EP0005890A2 - Process for depositing composite coatings containing inorganic particles from an electroplating bath - Google Patents
Process for depositing composite coatings containing inorganic particles from an electroplating bath Download PDFInfo
- Publication number
- EP0005890A2 EP0005890A2 EP79200272A EP79200272A EP0005890A2 EP 0005890 A2 EP0005890 A2 EP 0005890A2 EP 79200272 A EP79200272 A EP 79200272A EP 79200272 A EP79200272 A EP 79200272A EP 0005890 A2 EP0005890 A2 EP 0005890A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- surfactant
- bath
- inorganic particles
- cationic
- 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.)
- Granted
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- 239000010954 inorganic particle Substances 0.000 title claims abstract description 22
- 238000009713 electroplating Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 27
- 238000000576 coating method Methods 0.000 title abstract description 16
- 239000002131 composite material Substances 0.000 title description 9
- 238000000151 deposition Methods 0.000 title description 3
- 239000002245 particle Substances 0.000 claims abstract description 73
- 239000004094 surface-active agent Substances 0.000 claims abstract description 43
- 239000007787 solid Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 11
- -1 cationic fluorocarbon compound Chemical class 0.000 claims abstract description 9
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 5
- 229940126214 compound 3 Drugs 0.000 claims 1
- 239000011146 organic particle Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 11
- 150000002739 metals Chemical class 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
- 238000002474 experimental method Methods 0.000 description 24
- 229910052759 nickel Inorganic materials 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000010348 incorporation Methods 0.000 description 10
- 239000003093 cationic surfactant Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 229910003460 diamond Inorganic materials 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052580 B4C Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000013528 metallic particle Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical class B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N C1CCCCC1 Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910020968 MoSi2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
Definitions
- the invention relates to a process for the codeposition from an electroplating bath of a metal and solid inorganic particles on an object acting as cathode, which particles are kept suspended in the bath liquid.in the presence of a surfactant and have an average size of less than 300 ⁇ m and are used in a concentration of 10 to 150 grammes per litre of bath liquid, and relates to objects entirely or partially provided with a coating thus deposited.
- a disadvantage to the known process is that only a low percentage of particles can be incorporated into the composite layers. Mention is made of a weight percentage of silicium carbide of 3 to 5%. This percentage can only be obtained at a relatively high concentration (90 to 150 grammes per litre) of silicium carbide particles in the bath liquid. Other conditions are an exceptionally high electrolyte concentration and very vigorous agitation of the bath liquid. The latter requirement serves to inhibit sedimentation of the suspension and to obtain a sufficiently homogeneous distribution of the particles in the coating.
- particles of metals or metal alloys can in this way be included in composite metal coatings.
- the percentage of inorganic particles that may form part of composite coatings when use is made of the process according to the invention varies from a few per cent to the theoretically maximum volume percentage of around 70%. It has been found that the smaller the particles the more of them can be deposited fromrthe same amount'by weight per litre of bath liquid.
- the electroplating baths used in the process according to the invention may contain particles of some other inorganic or organic material.
- particles of some other inorganic or organic material As an example thereof may be mentioned a combination of SiC,MoS 2 and Pb-oxide + PTFE.
- the preparation of the dispersions to be employed in the present process may be carried out in any convenient manner. It may be effected by adding the calculated amount of cationic surfactant to the electroplating bath in which the envisaged particles have been taken up or, as is preferred, first adding the wetting agent to a very strongly agitated, concentrated suspension of the particles to be occluded and subsequently adding the resulting suspension to the electroplating bath.
- cationic surface active fluorocarbon compounds In the process according to the invention use should be made of cationic surface active fluorocarbon compounds.
- the structural formulae of some of these compounds are as follows: Of the above compounds the last-mentioned one is to be preferred in that it is a surfactant.that gives the most favourable results. In view of the possibility of electrochemical oxidation and precipitation it is preferred that the anion of said last-mentioned compound be replaced with a Cl - or SO 4 2- ion.
