US3764488A - Metallizing of plastic materials - Google Patents

Metallizing of plastic materials Download PDF

Info

Publication number
US3764488A
US3764488A US3764488DA US3764488A US 3764488 A US3764488 A US 3764488A US 3764488D A US3764488D A US 3764488DA US 3764488 A US3764488 A US 3764488A
Authority
US
United States
Prior art keywords
acid
metal
metallizing
weight
arsenic
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
Application number
Other languages
English (en)
Inventor
G Bernhardt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dynamit Nobel AG
Original Assignee
Dynamit Nobel AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dynamit Nobel AG filed Critical Dynamit Nobel AG
Application granted granted Critical
Publication of US3764488A publication Critical patent/US3764488A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • 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
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
    • 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
    • C23C18/285—Sensitising or activating with tin based compound or composition

Definitions

  • the travel-through principle is a chemogalvanic or chemo-electrolytic metallizing process in which the parts to be metallized remain plugged onto the same supporting element during both the chemical metalllzmg processes and the galvanic reinforcing processes so that all process phases can be performed in sequence without any interruption to re-mount the parts to be metallized.
  • the travel-through process hitherto known comprises the following steps:
  • Galvanic reinforcement by means of nickel, copper, chromium, silver, gold, or if desired by several of these metals.
  • the composition of the activating bath (2) makes it necessary, in order to achieve an optimum activation of immersed parts, working at increased bath temperature, namely within a narrow temperature range of 55-65 C. Further, frequently a loss of noble metal,
  • the object of the invention is a process for the chemo-galvanic or electrolytic metallization of plastics with adherent metal films, according to, for example, the travel-through principle which is characterized by the fact that sensitizing is achieved by means of acid solutions of compounds of trivalent elements of the 5th Main Group of the Periodic Table (Mendelyeev), preferably of trivalent arsenic, antimony, or a combination thereof.
  • the travel-through principle which is characterized by the fact that sensitizing is achieved by means of acid solutions of compounds of trivalent elements of the 5th Main Group of the Periodic Table (Mendelyeev), preferably of trivalent arsenic, antimony, or a combination thereof.
  • aqueous solutions combined with hydrochloric acid, sulfuric acid, or nitric acid, of the salts, e.g. halides, sulfates, nitrates, oxychlorides, oxynitrates, carbonates, or oxides, of arsenic or antimony, especially of the arsenic (III) oxide or AsCl in hydrochloric acid solution.
  • the Group III compound can be one which is soluble in and ionizes in aqueous acid, e.g. inorganic acid, solution.
  • the solution can have a pH of 0.3-2.5, preferably 0.5-1.5.
  • the sensitizing is performed preferably in the presence of hydrolyzable tin (IV) compounds acting as wetting agents, especially SnCl and in the presence of soluble halides or nitrates of ammonium and/ or the alkali metals (lithium, sodium, or potassium) and/or alkali earth metals (especially calcium and herein including magnesium) which acts as stabilizers.
  • hydrolyzable tin (IV) compounds acting as wetting agents especially SnCl
  • soluble halides or nitrates of ammonium and/ or the alkali metals (lithium, sodium, or potassium) and/or alkali earth metals (especially calcium and herein including magnesium) which acts as stabilizers.
  • An effect of sensitizing in accordance with the invention is that it makes possible the use, as a pickling bath, of diluted acids, e.g. diluted chromosulfuric acid (5-10 g. CrO /l. liter 50-60% by Weight sulfuric acid), and a pickling reaction temperature of 50-70" C.
  • diluted acids e.g. diluted chromosulfuric acid (5-10 g. CrO /l. liter 50-60% by Weight sulfuric acid)
  • the process makes it possible to perform the reductive sensitizing phase-as in the case of conventional processes-prior to the activation phase.
  • a dilute, aqueous, strongly acid palladium salt solution especially dilute hydrochloric or sulfuric acid, PdCl solution or PdSO solution in the pH range between 1 and 3, for instance of a strength of 0.2-5 g. PdCl in 5-20 ml. concentrated HCl/liter.
  • reaction steps can be performed in the following sequence:
