EP0066656A1 - Procédé pour la préparation d'une couche de nickel - Google Patents

Procédé pour la préparation d'une couche de nickel Download PDF

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Publication number
EP0066656A1
EP0066656A1 EP19810302442 EP81302442A EP0066656A1 EP 0066656 A1 EP0066656 A1 EP 0066656A1 EP 19810302442 EP19810302442 EP 19810302442 EP 81302442 A EP81302442 A EP 81302442A EP 0066656 A1 EP0066656 A1 EP 0066656A1
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EP
European Patent Office
Prior art keywords
nickel
glass plate
nickel salt
nickel layer
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19810302442
Other languages
German (de)
English (en)
Other versions
EP0066656B1 (fr
Inventor
Takayuki Kobayashi
Ryo Tamamura
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.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
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 Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to DE8181302442T priority Critical patent/DE3172414D1/de
Priority to EP19810302442 priority patent/EP0066656B1/fr
Publication of EP0066656A1 publication Critical patent/EP0066656A1/fr
Application granted granted Critical
Publication of EP0066656B1 publication Critical patent/EP0066656B1/fr
Expired legal-status Critical Current

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    • 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

Definitions

  • the present invention relates to a process for preparing a nickel layer by a chemical plating.
  • Glass plates having each thin transparent or translucent metal layer made of silver, nickel or aluminum which reflect or intercept heat radiation of solar or radiant heat have been known as heat radiation reflecting glass plates and have been used as a single glass plate, a double layer glass plate or a laminated glass plate in buildings, vehicles and various apparatuses and instruments.
  • the glass plate having a nickel layer has superior heat radiation reflectivity and superior durability to the glass plates having the other metal layer and has a transparent neutral grey color and accordingly, it is one of excellent heat radiation reflecting glass.
  • the nickel layer of said glass plate is usually formed by a vacuum evaporation process, a sputtering process, or a chemical plating process.
  • the chemical plating process for applying a nickel salt and a reducing agent on a glass plate and reducing said nickel salt by a chemical reaction to form a nickel layer on the glass plate has various advantages that the nickel layer can be formed at an ambient temperature, and it can be formed for a short time in high productivity and it can be easily formed without using an expensive apparatus as required in the vacuum evaporation process or the sputtering process.
  • the chemical plating process however, has disadvantages that a rate of deposition is not easily controlled and a nickel layer having a desired thickness or uniform thickness is not easily formed and color unevenness is caused, and pinholes are caused and a uniform dense layer is not easily formed.
  • a substrate made of glass, plastic or ceramic etc. is usually treated by a sensitizing treatment or an activating treatment before the chemical plating process of the present invention.
  • the typical treatment is a treatment for contacting the substrate with an aqueous solution of a stannous salt after water washing and further contacting it with an aqueous solution of a palladium salt.
  • the typical process for preparing a nickel layer on the substrate is a process for spraying or coating a chemical nickel plating solution comprising a nickel salt and a reducing agent and if necessary, the other additive such as a chelating agent, a pH buffering agent, a pH modifier, a stabilizer etc. on the substrate and forming the nickel layer on the substrate by a chemical reduction or a process for spraying both of a nickel plating solution comprising a nickel salt and if necessary the other additive such as a chelating agent, pH buffering agent, a pH modifier etc. and a solution comprising a reducing agent and a stabilizer on a glass surface and forming a nickel layer on the substrate by a chemical reduction.
  • the other additive such as a chelating agent, a pH buffering agent, a pH modifier etc.
  • the nickel salts used in the process of the present invention can be inorganic or organic water soluble nickel salts such as nickel chloride, nickel sulfate, nickel acetate, nickel bromide, nickel iodide or a mixture of at least two nickel salts.
  • the nickel salt is usually used in a form of an aqueous solution. It is also possible to use the nickel salt in a form of an organic solvent solution or a solution of an organic solvent with water.
  • a nickel salt it is possible to incorporate a pH modifier which results in an alkaline condition and a chelating agent such as Rochelle salt, EDTA, sodium citrate and sodium gluconate, and a pH buffering agent such as malic acid and/or boric acid so as to easily perform the chemical reduction.
  • a pH modifier which results in an alkaline condition and a chelating agent such as Rochelle salt, EDTA, sodium citrate and sodium gluconate, and a pH buffering agent such as malic acid and/or boric acid so as to easily perform the chemical reduction.
  • the typical reducing agents can be sodium borohydride, potassium borohydride, formaldehyde, sodium hypophosphite, hydrazine, hydrazinium sulfate, glyoxal, dimethylamine borazane, hydrosulfite, diethyl borazane or a mixture of at least two reducing agents with a stabilizer.
  • a concentration of a nickel salt in an aqueous solution of a nickel salt used in the process of the present invention is preferably in a range of about 0.1 to 10%.
  • diethylenetriamine, imidazole. or a mixture thereof is incorporated in the chemical reduction of the nickel salt.
