CN1307648A - Coating compositions containing nickel and boron - Google Patents
Coating compositions containing nickel and boron Download PDFInfo
- Publication number
- CN1307648A CN1307648A CN99805724A CN99805724A CN1307648A CN 1307648 A CN1307648 A CN 1307648A CN 99805724 A CN99805724 A CN 99805724A CN 99805724 A CN99805724 A CN 99805724A CN 1307648 A CN1307648 A CN 1307648A
- Authority
- CN
- China
- Prior art keywords
- coating
- nickel
- gallon
- goods
- boron
- 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
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 134
- 229910052759 nickel Inorganic materials 0.000 title claims description 59
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims description 30
- 229910052796 boron Inorganic materials 0.000 title claims description 30
- 239000008199 coating composition Substances 0.000 title claims description 8
- 238000000576 coating method Methods 0.000 claims abstract description 162
- 239000011248 coating agent Substances 0.000 claims abstract description 151
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 26
- 238000007747 plating Methods 0.000 claims abstract description 20
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 40
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000007669 thermal treatment Methods 0.000 claims description 18
- 230000002829 reductive effect Effects 0.000 claims description 15
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000521 B alloy Inorganic materials 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000003628 erosive effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 claims 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 4
- 229910052700 potassium Inorganic materials 0.000 claims 4
- 239000011591 potassium Substances 0.000 claims 4
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- NKTZYSOLHFIEMF-UHFFFAOYSA-N dioxido(dioxo)tungsten;lead(2+) Chemical compound [Pb+2].[O-][W]([O-])(=O)=O NKTZYSOLHFIEMF-UHFFFAOYSA-N 0.000 abstract 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000008139 complexing agent Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- 239000002585 base Substances 0.000 description 11
- 238000004062 sedimentation Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000000151 deposition Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000003287 bathing Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910001092 metal group alloy Inorganic materials 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 229910052716 thallium Inorganic materials 0.000 description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 241000132028 Bellis Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical group 0.000 description 1
- -1 amino, imino- Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- HZEIHKAVLOJHDG-UHFFFAOYSA-N boranylidynecobalt Chemical compound [Co]#B HZEIHKAVLOJHDG-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010276 construction Methods 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
- 238000005034 decoration Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- BXBMHLIYMZRCNK-UHFFFAOYSA-H thallium(3+);trisulfate Chemical compound [Tl+3].[Tl+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BXBMHLIYMZRCNK-UHFFFAOYSA-H 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
-
- 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
- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Physical Vapour Deposition (AREA)
Abstract
This invention is directed to plating using a coating bath that provides a hard, wear and corrosion resistant, ductile coating on a substrate, said bath having a pH of about 10 to about 14 and comprising: (1) about 0.175 to about 2.10 moles per gallon of coating bath of nickel ions; (2) an effective amount of lead tungstate to stabilize the bath and to form a continuous coating free from blotches without any substantial deposition of lead tungstate in the coating; (3) an effective amount of metal ion complexing agent in an amount sufficient to inhibit precipitation of said metal ions from the coating bath; and (4) an effective amount of a borohydride reducing agent.
Description
The present invention is that the part of Application No. 09/074703 (submission on May 8th, 1998) continues.
Background of the present invention
The present invention relates to have the novel metal coating of abnormal consistency.More particularly, the present invention relates to comprise the metallic paint of nickel and boron and described coating under the alkaline pH value by the aqueous solution at the lip-deep reduce deposition of substrate article.
Well knownly electroplate or deposit metal alloy, can be decoration and functional purpose like this and improve its surface property by the metal ion on chemistry or the electrochemical reduction product surface.Special tool commercial value be the deposition of metal/metal alloy coating on metal and activation non-metallic substrate, can strengthen surface hardness and erosion resistance and wear resistance like this.The hardness of this area approval nickel-boron and cobalt-boron alloy coating and corresponding wear resistance.Patent documentation shows, harder in order to produce, more corrosion resistant coating, and is is constantly researching and developing in nickel-boron dope field.For example, referring to United States Patent (USP) 5019163,3738849,3674447,3342338,3378400,30453342 and 726710.This area is known, if use borohydride in nickel/boron plating bath, can obtain harder coating.But borohydride is very unstable in this is bathed.The scheme that solves stability problem is to add stablizer, as thallic sulfate or lead chloride.Add stablizer and can hinder the formation nickel coating, thereby the hardness of coating is had a negative impact.According to the present invention and since stablizer be not codeposition in coating, so nickel coating is obviously harder than the description of prior art.
Nickel/boron dope so far always comprises that stablizer is as three elements.Sole exception is a dimethyl borine coating.This coating is not present in the stablizer of this coating.The application of this method is limited to very much, because the sedimentation rate of bathing is very slow and coating is very thin.The order of magnitude of sedimentation rate is 0.00015 inch per hour.Deposit thickness is confined to about 0.0001-0.0002 inch.These settlings are too thin, can not be used for wear surface.