- the electroplating bath also to contain a stress reducing agent, such as p-toluene sulphonamide or saccharin.
- the zeta-potential of the solid inorganic particles to be incorporated by electrodeposition was measured as a function of the amount of surfactant. This was done in order to determine at what amount of surfactant the particle potential exceeded +40 mV. In the actual experiments in the electrolyte bath then a somewhat larger amount of surfactant was used than the amount thus determined. Moreover, in Example I experiments were carried out with the same surfactant in 2 concentrations that were lower than that of said determined amount. The measurement of the zeta-potential was so carried out that as far as possible the same concentrations of the solid inorganic particles in the aqueous dispersions were used as those that were to be employed in the electroplating bath.
- the contents of the beakers were homogenized for 2 minutes with an Ultra Turrax stirrer, type T 45/N of the German firm of Janke und Kunkel A.G., operating at a speed of 10 000 revolutions per minute. Subsequently, the dispersions were allowed to stand for 15 hours to permit the air to escape. Next, the dispersions were stirred with a magnetic stirrer for about 10 minutes without air occlusion and visually inspected then for stability, flocculation symptoms and sedimentation speed.
- Ultra Turrax stirrer type T 45/N of the German firm of Janke und Kunkel A.G.
- Example I the procedure used in the experiments will be further described. The same procedure, mutatis mutandis, is used in all the other examples. Differences, if any, between the examples will appear from the respective tables. In these tables are summarized the various conditions used in the experiments and the results obtained with the experiments.
- a 11 ⁇ 2 1-Watt's nickel plating bath was prepared employing the following composition ingredients: grammes/litre The pH was 4,2 and the temperature 52 C.
- surfactant i.e. 5 mg of surfactant per 1 gramme of SiC.
- the surfactant had the following structual formula: In a 200 ml-beaker this mixture was homogenized with an Ultra Turrax stirrer of the type mentioned before at a speed of 10 000 revolutions per minute. Subsequently, the resulting dispersion was gently stirred for half an hour at a temperature of 52 0 C with an IKA Com- bimag magnetic stirrer to allow the escape of air occluded in the preceding stirring operation.
- the current density was 10 A/dm 2 .
- the electrodepositing lasted 15 minutes, the bath being moderately stirred to prevent sedimentation of SiC particles.
- the cathode and the anode were removed from the beaker, rinsed with water and transferred to a beaker of the same dimensions containing a normal Watt's nickel plating bath (without SiC or surfactant).
- the cathode bar was subjected to a continued electroplating treatment lasting 30 minutes at a current density of 5 A/dm .
- a second, entirely nickel coating.. was deposited on the composite coating of nickel and silicium carbide formed in the first electroplating step.
- the uniformity of distribution of the SiC particles in the nickel could therefore be very well determined;visually.
- the volume percentage of incorporated SiC particles was determined with a Zeiss microvideomat. The experiment was carried out at 3 different concentrations of surfactant, based on the amount by weight of SiC particles:
- zeta-potential without surfactant used in this table and also in other tables is meant the zeta-potential which was measured with the dispersion which exclusively contained the respective inorganic particles and demineralized water.
- the material of the solid inorganic particles in this experiment was a diamond powder supplied by the Swiss firm of Rudolf Spring A.G. under the name Diamond grade 3. Use was made of a nickel sulfamate bath and the same type of surfactant as employed in Example III. Table 5 gives- further particulars about the conditions used in and the results obtained by the experiment. Considering the relatively small concentration of diamond powder (as little as 20 g/litre bath liquid) a remarkably high percentage of incorporated diamond powder was reached (28%) compared with the percentage obtained with the known electroplating process for deposition of metals and diamond powder .
- the solid inorganic substance consisted of chromium powder having a particle size of about 2 pm.
- the powder had been supplied by the American firm of Alfa Products at Danvers.
- the experiment was again carried out in a Watt's nickel plating bath, use being made of the same surfactant as in Example I.
- the conditions and the results of the experiment are given in Table 6.
- the composite layer contained 47 per cent by volume of chromium powder which was homogeneously distributed in it.
