US2690402A - Processes of chemical nickel plating of nonmetallic bodies - Google Patents
Processes of chemical nickel plating of nonmetallic bodies Download PDFInfo
- Publication number
- US2690402A US2690402A US279945A US27994552A US2690402A US 2690402 A US2690402 A US 2690402A US 279945 A US279945 A US 279945A US 27994552 A US27994552 A US 27994552A US 2690402 A US2690402 A US 2690402A
- Authority
- US
- United States
- Prior art keywords
- nickel
- palladium
- nickel plating
- metallic
- fresh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 148
- 229910052759 nickel Inorganic materials 0.000 title claims description 76
- 238000007747 plating Methods 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 26
- 230000008569 process Effects 0.000 title claims description 25
- 239000000126 substance Substances 0.000 title description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 3
- 150000002940 palladium Chemical class 0.000 description 25
- -1 hypophosphite anion Chemical class 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229920001875 Ebonite Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YWMAPNNZOCSAPF-UHFFFAOYSA-N Nickel(1+) Chemical compound [Ni+] YWMAPNNZOCSAPF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229940006444 nickel cation Drugs 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229940074404 sodium succinate Drugs 0.000 description 2
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 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
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- 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
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Definitions
- the present invention relates to processes of chemical nickel plating of non-metallic bodies, and constitutes an improvement over that disclosed and claimed in the copending application of Gregoire Gutzeit, William J. Crehan and Abraham Krieg, Serial No. 230,352, filed June '7, 1951.
- the initial surface of the body is freshened in order to remove the polarized outer skin thereof by sanding, blasting, brushing, grinding, buffing, abrading, tumbling, chemical etching, etc.; and the catalytic material with which the freshened surface of the body is contaminated essentially comprises one or more elements selected from the group consisting of copper, silicon, gold, beryllium, boron, germanium, aluminum, thallium, silicon, carbon, vanadium, molybdenum, tungsten, chromium, selenium, tellurium, titanium, iron, cobalt, nickel, palladium and platinum.
- the prepared body is immersed for a suitable time interval in a chemical nickel plating bath of the nickel cation-hypophosphite anion type.
- the freshened surface thereof is contaminated with a sufiicient amount of the catalytic material so as to form thereon firmly anchored growth nuclei, it being unnecessary to achieve a complete coverage of the freshened surface of the body with the growth nuclei since the nickel plating spreads for a certain distance from each growth nucleus in the two dimensions along the surface of the material as it builds up in the third dimension upon the growth nucleus, the freshened surface areas between the growth nuclei accommodating the intimate bonding of the nickel plating in these areas; whereby a complete and homogeneous coating of nickel upon the surface of the body is obtained.
- Another object of the invention is to provide a process of producing an intimately bonded layer of nickel upon a non-metallic body formed essentially of such materials as synthetic plastics, hard rubber, wood, quartz, glass, ceramics, or the like, that involves exposing a fresh surface of the body, applying a palladium salt to the fresh surface of the body, chemically reducing the palladium salt applied to the fresh surface of the body to metallic palladium intimately bonded thereto, and then chemically depositing nickel upon the metallic palladium and upon the fresh surface of the body.
- a further object of the invention is to provide a process of the character described, wherein the palladium salt is applied to the fresh surface of the non-metallic body by immersing the body in a first aqueous solution of the palladium salt, the palladium salt applied to the fresh surface of the body is reduced to metallic palladium by immersing the body in a second aqueous solution of a reducing agent, and the nickel is chemically deposited upon the metallic palladium and upon the fresh surface of the body by immersing the body in an aqueous chemical nickel plating bath of the nickel cation-hypophosphite anion type.
- a still further object of the invention is to provide a process of the character described, wherein the concentration of the palladium salt in the aqueous solution mentioned is quite low, so that after the palladium salt is applied to the fresh surface of the body and then chemically reduced to metallic palladium, the metallic palladium is applied uniformly to the fresh surface of the body, although not necessarily continuously, and adequately to provide securely anchored growth nuclei thereon in order that subsequently the nickel may be chemically deposited upon the metallic palladium and upon the fresh surface of the body to provide a continuous layer of the nickel of the required thickness upon the body.
- the non-metallic body formed essentially of such materials as synthetic plastics, hard rubber, wood, quartz, glass, ceramics, or the like is first prepared by freshening the surface thereof upon which the nickel is to be ultimately deposited employing any conventional step, such as,
- liquid honing with Vapor Blast equipment using Novacuiite 325 or 1250 mesh abrasive or dry blasting with 325 mesh emery powder is very effective to prepare or freshen the surface of the body, particularly when it is formed of a synthetic plastic material, such as Bakelite, methacrylate, polystyrene, etc.
- the body is immersed for a short time interval in a first aqueous solution containing a soluble salt of palladium, such as, the chloride, nitrate, bromide, or sulfate; and is then removed therefrom and rinsed with water, or the like.
- a suitable quantity of the palladium salt is applied to the fresh surface and remains thereon for the present purposes.
