US3484282A - Process for the chemical nickel-plating of non-metallic articles - Google Patents
Process for the chemical nickel-plating of non-metallic articles Download PDFInfo
- Publication number
- US3484282A US3484282A US651968A US3484282DA US3484282A US 3484282 A US3484282 A US 3484282A US 651968 A US651968 A US 651968A US 3484282D A US3484282D A US 3484282DA US 3484282 A US3484282 A US 3484282A
- Authority
- US
- United States
- Prior art keywords
- nickel
- bath
- plating
- articles
- ions
- 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
- 238000007747 plating Methods 0.000 title description 40
- 238000000034 method Methods 0.000 title description 20
- 239000000126 substance Substances 0.000 title description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 53
- 229910052759 nickel Inorganic materials 0.000 description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- -1 hypophosphite ions Chemical class 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000002940 palladium Chemical class 0.000 description 7
- 229940116254 phosphonic acid Drugs 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000008363 phosphate buffer Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229920001342 Bakelite® Polymers 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
- 101150003085 Pdcl gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 239000012928 buffer substance Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229940005605 valeric acid Drugs 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
- C23C18/31—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 a process for the chemical nickel-plating of non-metallic articles by means of a bath containing nickeland hypophosphite ions, and a complex former for stabilizing the bath and for accelerating the precipitation of nickel on the surface of the article.
- a process for the chemical nickel-plating of articles treated to have a catalytic surface has been described in German Patent 1,077,940, which process essentially comprises treating the articles by means of a bath containing nickeland hypophosphite ions.
- catalytic as used in this content is intended to mean that at least the surface material of the article is capable of catalyzing the oxidation-reduction reaction between the nickel ions and the hypophosphite ions, that causes the nickel to precipitate on the catalytic surface.
- the bath is primarily required to contain the reactants in specific proportions, i.e. the bath is required to contain:
- Ni++ and H PO --ions in a quantitative ratio between i 0.25 and 1.60;
- T PO in an absolute concentration between 0.15 and 1.20 mols/liter
- the bath is required to contain so-called activating agents formed of saturated, aliphatic dicarboxylic acids having 3 to 6 carbon atoms, such as succinic acid.
- the reaction is ultimately required to be carried out at a temperature be tween 95 and 99 C. .As the applicability of the above process is limited to the chemical nickel-plating of articles having a catalytic" surface, it cannot simply be used for metallizing nonmetallic articles, as proposed in the present invention.
- the surfaces of nonmetallic articles can be treated to receive, for example, a metallic nickel plating.
- the article is first purified to activate its surface which is roughened thereafter, and pre-treated by means of a palladium salt solution, for example a palladium chloride solution.
- the palladium chloride is reduced to palladium and the article so activated is immersed thereafter in a bath containing nickeland hypophosphite ions.
- the palladium chloride solution suitable for surface activation preferably has a concentration of 35 milligrams per liter.
- hypophosphite is the reducing agent, it is advantageous to dissolve it in the metallization bath in a concentration of 0.225 mol/liter.
- the palladium-activated article should preferably be nickel-plated first with the use of a dilute preliminary bath containing Ni++ and H PO in a molar concentration of about 0.25 and, after formation of a continuous nickel plating, the article should be treated further by means of a bath customary in nickel-plating.
- the preliminary nickel-plating bath is said to avoid the induction period usually needed for the nickel to precipitate on the dispersed palladium particles as the growthpromoting nuclei, and to improve the bond strength of the nickel plating.
- the preliminary nickel-plating bath may contain, for example, the following components:
- the preliminary bath used in carrying out the nickelplating should have a pH-value between 5.5 and 7 and a temperature between 10 and 30 C.
- the bath may be mixed with an ordinary,
- short-chain, saturated aliphatic monocarboxylic acid such as acetic, butyric or valeric acid, which is added in salt form.
- the disadvantage associated with the use of a preliminary bath in carrying out the nickel-plating is seen to reside in the relatively low precipitation velocity of the nickel on the surface of the article to be plated therewith, in the suggested temperature range of 10 to 30 C., so that a layer not thicker than 1 to 1.2 is produced per hour. In the event that the temperature is increased to a value higher than 30 C., the preliminary nickel-plating bath is found to undergo spontaneous self-decomposition with the resultant formation of colloidal nickel, and to become useless. h
- German Patent 1,077,940 mentioned above is not applicable to the direct nickel-plating'of nonmetallic articles, for example plastics.
- the reason is that thermoplastics, for example, undergo plastic deformation at a temperature of -99 C. needed for the nickel-plat lng bath, and that the precipitated layer of nickel would be found to have no more than a poor bond strength.
- the present process of the present invention for the chemical nickel-plating of non-metallic articles which are (a) purified by mechanical and/or chemical treatment,
- a buffer substance and is maintained at a pH-value' between 3 and 9, comprises nickel-plating the said articles in the presence of nitrilo-trismethylene-phosphonic acid, at a temperature between 30 and 70 C.