- Example I use was made, as in Example I, of a Watt's nickel plating bath containing dispersed silicium carbide particles referred to as SiC 1200 .
- the treatment was carried out in the presence of cationic hydrocarbon surfactants.
- the cationic surfactant used here had the following structural formula: Further data are mentioned in Table 8.
- Example VIII In the experiment according to this example use was made of a mixture of two inorganic substances.
- One substance was SiC 1200 , as employed in Example VIII.
- the other substance was molybdenum disulphide having a particle size of about 25 ⁇ m. It had been obtained from the Swiss firm of Fluka A.G.
- the experiment was again carried out in a Watt's nickelplating bath, use being made of the same surfactant as in Example I.
- tabel 10 the conditions used and the results obtained are summarized.
- the composite layer contained 27 per cent by volume of silicium carbide and 18 per cent by volume of molybdenum disulphide. Both substances were homogeneously distributed in the metal coating.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
- Process for depositing composite coatings containing inorganic particles from an electroplating bath.
- The invention relates to a process for the codeposition from an electroplating bath of a metal and solid inorganic particles on an object acting as cathode, which particles are kept suspended in the bath liquid.in the presence of a surfactant and have an average size of less than 300 µm and are used in a concentration of 10 to 150 grammes per litre of bath liquid, and relates to objects entirely or partially provided with a coating thus deposited.
- A process of the type indicated above is described in the United States Patent Specification 3 891 542. From a bath nickel and silicium carbide particles are codeposited electrolytically on an object which serves as cathode. The silicium carbide particles are kept suspended in the bath with the aid of a surfactant.Mention is made, inter alia, of sodium lauryl sulphate.
- A disadvantage to the known process is that only a low percentage of particles can be incorporated into the composite layers. Mention is made of a weight percentage of silicium carbide of 3 to 5%. This percentage can only be obtained at a relatively high concentration (90 to 150 grammes per litre) of silicium carbide particles in the bath liquid. Other conditions are an exceptionally high electrolyte concentration and very vigorous agitation of the bath liquid. The latter requirement serves to inhibit sedimentation of the suspension and to obtain a sufficiently homogeneous distribution of the particles in the coating.
- The present invention provides a process which makes it possible to incorporate far higher percentages of solid particles into the coatings with the use of an electroplating bath having a far lower concentration of solid particles and electrolyte and far less vigorous agitation of the bath. The invention consists in that in a process of the known type indicated above use is made of a surfactant in the form of a cationic fluorocarbon compound in at least the same weight ratio to the particles in the bath liquid as in an 0,005 N KNO3-solution in which the particles assume a zeta-potential of at least +40 mV with the exclusive use of said cationic fluorocarbon compound . It should be added that the use of a cationic compound for the codeposition from an electroplating bath of a metal and solid inorganic particles on an object acting as cathode has been proposed before in the United States Patent Specification 3 844 910. An amino-organosilicium compound, for instance gamma-propyltriethoxysilane is employed then to promote the incorporation into a matrix of metal of non-metallic particles such as silicium carbide. Although the results obtained with that process are better than those of the previous processes, for a great number of uses the percentage of particles incorporated is still insufficient.
- Moreover, in the case of a particle size of over 10 microns the amount of non-metallic particles that can be incorporated in that way has been found to decrease with increasing average particle size.
- The use of a cationic surfactant in the incorporation of solid inorganic particles into a matrix of metal also is mentioned in British Patent Specification 1 070 343. The amount of cationic surfactant employed, viz.cetylttimethylammonium bromide, is only 10 mg per 25 grammes of particles and is insufficient to cause the particles to assume a zeta-potential of at least +40 mV in an 0,005 N KN03-solution. Moreover, the surfactant then employed is of the hydrocarbon type, which has a very unfavourable influence on the quality of the electrodeposited coating (ductility).