  • Activating the surface for chemically plating thereon of a first metal coating in, e.g. dilute noble metal, e.g. palladium salt, solution, especially in hydrochloric or sulfuric acid palladium chloride solution.
  • a first metal coating in, e.g. dilute noble metal, e.g. palladium salt, solution, especially in hydrochloric or sulfuric acid palladium chloride solution.
  • the items to be metallized can remain on the supports designed as electrodes.
  • the support electrodes can be dipped briefly into an oxidizing acid, for instance chromosulfuric acid, nitric acid etc. and can then be used again.
  • the support electrode can be isolated by a coating resistant to chromosulfuric acid, e.g. a coating of polyvinyl chloride.
  • the invention is generally applicable to the known metallizable plastics.
  • This process is particularly valuable in the metallizing of metallizable polyvinyl types and in metallizing processes in which one conductor layer is to be deposited by reduction from nickel salt solutions while the support electrodes remain free of metal.
  • metallizable polyvinyl types there can be used for instance the copolymers of vinyl chloride with 420% by Weight fumaric acid diesters, and/r maleic acid diesters wherein at least one of the alcohol moieties of the diester is a C -C or C to C group or copolymers of the vinyl chloride with polymerizable comonomers containing long chain alkyl groups (e.g.
  • chlorinated polyethylene chlorinated polyethylene, mixtures of chlorinated polyethylene and polyvinyl chloride, mixtures of polyethylene and chlorinated polyvinyl chlorides, copolymers of vinyl chloride with ethylene as well as graft polymers of vinyl chloride on vinyl chloride copolymers, and also polyolefins, such as polypropylene or poly-4-methyl-pentene-(1), polyester, etc.
  • the invention is not limited to the plastics particularly referred to but, generally speaking is applicable to metallizable plastics, including such as ABS polymers, i.e. copolymers and graft polymers of the acrylonitrile, butadiene and styrene, containing as a rule 10-30% by weight acrylonitrile, 50-70% by Weight styrene and 8-25 by weight butadiene, metallizable polypropylene types consisting for instance of isotactic polypropylene containing relatively large amounts of an ionogenic, conductive filler material such as zinc sulfide, titanium dioxide, barium sulfate, etc., polysufones, polyacetals, polyesters, polyamides, and others, as well as mixtures of the plastics mentioned.
  • ABS polymers i.e. copolymers and graft polymers of the acrylonitrile, butadiene and styrene, containing as a rule 10-30% by weight acryl
  • Metallizable PVC types have been described in the Belgium Pats. 713,290 and 718,487. Those materials can be used in the instant process.
  • Polyvinylchloride, modified polyvinyl chloride, or other plastics resistant to chromosulfuric acid can be ,used as electrode insulating material. In his way coating of the electrode with metal during a travel-through process can be prevented.
  • THE SENSITIZING SOLUTION Another object of the invention is a sensitizing solution for the sensitizing of plastics to be metallized and consisting of acid solutions of compounds of the trivalent arsenic or antimony.
  • This sensitizing solution can contain 0.5-40 g./ liter, preferably 1-10 g./liter of compounds of the trivalent arsenic, computed on a chemically equivalency basis as PRODUCTS
  • PRODUCTS The metallized plastics manufactured by means of this sensitizing solution exhibit a perfectly smooth surface and a good adhesion of the metal coating onto the plastic surface.
  • Example 1 (a) 2.5 arsenic (III) oxide are dissolved in 20 cc. conc.
  • Example 2 (a) 4 g. arsenic (III) oxide are dissolved in 30 cc. conc.
  • Example 3 (a) 15 g. arsenic (III) oxide are dissolved in 50 cc. conc.
  • the solution is filled with water to 1 liter.
  • Example 4 As metallizable polyvinyl chloride types one can use the following copolymers of the vinyl chloride:
  • a pressed sheet made of any one of the said materials and having the dimensions 4.0 x 9.0 x 0.4 is treated by the travel-through process as follows:
  • the plate is dipped into an arsenic containing sensitizing bath (prepared discretionally according to Examples 1, 2 or 3) for 2-5 minutes at 25 C.;
  • the plate is dipped into hydrochloric acid or sulfuric acid containing palladium salt solution for a period of 2-5 minutes (e.g. 0.1 to 0.25 PdCl dissolved in 10 cc. conc. HCl and filled with water to 4 liters) at 25 C.;