- the concentration of the palladium salt in the first solution is exceedingly low; for example, employing a first solution essentially comprising only water and palladium chloride, it was discovered that the concentration of the palladium chloride in the water is effective above 35 parts of palladium chloride to each 1,000,000 part of water, by weight.
- the non-metallic body is immersed for a short time interval in a second aqueous solution containing a soluble chemical reducing agent, such as, hypophosphorous acid, hydrazine hydrochloride, hydroquinone, etc.; and is then removed therefrom and rinsed with water, or the like.
- a suitable quantity of the palladium salt applied to the fresh surface of the body is chemically reduced to metallic palladium to form substantially uniformly distributed growth nuclei securely anchored thereto.
- the metallic palladium nuclei thus securely anchored to the fresh surface of the body need not be continuous or provide a monatomic layer since the nickel subsequently deposited upon each metallic palladium nucleus will spread therefrom in the two directions along the fresh surface of the body as it builds up in the third dimension upon the nucleus, thereby obtaining ultimately a complete and homogeneous coating of nickel upon the surface of the body.
- the fresh surface areas of the body between the growth nuclei permit ready spreading of the nickel deposit by virtue of the elimination of the polarization thereof.
- the second solution essentially comprising only water and a soluble hypophosphite, i. e., about 0.225 mole/liter of hypophosphite anion derived from sodium hypophosphite, the palladium chloride applied to the fresh surface of the non-metallic body is quickly and completely reduced to metallic palladium.
- the non-metallic body is then immersed for the required time interval in a chemical nickel plating bath of the nickel cationhypophosphite anion type, the time interval required being dependent upon the thickness of the nickel plating that is desired upon the surface of the body; and is then removed therefrom and rinsed with water, or the like.
- a chemical nickel plating bath of the nickel cationhypophosphite anion type the time interval required being dependent upon the thickness of the nickel plating that is desired upon the surface of the body; and is then removed therefrom and rinsed with water, or the like.
- a chemical nickel plating bath of the nickel cationhypophosphite anion type, the time interval required being dependent upon the thickness of the nickel plating that is desired upon the surface of the body; and is then removed therefrom and rinsed with water, or the like.
- an intimately bonded layer of nickel containing some phosphorus
- the temperature of the bath is preferably slightly below the boiling point thereof, about 98 C. or 99 C.
- Thebath disclosed in the Gutzeit and Krieg application essentially comprises an aqueous acid solution containing nickel cations, hypophosphite anions and a buffer in the form of a soluble salt of monocarboxylic acid; the initial pH of the bath being within the approximate range 4.5 to 5.6.
- the ratio between nickel cations and hypophosphite anions, expressed in molar concentrations, is within the range 0.25 to 0.60; the absolute concentration of hypophosphite anions, expressed in mole/liter, is within the range 0.15 to 0.35; the absolute concentration of the buffer is equivalent to two carboxyl groups for every nickel cation that can be deposited, for instance, in the case of sodium acetate, at least 0.120 mole/liter of acetate anion.
- the bath may be formed by dissolving in a water solution of hydrochloric acid, nickel chloride, sodium hypophosphite and sodium acetate, the pH of the bath being adjusted with a weak alkali, such as sodium bicarbonate.
- the bath disclosed in the Gutzeit and Ramirez application essentially comprises an aqueous acid solution containing nickel cations, hypophosphite anions and an exaltant in the form of a soluble salt of a simple short chain aliphatic dicarboxylic acid, the initial pH of the bath being within the approximate range 4.3 to 6.8.
- the ratio between nickel cations and hypophosphite anions, expressed in molar concentrations, is within the range 0.25 to 0.60; the absolute concentration of hypophosphite anions, expressed in mole/liter is within the range 0.15 to 0.20; the absolute concentration of the exaltant is equivalent to two carlboxyl groups for every nickel cation that can be deposited, for instance in the case of sodium succinate, at least 0.05 mole/liter of succinate anion.
- the bath may be formed by dissolving in a water solution of hydrochloric acid, nickel chloride, sodium hypophosphite and sodium succinate, the pH of the bath being adjusted with a weak alkali, such as, sodium bicarbonate.
- the palladium salt applied to the fresh surface of the non-metallic body be chemically reduced to metallic palladium to provide the growth nuclei securely anchored to the surface of the body before the body is immersed in the chemical nickel plating bath, as otherwise the palladium salt will become diffused throughout the chemical nickel lating bath incident to the immersion of the body, whereby black precipitate will quickly form in the chemical nickel plating bath.
- black precipitate in the chemical nickel plating bath objectionable, as it comprises a random reduction of the nickel cations therein, as contrasted with catalytic reduction of nickel cations therein upon the surface of the body undergoing the plating, but the chemical nickel plating bath is quickly depleted once the formation of black precipitate therein is initiated, since the reaction producing the black precipitate in the chemical nickel plating bath is autocatalytic.
- black precipitate begins to form in the chemical nickel plating bath, further deposition of nickel upon the surface of the body is quickly arrested and the deposit of metallic nickel thereon is rendered rough or at least the normal brightness thereof is seriously impaired.