- In the Japanese Patent Specification 50-45735 use is made of a surfactant of the fluorocarbon type for the codeposition from an electroplating bath of gold and abrasion-resistant non-metallic particles on an object acting as cathode. In the example given in it the incorporation of titanium nitride (Ti N) is carried out with the use of 3 g of surfactant of the fluorocarbon type per 20 g of particles. As the particles used than are very small, viz. 0,05 µm, so that the specific surface area is very large, said amount of surfactant will not be sufficient to obtain a zeta-potential in an 0,005 KNO3-solution of at least +40 mV. Moreover, nothing is said in this patent specification about the charge of the fluorocarbon surfactant used in the example.
- Finally, mention should still be made of the United States Patent Specification 3 787 294. Use is made in it of a cationic surfactant of the fluorocarbon type for the codeposition from an electroplating bath of a metal and graphite fluoride particles on an object acting as cathode. Of graphite fluoride particles, however, it is generally known that they rather resemble polyfluorocarbon particles than particles whose incorporation forms the subject of the present invention. Said United States Patent Specification can therefore not be considered to contain a general teaching with regard to the incorporation of inorganic solid particles into a metal coating. For the determination of the surface area of the particles use is preferably made of the nitrogen adsorption method of Brunauer, Emmett and Teller (BET), which is standardized in the German Industrl Standard DIN 66132. By solid inorganic particles that can be incorporated when use is made of the present process. according to the invention are to be understood here not only all particles, that are of solid inorganic compounds which are inert relative to the bath.. conditions, such as the carbides, borides, silicides or nitrides of titanium, zirconium, wolfram, hafnium, niobium, tantalum, chromium, molybdenum, vanadium and thorium, but also particles of simple or composite metal oxides such as A1203; Si02; IrO2; Cr2O3; ZrO2; Pb0 2; Pb 3 0 4; A1 203.2Ti02; BeO.SiO2 and ZrO2Si. To obtain an abrasion-resistant coating especially the incorporation of SiC or B4C particles i's mentioned. Also particles of metals or metal alloys can in this way be included in composite metal coatings. Also suitable are graphite, sulphur, silicium, diamond, sulphides (such as molybdenum disulphide) and silicates (talc, mica).
- The percentage of inorganic particles that may form part of composite coatings when use is made of the process according to the invention varies from a few per cent to the theoretically maximum volume percentage of around 70%. It has been found that the smaller the particles the more of them can be deposited fromrthe same amount'by weight per litre of bath liquid.
- It will be clear that for the number of metals that may be used the same limitation holds as for the number that can be deposited from an electroplating bath in the known manner. As examples of these metals may be mentioned silver, iron, lead, nickel, cobalt, cadmium, copper, zinc.and metallic alloys such as bronze, brass and the like,
- In addition to solid inorganic particles the electroplating baths used in the process according to the invention may contain particles of some other inorganic or organic material. As an example thereof may be mentioned a combination of SiC,MoS2 and Pb-oxide + PTFE. Of particular importance in this connection are resinous particles of, inter alia, polyfluorocarbon compounds, polyvinyl chloride, polyvinylidene chloride, polyolefins, polyesters, polystyrene, polyacrylates, polyamides, polyimides, aromatic polyamides and polyurethanes. If use is made of such combination of different particles it is advisable as much as possible to choose the same particle size.,
- The preparation of the dispersions to be employed in the present process may be carried out in any convenient manner. It may be effected by adding the calculated amount of cationic surfactant to the electroplating bath in which the envisaged particles have been taken up or, as is preferred, first adding the wetting agent to a very strongly agitated, concentrated suspension of the particles to be occluded and subsequently adding the resulting suspension to the electroplating bath.
- Particularly in the simultaneous incorporation of resinous particles it is very much advisable that the various dispersions should be prepared separately prior to their being added to the electroplating bath.
- In the process according to the invention use should be made of cationic surface active fluorocarbon compounds. The structural formulae of some of these compounds are as follows:
- Under some circumstances it may be desirable for the electroplating bath also to contain a stress reducing agent, such as p-toluene sulphonamide or saccharin.