  • diethylenetriamine, and/or imidazole is incorporated as an additive in a solution of a nickel salt a solution of a reducing agent or a nickel plating solution containing both of a nickel salt and a reducing agent or diethylenetriamine, and/or imidazole is applied in a chemical reduction.
  • Diethylenetriamine, and/or imidazole can be present in the chemical reduction of the nickel salt to deposit the nickel layer. Therefore, the other methods of incor p orating the additive can be employed.
  • a concentration of diethylenetriamine, and/or imidazole is preferably in a range of 1 to 1,000 ppm based on a solution of a nickel salt when the additive is mixed with the nickel salt.
  • An amount of diethylenetriamine, and/or imidazole is in a range of 0.02 to 20 wt. based on the nickel salt.
  • a time for plating in the deposition of the nickel layer by the chemical plating process is usually in a range of 30 sec. to 10 min. preferably about 1 min. to 5 min.
  • a temperature of the solution of a nickel salt, the solution of a reducing agent or the solution of a nickel salt and a reducing salt in the deposition of the nickel layer by the chemical plating process is usually in a range of 10°C to 60°C especially about 30°C.
  • the rate of nickel deposition is varied depending upon the temperature in the chemical plating whereby it is important to maintain the termper- ature in the chemical plating in constant such as in a range of ⁇ 3°C so as to prevent unevenness of color.
  • a temperature of the substrate in he chemical plating is usually in a range of 10 to 60°C preferably about room temperature.
  • a thickness of the nickel layer formed in the process of the present invention can be selected to be transparent or translucent and to give desired optical characteristics such as desired heat radiation reflectivity and transmissivity etc. and is preferably in a range of 0 100 to 1000 A .
  • a composition a flow rate of the plating solution, a plating time and a temperature are selected so as to give a desired thickness of the nickel layer.
  • the nickel layer of the present invention it is possible to form a composite layer of nickel and the other metal by incorporating a salt of the other metal such as copper, cobalt, iron, silver, gold and platinum together with the nickel salt.
  • a salt of the other metal such as copper, cobalt, iron, silver, gold and platinum
  • a glass plate (300 mm x 300 mm x 5 mm) was polished with ceria and rinsed with water.
  • An aqueous solution of stannous chloride (SnCl 2 ⁇ 2H 2 O : 1 g/1 liter of water) was sprayed on the surface of the glass plate to perform a sensitizing treatment for 30 seconds and then, the glass plate was rinsed with water and an aqueous solution of palladium chloride (PdCl2 ⁇ nH 2 O : 0.05 g/1 liter of water; 1.0 ml of 35% HCl/1 liter of water) was sprayed on the surface of the glass plate to perform an activating treatment for 30 seconds and then, the glass was rinsed with deionized water.
  • PdCl2 ⁇ nH 2 O 0.05 g/1 liter of water
  • 1.0 ml of 35% HCl/1 liter of water was sprayed on the surface of the glass plate to perform an activating treatment for 30 seconds and then, the glass was rinse
  • aqueous solution of the nickel salt and the solution of the reducing agent (30°C) were respectively sprayed on the treated surface of the glass plate at 30°C by each spray-gun at each rate of 0.64 liter/min. and they were kept for 2 minutes to deposit a nickel layer on the glass plate.
  • the resulting nickel layer formed on the glass plate had a thickness of 500 A and was a dense uniform layer without any pinhole and had uniform color distribution shown by the curve (a) in Figure 1 as visible transmissivity T V in the longitudinal direction of the glass plate having nickel layer.
  • the optical characteristics of the glass plate are shown in Table 1.
  • a glass plate (300 mm x 300 mm x 5 mm) was polished with ceria and rinsed with water.
  • An aqueous solution of stannous chloride (SnCl 2 ⁇ 2H 2 O : 1 g./1 liter of water) was sprayed on the surface of the glass plate to perform a sensitizing treatment for 30 seconds and then, the glass plate was rinsed with water and an aqueous solution of palladium chloride (PdCl 2 ⁇ nH 2 O : 0.05 g./1 liter of water; 1.0 mQ of 35% HCl/1 liter of water) was sprayed on the surface of the glass plate to perform an activating treatment for 30 seconds and then, the glass plate was rinsed with deionized water.
  • PdCl 2 ⁇ nH 2 O 0.05 g./1 liter of water
  • 1.0 mQ of 35% HCl/1 liter of water was sprayed on the surface of the glass plate to perform an activating treatment for 30 seconds and
  • aqueous solution of the nickel salt and the solution of the reducing agent (30°C) were respectively sprayed on the treated surface of the glass plate at 30°C by each spray-gun at each rate of 0.64 liter/min. and they were kept for 2 minutes to deposit a nickel layer on the glass plate.
  • the resulting nickel layer formed on the glass plate had a thickness of 500 A and was a dense uniform layer without any pinhole and had uniform color distribution shown by the curve (b) in Figure 1.
  • the optical characteristics of the glass plate are shown in Table 1.
  • Example 2 In accordance with the process of Example 1 except that diethylenetriamine was eliminated from the aqueous solution of the nickel salt, a nickel layer was formed on the surface of the glass plate.
  • the resulting nickel layer formed on the glass plate had a thickness of 700 A and had color distribution shown by the curve (c) in Figure 1.
  • the optical characteristics were respectively measured under the light incidence from each nickel layer of each sample of glass plate having a thickness of 5 mm.
  • the nickel layer having the uniform color distribution and less pinhole can be obtained in accordance with the process of the present invention.