Therefore, an object of the present invention is to provide a kind of goods, on its at least a portion surface, comprise nickel and boron, hard, flexible, wear resistance and corrosion-resistant metal coating because the disadvantageous effect that the stablizer codeposition produces scribbles by reducing.
Another object of the present invention provides coating and bathes, by this coating bathe can be at least a portion surface of metal or activation non-metallic substrate deposition hard, flexible, wear resistance and corrosion-resistant coating.
General introduction of the present invention
According to the present invention, provide a kind of novel metal coating composition that comprises nickel and boron and plumbous tungstate.This coating composition can comprise other metal ion, as cobalt.This coating composition be particularly useful for being deposited on be exposed to the corrodibility conditioned disjunction slide with another goods under inordinate wear and the bearing pressure or the surface of the goods of friction contact on.Metal coating composition of the present invention comprises the cobalt of the nickel of about 67.5-97.0% weight, about 0-48.5% weight, the boron of about 2.5-10% weight.The alternative nickel of cobalt is to the highest about 50% nickel.Cobalt preferably is lower than 25% nickel to substituting of nickel.The preferable range of this nickel coating is 94-97% weight nickel and 3-6% weight boron.The obviously hard and toughness of this coating, and very corrosion-resistant and wear-resisting.
Shockingly find, stablize nickel-boron plating bath, can form the nickel/boron coating that has even be higher than the hardness that is obtained in the past by using plumbous tungstate.Routine adds in these plating baths stablizer to postpone the precipitation of reductive agent in coating bath itself.These stablizers and nickel coating codeposition.This codeposition effect suppresses to be completed into nickel coating, thereby has limited the hardness and the wear resistance of nickel boron coating.According to discovery,, can improve the hardness of nickel/boron coating by suppressing the codeposition of stablizer basically.According to the present invention, plumbous tungstate comes out as solids precipitation in plating bath, rather than in coating codeposition.These particles can be removed by hold back this particle in filtration system.
Coating of the present invention under about 180-210 high temperature, contacts and chemistry is administered on the base material by base material and the coating that comprises nickel ion, plumbous tungstate ion, metal ion Synergist S-421 95 and borohydride reductive agent are bathed preferably under the pH of about 10-14 value.After beginning to electroplate in about 180-210 temperature range, this coating can be electroplated at a lower temperature.
Detailed description of the present invention
The base material that is applicable to electroless plating is to have those of so-called catalytic chemistry surface, comprises by those of nickel, cobalt, iron, steel, aluminium, zinc, palladium, platinum, copper, bronze, chromium, tungsten, titanium, tin, silver, carbon, graphite and alloy composition thereof.These materials have katalysis so that the metal ion in the plating bath is reduced by borohydride, cause deposit metal alloy on the surface of the base material that contacts with plating bath.The plating of aluminium usually the discharge coating of needing protection property in case dissolving when electroplating.Non-metallic substrate is the non-catalytic material as glass, pottery and plastics; But these base materials can sensitization has catalytic activity by the film that produces a kind of catalytic material in its surface.This can realize by the known the whole bag of tricks of those skilled in the art.A kind of preferable methods comprises, glass, pottery or plastics is immersed in the solution of tin protochloride, and treat surface contacts with the solution of Palladous chloride then.Like this, the palladium thin layer reduces on the treat surface at this.According to the present invention, these goods can be bathed by contact coating subsequently and be electroplated or be coated with metal composites, and details is as follows.Should be noted that magnesium, wolfram varbide and some plastics have certain anti-deposition to coating of the present invention.
The present invention is used for sedimentary coating bath and comprises:
(1) nickel ion, about 0.175-0.210 mole/gallon.Nickelous chloride scope according to 0.05-0.6 pound/gallon is calculated.The preferable range of nickel ion is about 0.35-1.57 mole/gallon, based on about 0.45 pound/gallon nickelous chloride of 0.1-.
(2) cobalt ion is the highest 1.05 moles/gallon but be no more than 50% nickel in this bath;
(3) chemical reagent of significant quantity is used for the pH value of this bath is adjusted to about 10-14;
(4) the metal ion Synergist S-421 95 of about 2.26-6.795 mole/gallon, preferred 3.3-3.8 mole/gallon;
(5) the borohydride reductive agent of about 0.01-0.8 mole/gallon coating bath, based on sodium borohydride, preferred 0.020-0.033 mole/gallon coating is bathed.
(6) the plumbous tungstate stablizer of significant quantity, its scope is about 0.0143-0.30 gram/gallon, preferred about 0.01 82-0.08 fills/gallon.