- The invention will be further described in the following examples, which are all directed to the codeposition from an electroplating bath of a metal and solid inorganic particles of various chemical compositions and particle sizes. First of all a description will be given of the general conditions used in the examples, after which the results of the experiments will be summarized in a number of tables.
- The experiments according to the process of the invention were carried out with the use of a cationic fluorocarbon-containing surfactant. For comparison, experiments also were carried out in the presence of a cationic surfactant not containing a fluorocarbon chain, viz. a surfactant of the hydrocarbon type.
- Preparatory to the experiments first the zeta-potential of the solid inorganic particles to be incorporated by electrodeposition was measured as a function of the amount of surfactant. This was done in order to determine at what amount of surfactant the particle potential exceeded +40 mV. In the actual experiments in the electrolyte bath then a somewhat larger amount of surfactant was used than the amount thus determined. Moreover, in Example I experiments were carried out with the same surfactant in 2 concentrations that were lower than that of said determined amount. The measurement of the zeta-potential was so carried out that as far as possible the same concentrations of the solid inorganic particles in the aqueous dispersions were used as those that were to be employed in the electroplating bath.
- In 350 ml-beakers a series of dispersions were prepared, one of them consisting of 12½ grammes of solid inorganic particles and 250 ml of demineralized water. The other dispersions of the series contained varying ampunits of surfactant as well as 12h g of solid inorganic particles and 250 ml of demineralized water. For each of the various kinds of particles a separate series of dispersions were prepared in this way. By "various kinds of particles" are not only to be understood here particles of different chemical compositions, but also those that only differ in particle size. The contents of the beakers were homogenized for 2 minutes with an Ultra Turrax stirrer, type T 45/N of the German firm of Janke und Kunkel A.G., operating at a speed of 10 000 revolutions per minute. Subsequently, the dispersions were allowed to stand for 15 hours to permit the air to escape. Next, the dispersions were stirred with a magnetic stirrer for about 10 minutes without air occlusion and visually inspected then for stability, flocculation symptoms and sedimentation speed. Subsequently, the dispersions were stirred with the magnetic stirrer for about 5 minutes, after which fro:n each beaker 1 ml of the dispersion was taken, which was diluted with 50 ml of an aqueous 0,05% - solution of KNO3 (0,005 N KN03- solution).
- Of the dispersions thus diluted the velocity of the solid inorganic particles under the influence of an electric field was measured.
- From this velocity, the electric conductivity of the dispersion and the electric field strength, the zeta-potential was calculated. For further particulars about the measurement of the zeta-potential reference is made to "Electrophoresis", Duncan J. Shaw, Academic Press, London, New York, 1969..
- In the following Example I the procedure used in the experiments will be further described. The same procedure, mutatis mutandis, is used in all the other examples. Differences, if any, between the examples will appear from the respective tables. In these tables are summarized the various conditions used in the experiments and the results obtained with the experiments.
- For the electrolyte bath use was made of a Watt's nickel plating bath, the solid inorganic particles of silicium carbide having being supplied by Kempten GmbH, Munich, under the name SiC 1200. They are particles having a mesh value of 1200 and an average size of about 5 µm.
-
- To this bath there were added 75 grammes of SiC1200 and 375 mg of a cationic fluorocarbon . surfactant, i.e. 5 mg of surfactant per 1 gramme of SiC. The surfactant had the following structual formula:
- As could afterwards be established , the dispersion obtained looked moderately stable.
- As cathode now a round bar of stainless steel 60 mm long and 4 mm in diameter was hung in the bath contained in the beaker. The bar had been pretreated successively by blasting with granular corundum having a mesh value of 220, rinsing, degreasing with an alkaline detergent, rinsing, activating in a boiling solution of FeCl3 and again rinsing with water.
- The anode hanging in the beaker consisted of a nickel plate 1 mm thick, 8 cm heigh, and 15 cm long and was so bent that it was. just touching the inside wall of the beaker. The anode and the cathode were then connected to a current source supplying a direct current of 0,75 A.
