner zugesetzt werden.') These basic solutions contain solids according to Table II suspended. In addition, brighteners can be added.
b) 25 g/l Nickelsulfat g/l Kobaltchlorid g/l Ammoniumchlorid g/l Natriumhypophosphit
' pH 9,5
95°Cb) 25 g / l nickel sulfate g / l cobalt chloride g / l ammonium chloride g / l sodium hypophosphite pH 9.5
95 ° C
Als Feststoffe können z. B. allein oder in Kombination verwendet werden:As solids, for. B. can be used alone or in combination:
Kaolin, Glasmehl, Talkum, Graphit, Kunststoffe, Diamant.Kaolin, glass powder, talc, graphite, plastics, diamond.
Oxide, Carbide, Nitride, Boride, Suizide, Sulfide, Silikate, Sulfate, Carbonate, Phosphate, Oxalate, Fluoride vonOxides, carbides, nitrides, borides, suicides, sulfides, silicates, sulfates, carbonates, phosphates, oxalates, fluorides from
Aluminium, Bor,Aluminum, boron,
Chrom, Hafnium, Molybdän, Silizium, Titan, Tantal, Vanadin, Wolfram, Zirkon, Nickel, Magnesium,Chromium, hafnium, molybdenum, silicon, titanium, tantalum, vanadium, tungsten, Zircon, nickel, magnesium,
Calcium,Calcium,
Barium,Barium,
Strontium,Strontium,
Cer,Cerium,
Eisen,Iron,
Mangan.Manganese.
Der Durchmesser der Feststoffteilchen kann je nach Verwendungszweck der Niederschläge in der Größenordnung von 0,01 bis 100 Mikron liegen.The diameter of the solid particles can be of the order of magnitude, depending on the intended use of the precipitates from 0.01 to 100 microns.
Claims (6)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB0090776 | 1967-01-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
DE1621206A1 DE1621206A1 (en) | 1971-06-03 |
DE1621206B2 true DE1621206B2 (en) | 1971-12-16 |
Family
ID=6985469
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19671621206 Ceased DE1621206B2 (en) | 1967-01-18 | 1967-01-18 | PROCESS FOR COATING WITH SLIDING FRICTION ON WORKPIECES STRESSED BY WEAR |
Country Status (5)
Country | Link |
---|---|
US (1) | US3617363A (en) |
BE (1) | BE709470A (en) |
DE (1) | DE1621206B2 (en) |
FR (1) | FR1551555A (en) |
GB (1) | GB1219813A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2443238A1 (en) * | 1974-09-10 | 1976-03-18 | Kugelfischer G Schaefer & Co | RIBROTOR |
DE2909739A1 (en) * | 1979-03-13 | 1980-09-18 | Stahlecker Fritz | Open=end spinning rotor - is made of steel for cladding with a wear-resistant material |
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US3920410A (en) * | 1971-04-28 | 1975-11-18 | Sherritt Gordon Mines Ltd | Cobalt coated composite powder |
USRE29285E (en) * | 1973-03-15 | 1977-06-28 | E. I. Du Pont De Nemours And Company | Method for concomitant particulate diamond deposition in electroless plating, and the product thereof |
US3936577A (en) * | 1971-12-15 | 1976-02-03 | E. I. Du Pont De Nemours & Company | Method for concomitant particulate diamond deposition in electroless plating, and the product thereof |
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DE1254935B (en) * | 1960-12-31 | 1967-11-23 | Bayer Ag | Aqueous bath for chemical deposition of boron-containing metal coatings |
US3077421A (en) * | 1961-03-13 | 1963-02-12 | Gen Am Transport | Processes of producing tin-nickelphosphorus coatings |
US3152009A (en) * | 1962-05-17 | 1964-10-06 | Dow Chemical Co | Electroless nickel plating |
GB1041753A (en) * | 1964-04-01 | 1966-09-07 | Res Holland Nv | Improved method of depositing bright-nickel/chromium |
US3378400A (en) * | 1965-07-30 | 1968-04-16 | Ralph E. Sickles | Autocatalytic deposition of nickel, cobalt and alloys thereof |
-
1967
- 1967-01-18 DE DE19671621206 patent/DE1621206B2/en not_active Ceased
-
1968
- 1968-01-16 US US698129A patent/US3617363A/en not_active Expired - Lifetime
- 1968-01-17 BE BE709470D patent/BE709470A/xx not_active IP Right Cessation
- 1968-01-17 GB GB2632/68A patent/GB1219813A/en not_active Expired
- 1968-01-17 FR FR1551555D patent/FR1551555A/fr not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2443238A1 (en) * | 1974-09-10 | 1976-03-18 | Kugelfischer G Schaefer & Co | RIBROTOR |
DE2909739A1 (en) * | 1979-03-13 | 1980-09-18 | Stahlecker Fritz | Open=end spinning rotor - is made of steel for cladding with a wear-resistant material |
Also Published As
Publication number | Publication date |
---|---|
DE1621206A1 (en) | 1971-06-03 |
FR1551555A (en) | 1968-12-27 |
BE709470A (en) | 1968-07-17 |
GB1219813A (en) | 1971-01-20 |
US3617363A (en) | 1971-11-02 |
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