The known borohydride that has good water solubility and stability in the optional comfortable aqueous solution of borohydride reductive agent.Sodium borohydride is preferred.In addition, can use substituted borohydride, wherein substitute this borohydride ionic and be no more than 3 hydrogen atom.Trimethoxy sodium borohydride [NaB (OCH
3)
3H] be the example of this compound.
The pH value that prepared coating is bathed is about 12-14.If the pH value of this bath remains in this scope, more preferably near pH value 13.5, can observe optimum in coating process.Coating is bathed the adjusting of pH value can be by adding any various basic salts or it carries out easily.Being preferred for setting up and keeping the chemical reagent of coating bath pH value is alkali metal hydroxide, especially sodium hydroxide and potassium hydroxide and ammonium hydroxide.The attendant advantages of ammonium hydroxide is that ammonium ion can help metal ion to cooperate in coating is bathed.
Because the high alkalinity that coating is bathed needs metal ion cooperation or sequestrant in case the precipitation of metal ion such as nickel and other metal hydroxides or other basic salt during coating is bathed.It is also important that the metal ion Synergist S-421 95 can reduce the reactivity of metal ion; That cooperate or chelated metal ion is reactive minimum with the borohydride ionic but can react on the catalytic surface of the base material that contacts with this solution in bulk solution.The term catalytic surface is meant the surface of any goods of being made up of aforementioned catalytic material or the surface of the non-catalytic material of sensitization by the film of using described catalytic material in its surface.
Be applicable to that cooperation of the present invention or sequestrant comprise that ammonia and the organic cooperation that comprises one or more following functional groups generate agent: primary amino, secondary amino group, uncle's amino, imino-, carboxyl and hydroxyl.Preferred Synergist S-421 95 is quadrol, diethylenetriamine, Triethylenetetramine (TETA), organic acid, oxalic acid, citric acid, tartrate and ethylenediamine tetraacetic acid (EDTA) and aqueous solution salt thereof.Quadrol most preferably.
Per gallon coating is bathed the Synergist S-421 95 that uses about 2.26-6.795 mole/gallon.This calculated value is based on the quadrol of about 0.3-0.9 pound/gallon.If per gallon coating is bathed to about 3.39-3.77 mole, can obtain best result.This calculated value is bathed based on per gallon coating, the quadrol of about 0.45-0.5 pound/gallon.
Metal ion during coating is bathed such as nickel ion provide by add corresponding water-soluble salt in bathing.Any salt of those metals with anionic group of non-confrontational theme coating process all is suitable.For example, the salt of oxidizing acid, undesirable as oxymuriate owing to can react with the borohydride reductive agent in bathing.Its negatively charged ion is gone up other composition inert cobalt and nickel, muriate, vitriol, formate, acetate and other salt in the alkaline coating bath all satisfactory substantially.
Plumbous tungstate can be added in the plating bath by the enriched material that comprises pH value conditioning agent and Synergist S-421 95.This Synergist S-421 95 can be selected from above-mentioned those.Preferred Synergist S-421 95 is a quadrol.This enriched material comprises the plumbous tungstate of about 2-31 gram/gallon.The preferable range of plumbous tungstate is about 7-12 gram/gallon.The concentration range of Synergist S-421 95 is the 100-700 milliliter.The preferable range of Synergist S-421 95 is about 300-400 milliliter.The pH value of this mixture surpasses 8, preferred 10.5.PH value conditioning agent is selected from the alkali to harmless sodium hydroxide of plating bath and so on.
Add enriched material and make that by dilution, the concentration range of plumbous tungstate in this bath can be about 0.0143-0.30 gram/gallon plating bath.Preferred concentration range is about 0.0182-0.082 gram/gallon plating bath.
Coating is bathed usually preparation like this: form the nickel of appropriate amount and the aqueous solution of cobalt salt, add Synergist S-421 95 and stablizer, the pH value is adjusted to about 12-14, be heated to about 195 °F, filter, before base material is added this bath, add the sodium borohydride (usually in alkaline aqueous solution) of aequum immediately at last.
Use the present invention to bathe coating or galvanized goods clean by machinery, degreasing, anode-alkalescence is cleaned, the pickling and making in acid bath of last standing procedure according to the Metal plating field.This base material can cover as required so that metal alloy coating only deposits on selected surface.Although coating of the present invention generally has the excellent adhesion with the suitable substrate surface of making when clagging is important or when having some adhesion issues, clagging can deposit on this base material with electrochemical means by the coating of before using coating of the present invention nickel being discharged usually and strengthen.
During the coating that cleans or the surface-treated goods are immersed in heat (about 180-210) bathed to begin coating process.This process proceeds to that coating deposition has proceeded to desired thickness or metal ion exhausts from solution.Under processing condition of the present invention, the variation range of sedimentation rate be about 0.1 mil (1 mil=one-thousandth of an inch)-Yue 1.5 mils/hour.