- So considering the cylindrical outer surface area of the cathode the current density was 10 A/dm2. The electrodepositing lasted 15 minutes, the bath being moderately stirred to prevent sedimentation of SiC particles. Next, the cathode and the anode were removed from the beaker, rinsed with water and transferred to a beaker of the same dimensions containing a normal Watt's nickel plating bath (without SiC or surfactant). In this bath. the cathode bar was subjected to a continued electroplating treatment lasting 30 minutes at a current density of 5 A/dm . As a result, a second, entirely nickel coating..was deposited on the composite coating of nickel and silicium carbide formed in the first electroplating step.
- Of the bar thus treated a 15 mm long piece was sawn off and entirely embedded in a solidifying mass. Then the integrated whole of embedding mass and bar was ground off until a semi-cylindrical part of the bar was left, the outer nickel coating serving as supporting layer. On the fine-ground face the incorporated darker SiC particles could be very well distinguished from the lighter nickel.
- The uniformity of distribution of the SiC particles in the nickel could therefore be very well determined;visually. The volume percentage of incorporated SiC particles was determined with a Zeiss microvideomat. The experiment was carried out at 3 different concentrations of surfactant, based on the amount by weight of SiC particles:
- a. 5 mg of surfactant per gramme of SiC
- b. 10mg of surfactant per gramme of SiC
- c. 20mg of surfactant per oramme ofSiC The results of the experiment are summarized in Table 1, which also gives the above-mentioned experimental conditions.
- By the term "zeta-potential without surfactant" used in this table and also in other tables is meant the zeta-potential which was measured with the dispersion which exclusively contained the respective inorganic particles and demineralized water.
- As is shown by Table 1, the use of respectively 5 and 10 mg of surfactant per gramme of particles resulted in incorporating only little SiC, which was moreover inhomogeneously distributed in the nickel. The zeta-potentials in the corresponding 0,005 N KNO3-solutions were below +40 mV and were -25 and +12mV, respectively. It was also found that during the dispersing of the electrolyte, the particles and the surfactant, using 5 and 10 mg of surfactant per gramme of SiC, respectively, a flocculent to very flocculent mixture was formed.
- Both quantitatively and qualitatively the incorporation was considerably better when use was made of 20 mg of surfactant per gramme of particles having a zero-potential of +76 mV. The volume percentage of the incorporated SiC particles was 57, and the particles were homogeneously distributed in the nickel.
- The procedure used in Example I was repeated with SiC particles having a size of about 15 µm and supplied by the Dutch firm of Norton at Rotterdam under the name SiC 500. The conditions and the results are given in Table 2.
- In the experiment relating to this example the solid inorganic particles were of B4C. Particles of this boron carbide having a particle size of about 2 µm, known under the name B4C1500, had been obtained from the German firm of Kempten GmbH, Munich. Use was made of a nickel sulfamate bath and a different cationic fluorocarbon surfactant from the.one used in the
- Examples I and II. The surfactant now had as structural formula
- In this example use was made of solid'inorganic MoSi2 particles supplied by the firm of Starck at West-Berlin, The bath was again a Watt's nickel plating bath and the surfactant again of the type used in the Examples I and II. Further data are mentioned in Table 4. Also in this experiment both a qualitatively and quantitavily satisfactory incorporation of particles was obtained
- The material of the solid inorganic particles in this experiment was a diamond powder supplied by the Swiss firm of Rudolf Spring A.G. under the name Diamond grade 3. Use was made of a nickel sulfamate bath and the same type of surfactant as employed in Example III. Table 5 gives- further particulars about the conditions used in and the results obtained by the experiment. Considering the relatively small concentration of diamond powder (as little as 20 g/litre bath liquid) a remarkably high percentage of incorporated diamond powder was reached (28%) compared with the percentage obtained with the known electroplating process for deposition of metals and diamond powder .