- the alladium salt applied to the surface of the body by dipping in the first solution is chemically reduced to metallic palladium by dipping in the second solution, preceding the immersion of the body in the chemical nickel plating bath, the palladium is immobilized upon the surface of the body, so that subsequently there is no tendency for the palladium cations to diffuse through the chemical nickel plating bath and initiate the production of the objectionable black precipitate, as explained above.
- a concentration of palladium chloride in excess of about 35 parts per 1,000,000 parts of water, by weight merely brings about the application to the surface of the nonmetallic body of additional growth nuclei, as a consequence of the chemical reduction thereof in the second solution, whereby the metallic palladium applied to the fresh surface of the body tends toward a monatomic layer, so that the initiation of the nickel plating thereon in the chemical nickel plating bath is accelerated.
- the initiation of chemical nickel plating upon the growth nuclei and upon the fresh surface of the body is substantially instantaneous when the body is immersed in the chemcal nickel plating bath, and the thickness of the nickel plating (containing some phosphorus) that may be built up thereon is dependent only upon the immersion time interval. For example, in a matter of only several hours a nickel coating of several mils in thickness may be deposited upon a non-metallic body, which coating is hard,
- said first aqueous solution is of palladium chloride containing by weight at least 35 parts of palladium chloride to 1,000,000 parts of water.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Description
Patented Sept. 28, 1954 PROCESSES OF CHEMICAL NICKEL PLATING OF NONMETALLIO BODIES William J. Crehan, Hinsdale, Ill., assignor to General American Transportation Corporation, Chicago, 111., a corporation of New York No Drawing. Application April 1, 1952, Serial No. 279,945
8 Claims.
The present invention relates to processes of chemical nickel plating of non-metallic bodies, and constitutes an improvement over that disclosed and claimed in the copending application of Gregoire Gutzeit, William J. Crehan and Abraham Krieg, Serial No. 230,352, filed June '7, 1951.
In this Gutzeit, Crehan and Krieg application, there is disclosed an improved process of chemi cally nickel plating a non-metallic body formed of such materials as plastics, hard rubber, wood, ceramics, and the like, by freshening the surface of the body (removing the outer skin thereof), then contaminating the freshened surface of the body with a catalytic material, and then contacting the body with a chemical nickel plating bath. In accordance with that process, the initial surface of the body is freshened in order to remove the polarized outer skin thereof by sanding, blasting, brushing, grinding, buffing, abrading, tumbling, chemical etching, etc.; and the catalytic material with which the freshened surface of the body is contaminated essentially comprises one or more elements selected from the group consisting of copper, silicon, gold, beryllium, boron, germanium, aluminum, thallium, silicon, carbon, vanadium, molybdenum, tungsten, chromium, selenium, tellurium, titanium, iron, cobalt, nickel, palladium and platinum. Finally, in that process, the prepared body is immersed for a suitable time interval in a chemical nickel plating bath of the nickel cation-hypophosphite anion type. In the preparation of the body, the freshened surface thereof is contaminated with a sufiicient amount of the catalytic material so as to form thereon firmly anchored growth nuclei, it being unnecessary to achieve a complete coverage of the freshened surface of the body with the growth nuclei since the nickel plating spreads for a certain distance from each growth nucleus in the two dimensions along the surface of the material as it builds up in the third dimension upon the growth nucleus, the freshened surface areas between the growth nuclei accommodating the intimate bonding of the nickel plating in these areas; whereby a complete and homogeneous coating of nickel upon the surface of the body is obtained.
While the process disclosed in this Gutzeit, Crehan and Krieg application is entirely satisfactory in the nickel plating of a non-metallic body, it is dependent upon the careful preparation of the surface of the body, and particularly upon the substantially uniform contamination of the freshened surface thereof with the catalytic material to provide a substantially uniform distribution of the growth nuclei firmly anchored thereon,
2 whereby the process is more expensive to carry out commercially than is desirable.
Accordingly, it is the general object of the present invention to provide an improved process of chemical nickel plating of non-metallic bodies that is simple and economical to carry out commercially.
Another object of the invention is to provide a process of producing an intimately bonded layer of nickel upon a non-metallic body formed essentially of such materials as synthetic plastics, hard rubber, wood, quartz, glass, ceramics, or the like, that involves exposing a fresh surface of the body, applying a palladium salt to the fresh surface of the body, chemically reducing the palladium salt applied to the fresh surface of the body to metallic palladium intimately bonded thereto, and then chemically depositing nickel upon the metallic palladium and upon the fresh surface of the body.
A further object of the invention is to provide a process of the character described, wherein the palladium salt is applied to the fresh surface of the non-metallic body by immersing the body in a first aqueous solution of the palladium salt, the palladium salt applied to the fresh surface of the body is reduced to metallic palladium by immersing the body in a second aqueous solution of a reducing agent, and the nickel is chemically deposited upon the metallic palladium and upon the fresh surface of the body by immersing the body in an aqueous chemical nickel plating bath of the nickel cation-hypophosphite anion type.