The preferable range of the composition of plating bath comprises the borohydride of the about 0.35-1.57 mole/nickel of gallon, the plumbous tungstate ion of about 0.0182-0.08 mole/gallon, about 0.017-0.035 mole/gallon.Nickel, cobalt, boron and the plumbous tungstate ratio in coating of the present invention can be regulated by changing metal salt component and the borohydride relative quantity in coating is bathed.
According to the present invention, under the regular service condition that coating is bathed, the amount when per hour plumbous tungstate and borohydride reductive agent being used for preparing this baths to be equivalent to it adds this coating bath.Depend on that with the demand of plumbous tungstate and borohydride supplementary copy invention coating coating bathes the ratio of volume and surface-area to be coated.Therefore, if handle less surface-area, need not usually plumbous tungstate and borohydride are added in the coating bath of the present invention.
1 gallon of bath of making according to the preferred embodiment of the invention can be coated to 1 mil thick with about 144 square inches.In order to realize this result, as described above replenishes this bath with these components when plumbous tungstate and borohydride exhaust from solution.
The pH value that coating is bathed often descends in coating process, therefore should make regular check on to guarantee that this value is in the preferable range of about 12-14.Have been found that in the process of using coating to bathe, relate to any problem that pH value keeps all can be simply by with high alkalinity (concentrated sodium hydroxide) solution of borohydride as required the borohydride content of additional this bath minimize.The coating sedimentation rate that chemical coating of the present invention is bathed be about 0.1-1 mil/hour and depend on that bath is warm, pH value and concentration of metal ions.Under about 185-195 preferred temperature, by the fresh coating made bathe the speed that deposits on most of metal bases be about 1 mil/hour.
The actual content that carries out chemical coating process is well known in the art.These technologies generally are disclosed in United States Patent (USP) 5109613 (authorizing McComas on April 28th, 1991), United States Patent (USP) 3338726 (authorizing Berzins on July 2nd, 1963), United States Patent (USP) 3045334 (authorizing Berzins on October 1st, 1958), United States Patent (USP) 3378400 (authorizing Stickles May 16 nineteen sixty-eight) and United States Patent (USP) 2658841 (authorizing Gutzeit and Krieg November 10 nineteen fifty-three), incorporate it into the present invention as a reference at this.
Chemical nickel coating of the present invention has unprecedented hardness and follows wear resistance.They are very pliable and tough so that coating along with the base material bending, keeps the strong ligation with coating material simultaneously.
After depositing to nickel coating on the base material, the conventional steps of prior art is that this coating of heat treated is to obtain highest hardness.Before thermal treatment, the Knoop hardness of prior art nickel/boron coating is about 925.After thermal treatment, the Knoop hardness of prior art nickel/boron coating is lower than 1373.On the contrary, by using plumbous tungstate as stablizer, the Knoop hardness of the nickel/boron coating before the thermal treatment is about 1000.After the thermal treatment, the Knoop hardness of nickel/boron coating surpasses 1375.
Thermal treatment under about 375-750 temperature about 1-24 hour.For about 550-750 comparatively high temps, preferably about 1-2 hour short period.Under about 375-450 lesser temps, long heat treatment time is favourable.
The structure of nickel/boron coating changes when thermal treatment.As if before thermal treatment, nickel and boron are combined into alloy.After the thermal treatment, formed nickel borides.This appears as the nickel borides dispersion in nickel/boron alloy.
Can obtain the coating of any thickness.Can obtain greater than 0.0001 inch to 0.01 inch or higher coat-thickness.Can produce the routine wearing and tearing coating of thickness range for about 0.0005-0.004 inch.
Coating of the present invention has various uses, and this is that those skilled in the art are known.They especially are used in the surface of standing the goods of high wearing and tearing, friction or sliding condition when coating is normal to be used under high temp/high pressure.These high abrasive conditions appear at the many positions and the various heavy equipment structure occasion of tool construction, oil engine (comprising internal combustion turbine), variator.
Following examples describe bath composition of the present invention, processing condition, coating composition and performance in detail.Embodiment is used to illustrate the present invention, should not limit scope of the present invention by any way.