- In the experiment relating to this example the solid inorganic substance consisted of chromium powder having a particle size of about 2 pm. The powder had been supplied by the American firm of Alfa Products at Danvers. The experiment was again carried out in a Watt's nickel plating bath, use being made of the same surfactant as in Example I. The conditions and the results of the experiment are given in Table 6. The composite layer contained 47 per cent by volume of chromium powder which was homogeneously distributed in it. When this experiment was carried out in accordance with the procedure described in said British Patent Specification 1 070 343, using as surfactant n-hexadecyltrimethyl ammonium bromide (CTAB) (a non-fluorocarbon-containing surfactant) the zeta potential was found to have a value not exceeding +20 mV. The particles were inhomogeneously distributed over the surface. The resulting coating was black and had a poor appearance.
- In the following three comparative examples use was made, as in Example I, of a Watt's nickel plating bath containing dispersed silicium carbide particles referred to as SiC1200. However, instead of with a cationic fluorocarbon surfactant the treatment was carried out in the presence of cationic hydrocarbon surfactants. `
-
-
-
- Although in all the comparative Examples VII - IX the zeta-potential can be seen to lie above the set lower limit of +40 mV, the use of a cationic surfactant which is not of the fluorocarbon type results in the incorporation of a considerably lower amount of SiC than is the case in Example I for a zero-potential of +76 mV (0, 12 and 10 per cent by volume in the Examples VII, VIII and IX, respectively, against 57 per cent by volume in Example I).
- In the experiment according to this example use was made of a mixture of two inorganic substances. One substance was SiC1200, as employed in Example VIII. The other substance was molybdenum disulphide having a particle size of about 25 µm. It had been obtained from the Swiss firm of Fluka A.G. The experiment was again carried out in a Watt's nickelplating bath, use being made of the same surfactant as in Example I. In tabel 10 the conditions used and the results obtained are summarized. The composite layer contained 27 per cent by volume of silicium carbide and 18 per cent by volume of molybdenum disulphide. Both substances were homogeneously distributed in the metal coating.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT79200272T ATE436T1 (en) | 1978-06-06 | 1979-06-05 | PROCESS FOR DEPOSITIONING COMPOSITE LAYERS CONTAINING INORGANIC PARTICLES FROM AN ELECTROLYTIC BATH. |
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NL7806118 | 1978-06-06 | ||
NL7806118 | 1978-06-06 |
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EP0005890A2 true EP0005890A2 (en) | 1979-12-12 |
EP0005890A3 EP0005890A3 (en) | 1980-01-09 |
EP0005890B1 EP0005890B1 (en) | 1981-11-25 |
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EP79200272A Expired EP0005890B1 (en) | 1978-06-06 | 1979-06-05 | Process for depositing composite coatings containing inorganic particles from an electroplating bath |
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EP (1) | EP0005890B1 (en) |
JP (1) | JPS54159343A (en) |
AT (1) | ATE436T1 (en) |
DE (1) | DE2961426D1 (en) |
ZA (1) | ZA792801B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4381228A (en) * | 1981-06-16 | 1983-04-26 | Occidental Chemical Corporation | Process and composition for the electrodeposition of tin and tin alloys |
GB2246144A (en) * | 1990-07-18 | 1992-01-22 | Nippon Piston Ring Co Ltd | Electro plating bath for depositing solid particles dispersed in nickel alloy matrix on sliding surfaces |