- the bath used for carrying out the nickel-plating contains the hypophosphite ions in a concentration of about 0.25 to 1 mol per liter, which is convenient. It is also 3 advantageous to provide for a molar ratio of Ni++-ions to H PO -ions of about 0.2 to 1.6 in the bath.
- the bath used for carrying out the nickel plating contains Ni++-ions and nitrilo-trismethylene-phosphonic acid in a molar ratio of about 0.7 to 2.0.
- a bath maintained at a pH- value of 3 to 9, preferably to 6, causes the nickel to precipitate under especially favorable conditions.
- Phosphate buffer containing, per liter, 0.02 to 0.1 mol, preferable 0.067 mol Na HPO -6H O, and 0.002 to 0.01 mol, preferably 0.0067 mol KH PO has proved very suitable for maintaining the above pH-values.
- the phosphate buffer is found to participate in the stabilization of the bath, at the pH-valnes indicated above.
- pH-values and temperatures higher than those specified above accelerate the precipitation of nickel, but they reduce the stability of the bath and impair the bond strength of the nickel plating
- a stabilizer such as lead sulfide or lead acetate, which is used in a proportion of 2 milligrams per liter.
- the bath temperature which should be conveniently used at a given pH-value, Where the bath is found to have a good stability and the nickel plating precipitated on the surface of the articles to be metallized is found to have the necessary bond strength.
- the precipitated nickel plating has a thickness of about 3 to 3.5
- the nickel plating which is really formed of a nickel-phosphorous alloy containing 5 to 15% phosphorus, adheres very tenaciously to non-metallic articles of which the surface has been activated in convenient manner, prior to the metallizationl
- the nickel plating precipitated by the process of the present invention can be used for reinforcing galvanic nickel, polished nickel and polished chromium coatings, or may receive a ductile copper coating as a first reinforcing coating.
- the steps of pre-treating the article to be plated in an attempt to activate its surface does not form part of the present invention.
- the activation can be achieved, for example, in the manner set forth in German Patent 1,182,015.
- the process of the present invention can be used for the nickel plating of non-metallic substances or articles, such as polypropylene or glass or Bakelite or plastics obtained by the graft-polymerization of acrylonitrile, butadiene and styrene. 7
- the bath of the present invention offers the following advantages:
- nitrilo-trismethylene-phosphonic acid means high precipitation velocity for the nickel at temperatures of the nickel-plating bath between 30 and 70 (3., so that non-metallic articles pretreated in convenient fashion, can be metallized more rapidly than heretofore.
- the bath used in carrying out the nickel-plating can be regenerated in customary manner by means of hypophosphite and nickel ions, for example by the process disclosed in German Patent 1,107,045.
- the regeneration is very easy to achieve as there is no need for cooling the bath liquid prior to the addition of the regenerating agent.
- Shaped plastics obtained by the graft polymerization of acrylonitrile, butadiene and styrene were chemically nickel-plated. Prior to being nickel-plated, they had been purified and degreased by means of an aqueous solution of a commercial wash-active substance, chemically roughened at 60 C. for 15 minutes with the use of chromo sulfuric acid and ultimately sensitized with an aqueous tin chloride solution in hydrochloric acid. Thereafter, the surface of the shapes had been activated by means of a PdCl solution in hydrochloric acid.
- the shaped plastics were nickel-plated by means of a nickel-plating bath prepared in accordance with the present invention, the bath containing:
- the bath was adjusted by means of sodium hydroxide solution to have a pH-value of 5.5, and heated to 55 C.
- a continuous, welladhering nickel plating was found to have precipitated on the shapes within a period of 15 seconds, which, after a further 3 minutes, was found to have a thickness of 3.5,.
- nickel-plating bath contains the hypophosphite ions in a concentration of about 0.25 to 1 mol per litter.