A still further object of the invention is to provide a process of the character described, wherein the concentration of the palladium salt in the aqueous solution mentioned is quite low, so that after the palladium salt is applied to the fresh surface of the body and then chemically reduced to metallic palladium, the metallic palladium is applied uniformly to the fresh surface of the body, although not necessarily continuously, and adequately to provide securely anchored growth nuclei thereon in order that subsequently the nickel may be chemically deposited upon the metallic palladium and upon the fresh surface of the body to provide a continuous layer of the nickel of the required thickness upon the body.
In accordance with the process of the present invention, the non-metallic body formed essentially of such materials as synthetic plastics, hard rubber, wood, quartz, glass, ceramics, or the like, is first prepared by freshening the surface thereof upon which the nickel is to be ultimately deposited employing any conventional step, such as,
sanding, blasting, brushing, grinding, buffing, abrading, tumbling, chemical etching, etc., so as to remove the outer skin thereof in order to eliminate any polarization of the surface of the body. For instance, liquid honing with Vapor Blast equipment using Novacuiite 325 or 1250 mesh abrasive or dry blasting with 325 mesh emery powder is very effective to prepare or freshen the surface of the body, particularly when it is formed of a synthetic plastic material, such as Bakelite, methacrylate, polystyrene, etc. After the surface of the non-metallic body is thus freshened, the body is immersed for a short time interval in a first aqueous solution containing a soluble salt of palladium, such as, the chloride, nitrate, bromide, or sulfate; and is then removed therefrom and rinsed with water, or the like. For instance, merely by dipping the pre" pared body into the first solution and. then rinsing with water, a suitable quantity of the palladium salt is applied to the fresh surface and remains thereon for the present purposes. It is particularly noted that the concentration of the palladium salt in the first solution is exceedingly low; for example, employing a first solution essentially comprising only water and palladium chloride, it was discovered that the concentration of the palladium chloride in the water is effective above 35 parts of palladium chloride to each 1,000,000 part of water, by weight.
Thereafter, the non-metallic body is immersed for a short time interval in a second aqueous solution containing a soluble chemical reducing agent, such as, hypophosphorous acid, hydrazine hydrochloride, hydroquinone, etc.; and is then removed therefrom and rinsed with water, or the like. For instance, merely by dipping the prepared body into the second solution and then rinsing with water, a suitable quantity of the palladium salt applied to the fresh surface of the body is chemically reduced to metallic palladium to form substantially uniformly distributed growth nuclei securely anchored thereto. It is particularly noted that the metallic palladium nuclei thus securely anchored to the fresh surface of the body need not be continuous or provide a monatomic layer since the nickel subsequently deposited upon each metallic palladium nucleus will spread therefrom in the two directions along the fresh surface of the body as it builds up in the third dimension upon the nucleus, thereby obtaining ultimately a complete and homogeneous coating of nickel upon the surface of the body. The fresh surface areas of the body between the growth nuclei permit ready spreading of the nickel deposit by virtue of the elimination of the polarization thereof. For example, employing the second solution essentially comprising only water and a soluble hypophosphite, i. e., about 0.225 mole/liter of hypophosphite anion derived from sodium hypophosphite, the palladium chloride applied to the fresh surface of the non-metallic body is quickly and completely reduced to metallic palladium.
Finally, the non-metallic body is then immersed for the required time interval in a chemical nickel plating bath of the nickel cationhypophosphite anion type, the time interval required being dependent upon the thickness of the nickel plating that is desired upon the surface of the body; and is then removed therefrom and rinsed with water, or the like. For instance, by immersing the prepared body into the chemical nickel plating bath and then rinsing with water, an intimately bonded layer of nickel (containing some phosphorus) is deposited upon the surface thereof. The temperature of the bath is preferably slightly below the boiling point thereof, about 98 C. or 99 C.
While there are several known chemical nickel plating baths of the nickel cation-hypophosphite anion type, the baths respectively disclosed in the copending application of Gregoire Gutzeit and Abraham Krieg, Serial No. 194,656, filed November 3,1950, now Patent No. 2,658,341, granted November 10, 1953, and in the copending application of Gregoire Gutzeit and Ernest J. Ramirez, Serial No. 204,424, filed January 4, 1951, now Patent No. 2,658,842, granted November 10, 1953, are specifically recommended.
Thebath disclosed in the Gutzeit and Krieg application essentially comprises an aqueous acid solution containing nickel cations, hypophosphite anions and a buffer in the form of a soluble salt of monocarboxylic acid; the initial pH of the bath being within the approximate range 4.5 to 5.6. In this bath, the ratio between nickel cations and hypophosphite anions, expressed in molar concentrations, is within the range 0.25 to 0.60; the absolute concentration of hypophosphite anions, expressed in mole/liter, is within the range 0.15 to 0.35; the absolute concentration of the buffer is equivalent to two carboxyl groups for every nickel cation that can be deposited, for instance, in the case of sodium acetate, at least 0.120 mole/liter of acetate anion. The bath may be formed by dissolving in a water solution of hydrochloric acid, nickel chloride, sodium hypophosphite and sodium acetate, the pH of the bath being adjusted with a weak alkali, such as sodium bicarbonate.