EP1201792A1 (en) * | 2000-03-06 | 2002-05-02 | Japan Science and Technology Corporation | Composite plating method |
ITUB20151322A1 (en) * | 2015-05-29 | 2016-11-29 | Metalcoating S R L | ELECTROLYTIC PROCESS FOR COATING METALLIC SURFACES IN ORDER TO GIVE HIGH RESISTANCE TO WEAR. |
WO2022129997A1 (en) * | 2020-12-17 | 2022-06-23 | Arcelormittal | A hydrogen embrittlement resistance coated steel |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2622283B2 (en) * | 1989-03-10 | 1997-06-18 | 三菱重工業株式会社 | Composite plating method |
JP3687722B2 (en) | 1999-01-12 | 2005-08-24 | 上村工業株式会社 | Electroless composite plating solution and electroless composite plating method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3677907A (en) * | 1969-06-19 | 1972-07-18 | Udylite Corp | Codeposition of a metal and fluorocarbon resin particles |
DE2632214A1 (en) * | 1975-07-17 | 1977-02-03 | Sony Corp | BATHROOM FOR GALVANIC DEPOSITION OF MATS NICKEL COATING |
DE2643758A1 (en) * | 1975-10-04 | 1977-04-14 | Akzo Gmbh | PROCESS FOR THE DEPOSITION OF METAL COATINGS CONTAINING POLYFLUORCARBON RESIN PARTICLES |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3787294A (en) * | 1971-12-07 | 1974-01-22 | S Kurosaki | Process for producing a solid lubricant self-supplying-type co-deposited metal film |
NL148957B (en) * | 1972-03-20 | 1976-03-15 | Akzo Nv | PROCEDURE FOR APPLYING A METAL COATING ALONG ELECTROLYTIC ROAD, INCLUDING PLASTIC PARTICLES. |
-
1979
- 1979-06-05 JP JP7053079A patent/JPS54159343A/en active Granted
- 1979-06-05 EP EP79200272A patent/EP0005890B1/en not_active Expired
- 1979-06-05 AT AT79200272T patent/ATE436T1/en not_active IP Right Cessation
- 1979-06-05 DE DE7979200272T patent/DE2961426D1/en not_active Expired
- 1979-06-06 ZA ZA792801A patent/ZA792801B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3677907A (en) * | 1969-06-19 | 1972-07-18 | Udylite Corp | Codeposition of a metal and fluorocarbon resin particles |
DE2632214A1 (en) * | 1975-07-17 | 1977-02-03 | Sony Corp | BATHROOM FOR GALVANIC DEPOSITION OF MATS NICKEL COATING |
DE2643758A1 (en) * | 1975-10-04 | 1977-04-14 | Akzo Gmbh | PROCESS FOR THE DEPOSITION OF METAL COATINGS CONTAINING POLYFLUORCARBON RESIN PARTICLES |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4381228A (en) * | 1981-06-16 | 1983-04-26 | Occidental Chemical Corporation | Process and composition for the electrodeposition of tin and tin alloys |
GB2246144A (en) * | 1990-07-18 | 1992-01-22 | Nippon Piston Ring Co Ltd | Electro plating bath for depositing solid particles dispersed in nickel alloy matrix on sliding surfaces |
DE4119710A1 (en) * | 1990-07-18 | 1992-01-30 | Nippon Piston Ring Co Ltd | VERBUNDPLATTIERUNGSBAD |
GB2246144B (en) * | 1990-07-18 | 1994-08-03 | Nippon Piston Ring Co Ltd | Composite plating bath |
EP1201792A1 (en) * | 2000-03-06 | 2002-05-02 | Japan Science and Technology Corporation | Composite plating method |
EP1201792A4 (en) * | 2000-03-06 | 2005-03-23 | Japan Science & Tech Agency | Composite plating method |
ITUB20151322A1 (en) * | 2015-05-29 | 2016-11-29 | Metalcoating S R L | ELECTROLYTIC PROCESS FOR COATING METALLIC SURFACES IN ORDER TO GIVE HIGH RESISTANCE TO WEAR. |
EP3098334A1 (en) * | 2015-05-29 | 2016-11-30 | Metalcoating S.r.l. | Electrolytic process for coating metal surfaces to provide high wear resistance |
WO2022129997A1 (en) * | 2020-12-17 | 2022-06-23 | Arcelormittal | A hydrogen embrittlement resistance coated steel |
Also Published As
Publication number | Publication date |
---|---|
DE2961426D1 (en) | 1982-01-28 |
JPS54159343A (en) | 1979-12-17 |
EP0005890A3 (en) | 1980-01-09 |
EP0005890B1 (en) | 1981-11-25 |
ATE436T1 (en) | 1981-12-15 |
ZA792801B (en) | 1980-06-25 |
JPS6257720B2 (en) | 1987-12-02 |
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