Embodiment
The coating of 1 gallon batch unit is bathed and is prepared as follows.With regard to this embodiment, prepare four kinds of solution: A (this bath), B (reductive agent), C (stablizer) and D (bath fill-in).At first, prepare 1 gallon batch of each solution.Solution A (this bath) is made up of deionized water, 0.2 pound of nickelous chloride, 0.5 pound of quadrol and 0.33 pound of sodium hydroxide.Solution B (reductive agent) is made up of deionized water, 2.5 pounds of sodium hydroxide and 0.8 pound of sodium borohydride.Solution C (stablizer) is made up of deionized water, 100 gram sodium hydroxide and 10 gram plumbous tungstates and 400 milliliters of quadrols.Solution D (bath fill-in) is formed (solution D is identical with solution A, but almost anhydrous) by deionized water, 0.6 pound of nickelous chloride, 1.5 pounds of quadrols with 1.0 pounds of sodium hydroxide.Solution A is heated to 192 °F: with two 1 of detergent washings " * 11 " stainless steel plate, remove the oil and the dirt of sheet material.Sheet material is fixed on the steel wire, is placed on 30%HCl and 20%H then
2SO
4Solution in 60 seconds to activate this parts.Just sheet material is placed in the bath electroplate before, will add in this solution A of being heated with 10 ml soln C blended, 10 ml soln B.For solution C, can use the 7-12 milliliter.
After 30 minutes, volumetric soiutions A is to determine existing and measuring of sodium borohydride.After every plating 30 minutes, add 10 ml soln B and the 10 ml soln C that mix in addition.Electroplate and continue 3 hours.
After 3 hours, sheet material from bathing, this is taken out and measures deposit thickness.Thermal treatment was carried out under 750 °F 90 minutes.Sheet material was determined as 0.0347 inch before electroplating, be 0.0407 inch after the plating, showed that total thickness increased value is 0.006 inch or 0.003 inch every, or the sedimentation rate of 0.001 inch per hour.
These sheet materials are successive, without any spot, also do not have hole.According to little thickness measuring research of standard, cut these sheet material then, install, transversal and inspection hardness.Can check the profile of interface region between the expression coating of this coating and base material subsequently.This zone does not have space and tramp material.
The hardness of coated sheet material uses the Knoop indentor with 100 gram loads to measure.Hardness value before the thermal treatment is about 950-1050.Hardness value after the thermal treatment is as follows: 1545,1685,1610,1785,1660,1710,1690,1820,1730 and 1710.If ignore the highest and Schwellenwert and its residual value is average, obtain final hardness value 1697.This shows that this novel electroplating composition has produced reproducible high hardness value.Other nickel boron coating than prior art is big by 25% at least for this value, so wear resistance has obviously improved 300% more than.
Use the remaining electroplated sample of ICP technical Analysis to determine the quantitative composition of coating.ICP result's (X-ray) shows, consists of the trace elements of 95.5% nickel and 4.5% boron and probable error 0.5%.Before the thermal treatment, this coating is nickel/boron alloy.After the thermal treatment, this coating is dispersed with nickel borides in nickel/boron alloy.
Have been found that the Knoop hardness value according to thermal treatment coating of the present invention is about 1400-2200.The optimal hardness value that when nickel boronation coating, provides before these values are higher than.
To use the present invention of plumbous tungstate to compare with the prior art nickel plating bath that uses thallium as stablizer.In the United States Patent (USP) 3674447 of Bellis, embodiment 3 obtains the coating with nickel 93%, boron 3.5%, thallium 3.5% that a kind of Knoop hardness is 900-1000.In the United States Patent (USP) 3295999 of Klein, embodiment 2 obtains the coating with nickel 93%, boron 4%, thallium 3% that a kind of Knoop hardness is 1000-1100.In the United States Patent (USP) 5109613 of McComas, embodiment 1 obtains the coating with nickel 90%, cobalt 4%, boron 4%, thallium 2% that a kind of Knoop hardness is 1200-1300.Bellis and the McComas coating Knoop measurement of hardness before thermal treatment is for being lower than about 925.
These comparison shows that and use the surprising effect of plumbous tungstate as stablizer, that is, the Knoop hardness of gained is 1385-2200 after the thermal treatment, be 950-1050 before the thermal treatment, and coating is continuous and without any spot.
Change the concentration of plumbous tungstate in this is bathed, obtain following result.In the gram number of plumbous tungstate in this is bathed: when 0.0025 gram, this bathes instability; When 0.003 gram, observe a little and improve; In 0.008 when gram, sedimentation rate is uncontrollable and appropriate drop out (drop-out) arranged 10 minutes after; When 0.0104 gram, this bath instability and particle are separated out (seed out) seriously; When 0.013 gram, this bath instability and particle are separated out seriously; When 0.0156 gram, this bath instability and particle are separated out seriously; When 0.0182 gram, this is bathed initial instability but in time self corrects; When 0.0208 gram, the result is good; In 0.05 when gram, excellence as a result; When 0.065 gram, the result is good but sedimentation rate is slow; When 0.07 gram, come to the same thing; When 0.09 gram, sedimentation rate is slower; In 0.1 when gram, sedimentation rate is slower, for about 0.0004 mil/hour; In 0.2 when gram, sedimentation rate is slow, for about 0.0003 mil/hour; Identical when 0.3 gram; When 0.4 gram, plating stops.