The bath disclosed in the Gutzeit and Ramirez application essentially comprises an aqueous acid solution containing nickel cations, hypophosphite anions and an exaltant in the form of a soluble salt of a simple short chain aliphatic dicarboxylic acid, the initial pH of the bath being within the approximate range 4.3 to 6.8. In this bath, the ratio between nickel cations and hypophosphite anions, expressed in molar concentrations, is within the range 0.25 to 0.60; the absolute concentration of hypophosphite anions, expressed in mole/liter is within the range 0.15 to 0.20; the absolute concentration of the exaltant is equivalent to two carlboxyl groups for every nickel cation that can be deposited, for instance in the case of sodium succinate, at least 0.05 mole/liter of succinate anion. The bath may be formed by dissolving in a water solution of hydrochloric acid, nickel chloride, sodium hypophosphite and sodium succinate, the pH of the bath being adjusted with a weak alkali, such as, sodium bicarbonate.
In carrying out the present process, it is very important that the palladium salt applied to the fresh surface of the non-metallic body be chemically reduced to metallic palladium to provide the growth nuclei securely anchored to the surface of the body before the body is immersed in the chemical nickel plating bath, as otherwise the palladium salt will become diffused throughout the chemical nickel lating bath incident to the immersion of the body, whereby black precipitate will quickly form in the chemical nickel plating bath. Not only is the formation of black precipitate in the chemical nickel plating bath objectionable, as it comprises a random reduction of the nickel cations therein, as contrasted with catalytic reduction of nickel cations therein upon the surface of the body undergoing the plating, but the chemical nickel plating bath is quickly depleted once the formation of black precipitate therein is initiated, since the reaction producing the black precipitate in the chemical nickel plating bath is autocatalytic. Furthermore, when black precipitate begins to form in the chemical nickel plating bath, further deposition of nickel upon the surface of the body is quickly arrested and the deposit of metallic nickel thereon is rendered rough or at least the normal brightness thereof is seriously impaired. However, when the alladium salt applied to the surface of the body by dipping in the first solution is chemically reduced to metallic palladium by dipping in the second solution, preceding the immersion of the body in the chemical nickel plating bath, the palladium is immobilized upon the surface of the body, so that subsequently there is no tendency for the palladium cations to diffuse through the chemical nickel plating bath and initiate the production of the objectionable black precipitate, as explained above.
In the first solution, a concentration of palladium chloride in excess of about 35 parts per 1,000,000 parts of water, by weight, merely brings about the application to the surface of the nonmetallic body of additional growth nuclei, as a consequence of the chemical reduction thereof in the second solution, whereby the metallic palladium applied to the fresh surface of the body tends toward a monatomic layer, so that the initiation of the nickel plating thereon in the chemical nickel plating bath is accelerated. However, since palladium salts are rather expensive and initiation of the nickel plating takes place, as previously described, when the concentraticn of the nickel chloride in the first solution is at least about 35 parts per 1,000,000 parts of water, by weight, it is uneconomical substantially to increase the concentration of the palladium salt in the first solution materially beyond that noted.
In carrying out the process of the present invention, the initiation of chemical nickel plating upon the growth nuclei and upon the fresh surface of the body is substantially instantaneous when the body is immersed in the chemcal nickel plating bath, and the thickness of the nickel plating (containing some phosphorus) that may be built up thereon is dependent only upon the immersion time interval. For example, in a matter of only several hours a nickel coating of several mils in thickness may be deposited upon a non-metallic body, which coating is hard,
smooth and bright, intimately bonded to the surface of the body, and exhibits great resistance to oxidation and corrosion.
From the foregoing, it is apparent that an improved process has been provided for the plating with nickel of non-metallic bodies formed of such materials as synthetic plastics, hard rubber, wood, glass, ceramics, etc., that involves the preliminary activation or preparation of the surface of the bodies employing the method of the present invention so as to provide thereon firmly anchored metallic palladium growth nuclei and nonpolarized areas therebetween accommodating the initiation of the chemical nickel plating thereupon incident to the immersion of the bodies in the chemical nickel plating bath of the nickel cation-hypophosphite anion type. It will be understood that the invention is not limited except as defined by the appended claims.
What is claimed is:
1. The process of producing an intimately bonded and continuous layer of nickel upon the surface of a solid non-metallic body, which comprises eXp-osing a fresh non-polarized surface of said body, then contacting said body with a first aqueous solution of a palladium salt, then contacting said body with a second aqueous solution of a reducing agent in order to effect the chemical reduction of said palladium salt to metallic pal lad ium so that dispersed minute metallic palladium particles are secured to the fresh nonpolarized surface of said body, and then contacting said body with a bath consisting essentially of an aqueous solution of a nickel salt and a hypophosphite during a sufficient time interval to cause initial nickel plating upon said particles and subsequent growth of the nickel plating into a continuous nickel layer upon the fresh nonpolarized surface of said body.