  • the plate is dipped into a chemical nickel bath containing 30 g./l. NiSO -7H O and 30 g./l. NaH PO -H O at 60 C. Within 3 minutes it becomes completely coated with metallic nickel; the support electrode remains free from metal;
  • the galvanic reinforcing of the metal coating can then be, alternatively, a per se known dull finish plating, high luster copper depositing, high luster nickel depositing or chromium plating.
  • the sheet is plated with high luster copper plating by a solution containing 255 g./l. CuS -H O; 120 g./l. H 80 conc. and 8 g./l. HCl.
  • the adhesive strength of the metal coating applied in this manner onto the plastic amounts, according to DIN 40,802, to between 6 and 8 kp.
  • the support electrode is dipped briefly into chromosulfuric acid or nitric acid and can then be reused.
  • Example 5 In the travel-through process, as ABS graft polymers one uses the following polymers of the composition (a) 25% by weight acrylonitrile, 10% by weight butadiene and 65% by weight styrene.
  • the plate is dipped into an arsenic containing sensitizing bath, according to Examples 1, 2 or 3, for 2-5 minutes;
  • the plate is dipped for 2-5 minutes into a palladium salt solution containing hydrochloric acid or a corresponding amount of sulfuric acid (e.g. 0.1-0.25 g. PdCl dissolved in 10 cc. conc. HCl and filled with water to 4 liter);
  • a palladium salt solution containing hydrochloric acid or a corresponding amount of sulfuric acid (e.g. 0.1-0.25 g. PdCl dissolved in 10 cc. conc. HCl and filled with water to 4 liter);
  • the plate is dipped into a chemical nickel bath. Within three minutes, the surface is completely coated with metallic nickel. The electrodes remain free from metal;
  • the adhesive strength of the metal coating applied in this manner is, according to DIN 40,802, 7.0 hp.
  • the electrode is treated as in Example 4.
  • Example 6 Pressed plates measuring 4.0 x 9.0 x04 made of ABS graft polymers of the following composition:
  • Example 1 At temperatures employed in Example 1, are treated by the travel-through process. They are pickled in chromosulfuric acid (300 g. CrO dissolved in one liter of 20% sulfuric acid) for 10 minutes. Following rinsing with water, the plates are dipped for 2-5 minutes into the arsenic-containing sensitizing bath (Examples 1-3). Following further rinsing with water, the plate is dipped into a dilute palladium salt solution containing hydrochloric or sulfuric acid (c.g. 0.25 g. to 5 g. PdCl dissolved in 10 cc. conc. HCl and filled with water to 4 liters) for 2-5 minutes.
  • a dilute palladium salt solution containing hydrochloric or sulfuric acid c.g. 0.25 g. to 5 g. PdCl dissolved in 10 cc. conc. HCl and filled with water to 4 liters
  • the plate is dipped into a chemical copper bath. Within 3 minutes, the plate is coated with a metallic copper layer. The electrodes remain free from metal.
  • the further galvanic treatment proceeds as described in Example 4.
  • the adhesive strength of the metal film deposited onto the plastic surface amounts, according to DIN 40,802, to 6.3 kp.
  • Example 7 As a metallizable polypropylene there is used an isotactic polypropylene having a filler content of 28.1% ZnS, 0.4% BaSO, and 1.4% ZnO, and treated in the travel-through process as follows.
  • a pressed plate measuring 4.0 x 9.0 x 0.4, at tempera tures employed in Example 1, is pickled for 10 minutes in chromosulfuric acid (54.5 g. CrO dissolved in 1 liter of a 92% sulfuric acid solution). Following rinsing with water, the plate is dipped for 3-5 minutes into the arsenic containing sensitizing bath (Example 1-3). Following further rinsing with water, the plate is dipped into an acid palladium salt solution for 2-5 minutes (2.5 g. PdCl dissolved in 10 cc. conc. HCl and filled with water to 4 liters). Following another rinsing, the plate is dipped into a chemical nickel bath.
  • Example 4 The adhesive strength of the metal film applied in this manner amounts, according to DIN 40,802, to 7.5 kp. Treatment of the electrodes is as in Example 4.
  • antimony can be used in place of arsenic.
  • metals which can be used in place of arsenic and antimony are bismuth, preferably in combination with arsenic.
  • concentrated HCl such of 38 weight percent HCl content in aqueous solution.
  • step (b) by contacting the pickled surface with an aqueous acid solution of: (1) a compound of trivalent arsenic or antimony or a mixture thereof, and (2) at least one quadrivalent hydrolyzable tin compound.
  • the sensitizing solution containing at least one of hydrochloric, sulfuric, and nitric acid; 1 to 10 g./1iter trivalent arsenic compound calculated as As O 4 to g./liter of SnCl -150 g./liter of NH Cl or NH NO or a mixture thereof.