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)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEK0059976 | 1966-08-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3484282A true US3484282A (en) | 1969-12-16 |
Family
ID=7229389
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US651968A Expired - Lifetime US3484282A (en) | 1966-08-06 | 1967-07-10 | Process for the chemical nickel-plating of non-metallic articles |
Country Status (6)
Country | Link |
---|---|
US (1) | US3484282A (de) |
BE (1) | BE702339A (de) |
CH (1) | CH480447A (de) |
DE (1) | DE1521350C3 (de) |
GB (1) | GB1131030A (de) |
NL (1) | NL6710406A (de) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3617343A (en) * | 1967-12-09 | 1971-11-02 | Knapsack Ag | Process for the chemical nickel-plating of nonmetallic articles |
US3632369A (en) * | 1969-12-11 | 1972-01-04 | Coaden Oil & Chemical Co | Polymer pigmentation |
US3653947A (en) * | 1968-08-01 | 1972-04-04 | Knapsack Ag | Surface-pretreatment of non-metallic articles for chemical nickel-plating |
USRE28361E (en) * | 1966-02-08 | 1975-03-11 | Polymer pigmentation | |
US3936577A (en) * | 1971-12-15 | 1976-02-03 | E. I. Du Pont De Nemours & Company | Method for concomitant particulate diamond deposition in electroless plating, and the product thereof |
USRE29285E (en) * | 1973-03-15 | 1977-06-28 | E. I. Du Pont De Nemours And Company | Method for concomitant particulate diamond deposition in electroless plating, and the product thereof |
USRE33767E (en) * | 1971-12-15 | 1991-12-10 | Surface Technology, Inc. | Method for concomitant particulate diamond deposition in electroless plating, and the product thereof |
US6468672B1 (en) | 2000-06-29 | 2002-10-22 | Lacks Enterprises, Inc. | Decorative chrome electroplate on plastics |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3011920A (en) * | 1959-06-08 | 1961-12-05 | Shipley Co | Method of electroless deposition on a substrate and catalyst solution therefor |
US3142582A (en) * | 1961-11-17 | 1964-07-28 | Ibm | Method of treating polyester polymer materials to improve their adhesion characteristics |
US3148072A (en) * | 1960-09-22 | 1964-09-08 | Westinghouse Electric Corp | Electroless deposition of nickel |
US3326700A (en) * | 1963-06-12 | 1967-06-20 | Rudolph J Zeblisky | Electroless copper plating |
US3420680A (en) * | 1966-04-08 | 1969-01-07 | Shipley Co | Compositions and processes for electroless nickel plating |
US3427197A (en) * | 1965-01-27 | 1969-02-11 | Lockheed Aircraft Corp | Method for plating thin titanium films |
US3438798A (en) * | 1965-08-23 | 1969-04-15 | Arp Inc | Electroless plating process |
-
1966
- 1966-08-06 DE DE1521350A patent/DE1521350C3/de not_active Expired
-
1967
- 1967-07-10 CH CH978967A patent/CH480447A/de not_active IP Right Cessation
- 1967-07-10 US US651968A patent/US3484282A/en not_active Expired - Lifetime
- 1967-07-24 GB GB33958/67A patent/GB1131030A/en not_active Expired
- 1967-07-27 NL NL6710406A patent/NL6710406A/xx unknown
- 1967-08-04 BE BE702339D patent/BE702339A/xx unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3011920A (en) * | 1959-06-08 | 1961-12-05 | Shipley Co | Method of electroless deposition on a substrate and catalyst solution therefor |
US3148072A (en) * | 1960-09-22 | 1964-09-08 | Westinghouse Electric Corp | Electroless deposition of nickel |
US3142582A (en) * | 1961-11-17 | 1964-07-28 | Ibm | Method of treating polyester polymer materials to improve their adhesion characteristics |
US3326700A (en) * | 1963-06-12 | 1967-06-20 | Rudolph J Zeblisky | Electroless copper plating |
US3427197A (en) * | 1965-01-27 | 1969-02-11 | Lockheed Aircraft Corp | Method for plating thin titanium films |
US3438798A (en) * | 1965-08-23 | 1969-04-15 | Arp Inc | Electroless plating process |
US3420680A (en) * | 1966-04-08 | 1969-01-07 | Shipley Co | Compositions and processes for electroless nickel plating |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE28361E (en) * | 1966-02-08 | 1975-03-11 | Polymer pigmentation | |
US3617343A (en) * | 1967-12-09 | 1971-11-02 | Knapsack Ag | Process for the chemical nickel-plating of nonmetallic articles |
US3653947A (en) * | 1968-08-01 | 1972-04-04 | Knapsack Ag | Surface-pretreatment of non-metallic articles for chemical nickel-plating |
US3632369A (en) * | 1969-12-11 | 1972-01-04 | Coaden Oil & Chemical Co | Polymer pigmentation |
US3936577A (en) * | 1971-12-15 | 1976-02-03 | E. I. Du Pont De Nemours & Company | Method for concomitant particulate diamond deposition in electroless plating, and the product thereof |
USRE33767E (en) * | 1971-12-15 | 1991-12-10 | Surface Technology, Inc. | Method for concomitant particulate diamond deposition in electroless plating, and the product thereof |
USRE29285E (en) * | 1973-03-15 | 1977-06-28 | E. I. Du Pont De Nemours And Company | Method for concomitant particulate diamond deposition in electroless plating, and the product thereof |
US6468672B1 (en) | 2000-06-29 | 2002-10-22 | Lacks Enterprises, Inc. | Decorative chrome electroplate on plastics |
Also Published As
Publication number | Publication date |
---|---|
BE702339A (de) | 1968-02-05 |
DE1521350B2 (de) | 1975-01-30 |
CH480447A (de) | 1969-10-31 |
DE1521350C3 (de) | 1975-09-11 |
DE1521350A1 (de) | 1969-06-12 |
GB1131030A (en) | 1968-10-16 |
NL6710406A (de) | 1968-02-07 |
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