2. The process of producing an intimately bonded and continuous layer of nickel upon the surface of a solid non-metallic body, which comprises exposing a fresh non-polarized surface of said body, then contacting said body with a first aqueous solution of a palladium salt, then rinsing said body, then contacting said body with a second aqueous solution of a reducing agent in order to effect the chemical reduction of said palladium salt to metallic palladium so that dispersed minute metallic palladium particles are secured to the fresh non-polarized surface of said body, then rinsing said body, and then contacting said body with a bath consisting essentially of an aqueous solution of a nickel salt and a hypo phosphite during a sufficient time interval to cause initial nickel plating upon said particles and subsequent growth of the nickel plating into a continuous nickel layer upon the fresh nonpolarized surface of said body.
3. The process set forth in claim 1, wherein said palladium salt is palladium chloride.
4. The process set forth in claim 1, wherein said first aqueous solution is of palladium chloride containing by weight at least 35 parts of palladium chloride to 1,000,000 parts of water.
5. The process set forth in claim 1, wherein said reducing agent is a hypophosphite.
6. The process set forth in claim 1, wherein said palladium salt is palladium chloride and said reducing agent is a hypophosphite.
7. The process of producing an intimately bonded and continuous layer of nickel upon the surface of a solid non-metallic body, which comprises exposing a fresh non-polarized surface of said body, applying a palladium salt to the fresh non-polarized surface of said body, then chemically reducing said palladium salt applied to the fresh non-polarized surface of said body to metallic palladium so that dispersed minute metallic palladium particles are secured to the fresh non-polarized surface of said body, and then contacting said body with a bath consisting essentially of an aqueous solution of a nickel salt and a hypophosphite during a sufiicient time interval to cause initial nickel plating upon said particles and subsequent growth of the nickel plating into a continuous nickel layer upon the fresh non-polarized surface of said body.
8. The process of producing an intimately bonded and continuous layer of nickel upon the surface of a solid non-metallic body, which comprises exposing a fresh non-polarized surface of said body, applying a palladium salt to the fresh non-polarized surface of said body by immersing said body in a first aqueous solution of said palladium salt, then chemically reducing said palladium salt applied to the fresh non-polarized surface of said body to metallic palladium by immersing said body in a second aqueous solution of a reducing agent so that dispersed minute metallic palladium particles are intimately bonded to the fresh non-polarized surface of said body, and then immersing said body in a bath consisting essentially of an aqueous solution of a nickel salt and a hypophosphite during a sufiicient time interval to cause initial nickel plating upon said particles and subsequent growth of the nickel plating into a continuous nickel layer upon the fresh nonpolarized surface of said body.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,430,581 Pessel Nov. 11, 1947 10 2,532,283 Brenner Dec. 5, 1950
Claims (1)
1. THE PROCESS OF PRODUCING AN INTIMATELY BONDED AND CONTINUOUS LAYER OF NICKEL UPON THE SURFACE OF A SOLID NON-METALLIC BODY, WHICH COMPRISES EXPOSING A FRESH NON-POLARIZED SURFACE OF SAID BODY, THEN CONTACTING SAID BODY WITH A FIRST AQUEOUS SOLUTION OF A PALLADIUM SALT, THEN CONTACTING SAID BODY WITH A SECOND AQUEOUS SOLUTION OF A REDUCING AGENT IN ORDER TO EFFECT THE CHEMICAL REDUCTION OF SAID PALLADIUM SALT TO METALLIC PALLADIUM SO THAT DISPERSED MINUTE METALLIC PALLADIUM PARTICLES ARE SECURED TO THE FRESH NONPOLARIZED SURFACE OF SAID BODY, AND THEN CONTACTING SAID BODY WITH A BATH CONSISTING ESSENTIALLY OF AN AQUEOUS SOLUTION OF A NICKEL SALT AND A HYPOPHOPHITE DURING A SUFFICIENT TIME INTERVAL TO CAUSE INITIAL NICKEL PLATING UPON SAID PARTICLES AND SUBSEQUENT GROWTH OF THE NICKEL PLATING INTO A CONTINUOUS NICKEL LAYER UPON THE FRESH NONPOLARIZED SURFACE OF SAID BODY.