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)
US3764488D 1969-09-01 1970-08-28 Metallizing of plastic materials Expired - Lifetime US3764488A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691944314 DE1944314A1 (de) 1969-09-01 1969-09-01 Verfahren zur Metallisierung von Kunststoffen

Publications (1)

Publication Number Publication Date
US3764488A true US3764488A (en) 1973-10-09

Family

ID=5744307

Family Applications (1)

Application Number Title Priority Date Filing Date
US3764488D Expired - Lifetime US3764488A (en) 1969-09-01 1970-08-28 Metallizing of plastic materials

Country Status (12)

Country Link
US (1) US3764488A (cs)
JP (1) JPS4817385B1 (cs)
AT (1) AT305722B (cs)
BE (1) BE755520A (cs)
CA (1) CA973308A (cs)
CH (1) CH556392A (cs)
DE (1) DE1944314A1 (cs)
FR (1) FR2060341B1 (cs)
GB (1) GB1318247A (cs)
NL (1) NL7012928A (cs)
NO (1) NO129754B (cs)
SE (1) SE369203B (cs)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904792A (en) * 1972-02-09 1975-09-09 Shipley Co Catalyst solution for electroless metal deposition on a substrate
US3915664A (en) * 1971-01-20 1975-10-28 Hoechst Ag Moulded article
US3956528A (en) * 1974-11-15 1976-05-11 Minnesota Mining And Manufacturing Company Selective plating by galvanic action
US3982054A (en) * 1972-02-14 1976-09-21 Rca Corporation Method for electrolessly depositing metals using improved sensitizer composition
US4770751A (en) * 1986-12-30 1988-09-13 Okuno Chemical Industry Co., Ltd. Method for forming on a nonconductor a shielding layer against electromagnetic radiation
CN105401149A (zh) * 2015-11-13 2016-03-16 北京卫星制造厂 一种铜金刚石复合材料金锡焊接镀层的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PH23907A (en) * 1983-09-28 1989-12-18 Rohm & Haas Catalytic process and systems

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3915664A (en) * 1971-01-20 1975-10-28 Hoechst Ag Moulded article
US3904792A (en) * 1972-02-09 1975-09-09 Shipley Co Catalyst solution for electroless metal deposition on a substrate
US3982054A (en) * 1972-02-14 1976-09-21 Rca Corporation Method for electrolessly depositing metals using improved sensitizer composition
US3956528A (en) * 1974-11-15 1976-05-11 Minnesota Mining And Manufacturing Company Selective plating by galvanic action
US4770751A (en) * 1986-12-30 1988-09-13 Okuno Chemical Industry Co., Ltd. Method for forming on a nonconductor a shielding layer against electromagnetic radiation
CN105401149A (zh) * 2015-11-13 2016-03-16 北京卫星制造厂 一种铜金刚石复合材料金锡焊接镀层的制备方法

Also Published As

Publication number Publication date
CH556392A (de) 1974-11-29
NO129754B (cs) 1974-05-20
GB1318247A (en) 1973-05-23
BE755520A (fr) 1971-02-01
SE369203B (cs) 1974-08-12
NL7012928A (cs) 1971-03-03
DE1944314A1 (de) 1971-03-11
AT305722B (de) 1973-03-12
FR2060341B1 (cs) 1974-09-20
CA973308A (en) 1975-08-26
FR2060341A1 (cs) 1971-06-18
JPS4817385B1 (cs) 1973-05-29

Similar Documents

Publication Publication Date Title
US4840820A (en) Electroless nickel plating of aluminum
US3370974A (en) Electroless plating on non-conductive materials
US3652351A (en) Processes for etching synthetic polymer resins with alkaline alkali metal manganate solutions
US4567066A (en) Electroless nickel plating of aluminum
US3515649A (en) Pre-plating conditioning process
US4448811A (en) Oxidizing agent for acidic accelerator in electroless metal plating process
US3764488A (en) Metallizing of plastic materials
US3607352A (en) Electroless metal plating
US3379556A (en) Electroless plating system
US3616296A (en) Method for metallizing plastics
US3024134A (en) Nickel chemical reduction plating bath and method of using same
JP3598163B2 (ja) 金属の表面処理方法
US3671274A (en) Baths for activating the surface of plastics to be chemically metal-plated
US3619243A (en) No rerack metal plating of electrically nonconductive articles
US4246320A (en) Plated acrylate/styrene/acrylonitrile article
US3284323A (en) Electroplating of aluminum and its alloys
US5316867A (en) Method for adhering metal coatings to thermoplastic addition polymers
US3454416A (en) Aqueous bath and method for deposition of copper by chemical reduction
US3667972A (en) Chemical nickel plating baths
US3692502A (en) Metal-coated thermoplastic article
US3728232A (en) Method of plating using a protective coating on an electroplating work support
JP2962496B2 (ja) マグネ基合金のめっき方法
US3741905A (en) Preparation of through hole printed circuit boards and compositions useful therefor
US3547784A (en) Process for metallizing formed objects made from thermoplastics
US3432337A (en) Process for the currentless deposition of copper-tin layers