When the plumbous tungstate of about 0.0104-0.014 gram/gallon, do not observe non-uniform coating.This coating has covered the surface with spot.The structure of coating is irregular.If the plumbous tungstate in this bath is increased to about more than 0.0142, coating becomes continuously and is even so.Spot disappears.
These results show that the concentration of plumbous tungstate in this bath can be about 0.0142-0.30 gram/gallon plating bath.Preferred concentration range for is about 0.0128-0.2 gram.
According to above description as can be seen, optimum proportion of the present invention, processing step and composition, comprise the variation of size, material, shape, form, function and the mode of operation, assembly and application, to those skilled in the art all is obvious, so the present invention means all equivalents that comprise the described content of specification sheets.
Therefore, aforementioned content is considered to only be used to illustrate principle of the present invention.In addition, because those skilled in the art carry out many improvement and variation easily, therefore limit the invention to concrete structure and operation and improper given and that describe, so can take any suitable improvement and equivalent within the scope of the present invention.
The present invention describes so far.
Claims (43)
1. goods with the amorphous coating of wear resistance, this coating comprises the nickel borides that is dispersed in nickel/boron alloy, and wherein nickel is 67.5-97.0% weight, and boron is 2.5-10% weight, and the Knoop hardness of this coating is greater than 1385, and wherein said coating is speckless continuously.
2. according to the goods of claim 1, wherein said abrasion resistant coatings comprises the nickel of 93-97% weight and the boron of 7-3% weight.
3. according to the goods of claim 2, the Knoop hardness of wherein said abrasion resistant coatings is at least about 1400-2200.
4. according to the goods of claim 1, the thickness of wherein said abrasion resistant coatings is about 0.001-0.04 inch.
5. according to the goods of claim 1, wherein use the cobalt replacement nickel to the highest about 50% nickel.
6. one kind is used for providing on base material hard, wear resistance and coating erosion resistance, flexible coating to bathe, and the pH value that described coating is bathed is about 10-14 and comprises:
(1) nickel ion of about 0.175-2.10 mole/gallon coating bath,
(2) plumbous tungstate of significant quantity to be stablizing this coating and bathe and to form a kind of be speckless continuous coated, and plumbous tungstate can not have any remarkable deposition in described coating;
(3) the metal ion Synergist S-421 95 of significant quantity presents in an amount at least sufficient to suppress described metal ion and bathes precipitation by coating:
(4) the borohydride reductive agent of significant quantity; With
(5) optionally, the highest 1.05 moles/gallon cobalt.
7. bathe according to the coating of claim 6, wherein said coating is bathed and is comprised the plumbous tungstate of about 0.0156-0.3 gram/gallon as stablizer.
8. bathe according to the coating of claim 6, wherein said metal ion Synergist S-421 95 is selected from water-soluble salt, quadrol, diethylenetriamine, diethylenetriamine, ethylenediamine tetraacetic acid (EDTA) and the ammonia of tartrate, citric acid, oxalic acid.
9. coating is according to Claim 8 bathed, and wherein said metal ion Synergist S-421 95 is a quadrol.
10. bathe according to the coating of claim 7, wherein said borohydride reductive agent is selected from sodium borohydride, potassium borohydrid, trimethoxy sodium borohydride and trimethoxy potassium borohydrid.
11. the coating according to claim 10 is bathed, wherein said borohydride reductive agent is a sodium borohydride.
12. bathe according to the coating of claim 10, wherein said borohydride concentration is about 0.017-0.035 mole/as logical sequence.
13. the coating according to claim 6 is bathed, the concentration of wherein said metal ion Synergist S-421 95 is that about 2.26-6.795 mole/gallon coating is bathed.
14. the coating according to claim 7 is bathed, wherein said nickel ion concentration is about 0.35-1.57 mole/gallon.
15. the coating according to claim 6 is bathed, wherein said plumbous tungstate ionic concn is about 0.0182-0.25 gram/gallon.
16. the metal coating composition that will comprise nickel and boron deposits to the method on the base material, this method comprises:
A kind of plating bath according to claim 6 is provided;
Described base material to be coated is immersed in the described bath; Then
This coatings chemistry is deposited on this base material.
17. according to the method for claim 16, the pH value of wherein said bath before coating is adjusted to about 12-14.
18. according to the method for claim 16, wherein said metal ion Synergist S-421 95 comprises a kind of compound that is selected from quadrol, tartaric water-soluble salt and ammonia.
19. according to the method for claim 18, wherein said metal ion Synergist S-421 95 is a quadrol.