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US279945A US2690402A (en) | 1952-04-01 | 1952-04-01 | Processes of chemical nickel plating of nonmetallic bodies |
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Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
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US2757104A (en) * | 1953-04-15 | 1956-07-31 | Metalholm Engineering Corp | Process of forming precision resistor |
US2848359A (en) * | 1955-06-20 | 1958-08-19 | Gen Am Transport | Methods of making printed electric circuits |
US2872312A (en) * | 1956-01-26 | 1959-02-03 | Sylvania Electric Prod | Electroless plating of non-conductors |
US2915406A (en) * | 1958-03-03 | 1959-12-01 | Int Nickel Co | Palladium plating by chemical reduction |
US2939804A (en) * | 1958-01-23 | 1960-06-07 | Uarco Inc | Resin particle coated with metal |
US2968578A (en) * | 1958-04-18 | 1961-01-17 | Corning Glass Works | Chemical nickel plating on ceramic material |
US3014818A (en) * | 1957-12-09 | 1961-12-26 | Du Pont | Electrically conducting articles and process of making same |
US3110622A (en) * | 1960-06-28 | 1963-11-12 | Allis Chalmers Mfg Co | Method of making fuel cell electrodes and the like |
US3116165A (en) * | 1960-08-16 | 1963-12-31 | Allen J Hipp | Method of making fuel cell electrodes and the like |
US3162512A (en) * | 1961-03-21 | 1964-12-22 | Engelhard Ind Inc | Immersion plating with noble metals and the product thereof |
US3167491A (en) * | 1960-07-29 | 1965-01-26 | Plasitron Corp | Polyfluorinated ethylene polymermetal article and method |
DE1193764B (en) * | 1954-12-31 | 1965-05-26 | Gen Am Transport | Process for chemical nickel-plating of solid, electrically non-conductive surfaces, in particular for the production of printed circuits |
US3250646A (en) * | 1960-08-16 | 1966-05-10 | Allis Chalmers Mfg Co | Fuel cell electrode |
US3296012A (en) * | 1965-04-30 | 1967-01-03 | Corning Glass Works | Electroless copper plating on ceramic material |
US3370974A (en) * | 1965-10-20 | 1968-02-27 | Ivan C. Hepfer | Electroless plating on non-conductive materials |
US3380817A (en) * | 1964-09-11 | 1968-04-30 | Bendix Corp | Method of making a vitreous off-axis light filter |
US3394023A (en) * | 1967-02-09 | 1968-07-23 | Thin Film Inc | Process for converting water-repellent surfaces of plastic into water-attractive surfaces |
US3393737A (en) * | 1966-09-14 | 1968-07-23 | Shell Oil Co | Electroless metal bonding of unconsolidated formations into consolidated formations |
US3438440A (en) * | 1967-12-22 | 1969-04-15 | Shell Oil Co | Electroless metal bonding of unconsolidated formations into consolidated formations |
US3438441A (en) * | 1967-12-22 | 1969-04-15 | Shell Oil Co | Electroless metal bonding of unconsolidated formations into consolidated formations |
US3467540A (en) * | 1966-01-25 | 1969-09-16 | Siemag Siegener Masch Bau | Method of increasing the adhesion of metal to a subsurface |
US3500927A (en) * | 1968-02-16 | 1970-03-17 | Shell Oil Co | Electroless metalization of unconsolidated earth formations |
US3513015A (en) * | 1967-05-03 | 1970-05-19 | Avisun Corp | Prevention of skip plating in an electroless nickel bath |
US3515649A (en) * | 1967-05-02 | 1970-06-02 | Ivan C Hepfer | Pre-plating conditioning process |
US3524754A (en) * | 1967-04-28 | 1970-08-18 | Shell Oil Co | Metal plating of plastics |
US3656952A (en) * | 1968-07-19 | 1972-04-18 | Minnesota Mining & Mfg | Non-reversal imaging process and recording elements produced thereby |
US3900601A (en) * | 1973-09-28 | 1975-08-19 | Ppg Industries Inc | Treatment of thin metallic films for increased durability |
US3914520A (en) * | 1971-04-05 | 1975-10-21 | Bunker Ramo | Method for plating of plastic |
US4287253A (en) * | 1975-04-08 | 1981-09-01 | Photocircuits Division Of Kollmorgen Corp. | Catalytic filler for electroless metallization of hole walls |
US4368221A (en) * | 1980-07-04 | 1983-01-11 | Bacs Megyei Allami Epitoipari Vallalat | Process for coating fibrous glass with amorphous nickel phosphorous glass metal |
US4472223A (en) * | 1982-10-06 | 1984-09-18 | Emerson Electric Co. | Method of forming glass seal |
US4639378A (en) * | 1984-01-17 | 1987-01-27 | Inoue Japax Research Incorporated | Auto-selective metal deposition on dielectric surfaces |
US4759952A (en) * | 1984-01-26 | 1988-07-26 | Learonal, Inc. | Process for printed circuit board manufacture |
US4761304A (en) * | 1984-01-26 | 1988-08-02 | Learonal, Inc. | Process for printed circuit board manufacture |
US4806159A (en) * | 1987-07-16 | 1989-02-21 | Sprague Electric Company | Electro-nickel plating activator composition, a method for using and a capacitor made therewith |
US4847114A (en) * | 1984-01-26 | 1989-07-11 | Learonal, Inc. | Preparation of printed circuit boards by selective metallization |
US5008157A (en) * | 1989-11-22 | 1991-04-16 | Paxos Michael N | Metallized article and process for metallizing a non-conductive article |
US5578187A (en) * | 1995-10-19 | 1996-11-26 | Enthone-Omi, Inc. | Plating process for electroless nickel on zinc die castings |