20. according to the method for claim 16, wherein said borohydride reductive agent is selected from sodium borohydride, potassium borohydrid, trimethoxy sodium borohydride and trimethoxy potassium borohydrid.
21. according to the method for claim 20, wherein said borohydride reductive agent is basic sodium borohydride.
22. according to the method for claim 16, wherein with described metallic coating thermal treatment.
23. the thickness of making by the method for claim 16 under the situation of getting rid of heat treatment step surpasses 0.00028 inch product, wherein said coating is made up of nickel and boron basically.
24. the thickness of making by the method for claim 22 surpasses about 0.0001 inch product.
25. the thickness of making by the method for claim 23 is the product of about 0.001-0.04 inch.
26. the Knoop hardness of making by the method for claim 22 is at least 1375 product.
27. the Knoop hardness of making by the method for claim 26 is the product of about 1400-2200.
28. the Knoop hardness of making by the method for claim 23 is greater than 950 to about 1050 product.
29. a pH value is greater than 8 enriched material, the quadrol that wherein comprises the plumbous tungstate of about 2-31 gram/gallon, about 100-700 milliliter is as metal ion Synergist S-421 95 and pH value conditioning agent.
30., wherein comprise the quadrol of 300-400 milliliter according to the enriched material of claim 29.
31. a pH value is about 10.5 enriched material, wherein comprises the quadrol and the pH value conditioning agent of the plumbous tungstate of about 7-12 gram/gallon, about 300-400 milliliter.
32. one kind is used for providing on base material hard, wear resistance and coating erosion resistance, flexible coating to bathe, the pH value that described coating is bathed is about 12-14 and comprises:
(1) nickel ion of about 0.35-1.57 mole/gallon coating bath,
(2) plumbous tungstate of about 0.0208-0.08 gram/gallon is as stablizer;
(3) the metal ion Synergist S-421 95 of about 3.3-3.8 mole/gallon is bathed precipitation to suppress described metal ion from coating;
(4) the borohydride reductive agent of about 0.045-0.08 mole/gallon; With
(5) dispensable cobalt.
33. goods with the amorphous coating of wear resistance, wherein said coating comprises the nickel of 67.5-97% weight, the boron of 2.5-10% weight, the thickness of described coating surpasses 0.0003 inch and Knoop hardness at least about 950-1050, and wherein said coating is not heat-treated and described coating continuously and immaculate.
34. according to the goods of claim 33, wherein said abrasion resistant coatings comprises the nickel of 93-97% weight and the boron of 3-7% weight.
35. according to the goods of claim 34, the thickness of wherein said abrasion resistant coatings is about 0.001-0.04 inch.
36. according to the goods of claim 34, wherein the cobalt replacement nickel is to the highest about 50% nickel.
37. bathe according to the coating that claim 6 is produced, wherein said bath is made by composition (1), (2), (3), (4) and dispensable (5) are mixed.
38. according to the goods of claim 4, the thickness of wherein said coating is above 0.00025 inch.
39. according to the goods of claim 4, wherein said goods are metal.
40. goods with the amorphous coating of continuous wear resistance that is speckless, described coating is made up of the nickel borides that is dispersed in nickel/boron alloy basically, wherein nickel is 67.5-97% weight, and boron is 2.5-10% weight, and the Knoop hardness of described coating is greater than about 1385.
41. goods with the amorphous coating of continuous wear resistance that is speckless, wherein said coating is basically by the nickel of 67.5-97% weight, the boron of 0.5-10% weight is formed, the thickness of described coating surpasses 0.0003 inch and Knoop hardness at least about 950-1050, and wherein said coating is not heat-treated.
42. the thickness of producing according to the method for claim 16 under the situation of getting rid of heat treatment step surpasses 0.00028 inch product, wherein lead or the tungstate concentration limit in this coating is at trace.