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Cited By (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2757104A (en) * | 1953-04-15 | 1956-07-31 | Metalholm Engineering Corp | Process of forming precision resistor |
DE1193764B (en) * | 1954-12-31 | 1965-05-26 | Gen Am Transport | Process for chemical nickel-plating of solid, electrically non-conductive surfaces, in particular for the production of printed circuits |
US2848359A (en) * | 1955-06-20 | 1958-08-19 | Gen Am Transport | Methods of making printed electric circuits |
US2872312A (en) * | 1956-01-26 | 1959-02-03 | Sylvania Electric Prod | Electroless plating of non-conductors |
US3014818A (en) * | 1957-12-09 | 1961-12-26 | Du Pont | Electrically conducting articles and process of making same |
US2939804A (en) * | 1958-01-23 | 1960-06-07 | Uarco Inc | Resin particle coated with metal |
US2915406A (en) * | 1958-03-03 | 1959-12-01 | Int Nickel Co | Palladium plating by chemical reduction |
US2968578A (en) * | 1958-04-18 | 1961-01-17 | Corning Glass Works | Chemical nickel plating on ceramic material |
US3110622A (en) * | 1960-06-28 | 1963-11-12 | Allis Chalmers Mfg Co | Method of making fuel cell electrodes and the like |
US3167491A (en) * | 1960-07-29 | 1965-01-26 | Plasitron Corp | Polyfluorinated ethylene polymermetal article and method |
US3250646A (en) * | 1960-08-16 | 1966-05-10 | Allis Chalmers Mfg Co | Fuel cell electrode |
US3116165A (en) * | 1960-08-16 | 1963-12-31 | Allen J Hipp | Method of making fuel cell electrodes and the like |
US3162512A (en) * | 1961-03-21 | 1964-12-22 | Engelhard Ind Inc | Immersion plating with noble metals and the product thereof |
US3380817A (en) * | 1964-09-11 | 1968-04-30 | Bendix Corp | Method of making a vitreous off-axis light filter |
US3296012A (en) * | 1965-04-30 | 1967-01-03 | Corning Glass Works | Electroless copper plating on ceramic material |
US3370974A (en) * | 1965-10-20 | 1968-02-27 | Ivan C. Hepfer | Electroless plating on non-conductive materials |
US3467540A (en) * | 1966-01-25 | 1969-09-16 | Siemag Siegener Masch Bau | Method of increasing the adhesion of metal to a subsurface |
US3393737A (en) * | 1966-09-14 | 1968-07-23 | Shell Oil Co | Electroless metal bonding of unconsolidated formations into consolidated formations |
US3394023A (en) * | 1967-02-09 | 1968-07-23 | Thin Film Inc | Process for converting water-repellent surfaces of plastic into water-attractive surfaces |
US3524754A (en) * | 1967-04-28 | 1970-08-18 | Shell Oil Co | Metal plating of plastics |
US3515649A (en) * | 1967-05-02 | 1970-06-02 | Ivan C Hepfer | Pre-plating conditioning process |
US3513015A (en) * | 1967-05-03 | 1970-05-19 | Avisun Corp | Prevention of skip plating in an electroless nickel bath |
US3438440A (en) * | 1967-12-22 | 1969-04-15 | Shell Oil Co | Electroless metal bonding of unconsolidated formations into consolidated formations |
US3438441A (en) * | 1967-12-22 | 1969-04-15 | Shell Oil Co | Electroless metal bonding of unconsolidated formations into consolidated formations |
US3500927A (en) * | 1968-02-16 | 1970-03-17 | Shell Oil Co | Electroless metalization of unconsolidated earth formations |
US3656952A (en) * | 1968-07-19 | 1972-04-18 | Minnesota Mining & Mfg | Non-reversal imaging process and recording elements produced thereby |
US3914520A (en) * | 1971-04-05 | 1975-10-21 | Bunker Ramo | Method for plating of plastic |
US3900601A (en) * | 1973-09-28 | 1975-08-19 | Ppg Industries Inc | Treatment of thin metallic films for increased durability |
US4287253A (en) * | 1975-04-08 | 1981-09-01 | Photocircuits Division Of Kollmorgen Corp. | Catalytic filler for electroless metallization of hole walls |
US4368221A (en) * | 1980-07-04 | 1983-01-11 | Bacs Megyei Allami Epitoipari Vallalat | Process for coating fibrous glass with amorphous nickel phosphorous glass metal |
US4472223A (en) * | 1982-10-06 | 1984-09-18 | Emerson Electric Co. | Method of forming glass seal |
US4639378A (en) * | 1984-01-17 | 1987-01-27 | Inoue Japax Research Incorporated | Auto-selective metal deposition on dielectric surfaces |
US4822633A (en) * | 1984-01-17 | 1989-04-18 | Inoue Japax Research Incorporated | Auto-selective metal deposition on dielectric surfaces |
US4759952A (en) * | 1984-01-26 | 1988-07-26 | Learonal, Inc. | Process for printed circuit board manufacture |
US4761304A (en) * | 1984-01-26 | 1988-08-02 | Learonal, Inc. | Process for printed circuit board manufacture |
US4847114A (en) * | 1984-01-26 | 1989-07-11 | Learonal, Inc. | Preparation of printed circuit boards by selective metallization |
US4806159A (en) * | 1987-07-16 | 1989-02-21 | Sprague Electric Company | Electro-nickel plating activator composition, a method for using and a capacitor made therewith |
US5008157A (en) * | 1989-11-22 | 1991-04-16 | Paxos Michael N | Metallized article and process for metallizing a non-conductive article |
US5578187A (en) * | 1995-10-19 | 1996-11-26 | Enthone-Omi, Inc. | Plating process for electroless nickel on zinc die castings |
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