43. according to the product that the method for claim 21 is produced, wherein lead or the tungstate concentration limit in this coating is at trace.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/074,703 US6066406A (en) | 1998-05-08 | 1998-05-08 | Coating compositions containing nickel and boron |
| US09/074,703 | 1998-05-08 | ||
| US30684899A | 1999-05-07 | 1999-05-07 | |
| US09/306,848 | 1999-05-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1307648A true CN1307648A (en) | 2001-08-08 |
| CN1220790C CN1220790C (en) | 2005-09-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB99805724XA Expired - Fee Related CN1220790C (en) | 1998-05-08 | 1999-05-10 | Coating compositions containing nickel and boron |
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| Country | Link |
|---|---|
| EP (1) | EP1078114A4 (en) |
| JP (1) | JP4467794B2 (en) |
| KR (1) | KR100623278B1 (en) |
| CN (1) | CN1220790C (en) |
| AU (1) | AU757657B2 (en) |
| BR (1) | BR9910239A (en) |
| EA (1) | EA200001163A1 (en) |
| HU (1) | HUP0102519A3 (en) |
| IL (1) | IL139149A0 (en) |
| PL (1) | PL344638A1 (en) |
| TR (1) | TR200003236T2 (en) |
| WO (1) | WO1999058741A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443853A (en) * | 2011-12-02 | 2012-05-09 | 中国科学院上海硅酸盐研究所 | Preparation method of rare earth ion-doped large lead tungstate crystal |
| CN103923511A (en) * | 2014-04-17 | 2014-07-16 | 任国华 | Water-based metal paint |
| CN115807220A (en) * | 2021-09-15 | 2023-03-17 | 西部数据技术公司 | Nickel-boron coating for housings and shells |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ATE414620T1 (en) * | 2000-09-18 | 2008-12-15 | Mccomas Technologies Ag | METHOD AND DEVICE FOR PRODUCING GRAPH PRESSURE CYLINDERS |
| US6319308B1 (en) * | 2000-12-21 | 2001-11-20 | Mccomas Edward | Coating compositions containing nickel and boron and particles |
| JP5563195B2 (en) | 2005-01-21 | 2014-07-30 | コモンウェルス サイエンティフィック アンドインダストリアル リサーチ オーガナイゼーション | Activation method using a modifying substance |
| US7344019B2 (en) | 2005-07-08 | 2008-03-18 | Fmc Technologies, Inc. | Boron coated stainless steel wire belt assembly |
| ITCO20120015A1 (en) * | 2012-04-12 | 2013-10-13 | Nuovo Pignone Srl | METHOD FOR THE PREVENTION OF CORROSION AND COMPONENT OBTAINED THROUGH THIS METHOD |
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| US4833041A (en) * | 1986-12-08 | 1989-05-23 | Mccomas C Edward | Corrosion/wear-resistant metal alloy coating compositions |
| AU619486B2 (en) * | 1987-05-12 | 1992-01-30 | Charles Edward Mccomas | Stabilized electroless baths for wear-resistant metal coatings |
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1999
- 1999-05-10 TR TR2000/03236T patent/TR200003236T2/en unknown
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- 1999-05-10 WO PCT/US1999/010032 patent/WO1999058741A1/en active IP Right Grant
- 1999-05-10 CN CNB99805724XA patent/CN1220790C/en not_active Expired - Fee Related
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- 1999-05-10 JP JP2000548529A patent/JP4467794B2/en not_active Expired - Lifetime
- 1999-05-10 EP EP99921772A patent/EP1078114A4/en not_active Withdrawn
- 1999-05-10 KR KR1020007012426A patent/KR100623278B1/en not_active IP Right Cessation
- 1999-05-10 EA EA200001163A patent/EA200001163A1/en unknown
- 1999-05-10 BR BR9910239-0A patent/BR9910239A/en not_active Application Discontinuation
- 1999-05-10 AU AU38892/99A patent/AU757657B2/en not_active Ceased
- 1999-05-10 PL PL99344638A patent/PL344638A1/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443853A (en) * | 2011-12-02 | 2012-05-09 | 中国科学院上海硅酸盐研究所 | Preparation method of rare earth ion-doped large lead tungstate crystal |
| CN102443853B (en) * | 2011-12-02 | 2014-11-05 | 中国科学院上海硅酸盐研究所 | Preparation method of rare earth ion-doped large lead tungstate crystal |
| CN103923511A (en) * | 2014-04-17 | 2014-07-16 | 任国华 | Water-based metal paint |
| CN103923511B (en) * | 2014-04-17 | 2016-03-23 | 任国华 | A kind of waterborne metallic paint |
| CN115807220A (en) * | 2021-09-15 | 2023-03-17 | 西部数据技术公司 | Nickel-boron coating for housings and shells |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9910239A (en) | 2001-01-09 |
| HUP0102519A3 (en) | 2002-09-30 |
| EA200001163A1 (en) | 2001-04-23 |
| EP1078114A1 (en) | 2001-02-28 |
| JP2002514686A (en) | 2002-05-21 |
| HUP0102519A2 (en) | 2001-11-28 |
| WO1999058741A1 (en) | 1999-11-18 |
| CN1220790C (en) | 2005-09-28 |
| IL139149A0 (en) | 2001-11-25 |
| AU3889299A (en) | 1999-11-29 |
| JP4467794B2 (en) | 2010-05-26 |
| TR200003236T2 (en) | 2001-03-21 |
| EP1078114A4 (en) | 2006-12-06 |
| KR20010043399A (en) | 2001-05-25 |
| PL344638A1 (en) | 2001-11-19 |
| AU757657B2 (en) | 2003-02-27 |
| KR100623278B1 (en) | 2006-09-12 |
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