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  • 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)
EP19810302442 1981-06-02 1981-06-02 Procédé pour la préparation d'une couche de nickel Expired EP0066656B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8181302442T DE3172414D1 (en) 1981-06-02 1981-06-02 Process for preparing nickel layer
EP19810302442 EP0066656B1 (fr) 1981-06-02 1981-06-02 Procédé pour la préparation d'une couche de nickel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19810302442 EP0066656B1 (fr) 1981-06-02 1981-06-02 Procédé pour la préparation d'une couche de nickel

Publications (2)

Publication Number Publication Date
EP0066656A1 true EP0066656A1 (fr) 1982-12-15
EP0066656B1 EP0066656B1 (fr) 1985-09-25

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19810302442 Expired EP0066656B1 (fr) 1981-06-02 1981-06-02 Procédé pour la préparation d'une couche de nickel

Country Status (2)

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EP (1) EP0066656B1 (fr)
DE (1) DE3172414D1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0067257B1 (fr) * 1981-06-15 1986-02-05 Asahi Glass Company Ltd. Verre réfléchissant la radiation de chaleur et procédé pour sa fabrication
EP0102874B1 (fr) * 1982-07-30 1986-12-03 Office National d'Etudes et de Recherches Aérospatiales (O.N.E.R.A.) Bain pour le dépôt chimique de nickel et/ou de cobalt utilisant un réducteur à base de bore ou de phosphore

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD125143A1 (fr) * 1975-12-31 1977-04-06
US4204013A (en) * 1978-10-20 1980-05-20 Oxy Metal Industries Corporation Method for treating polymeric substrates prior to plating employing accelerating composition containing an alkyl amine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD125143A1 (fr) * 1975-12-31 1977-04-06
US4204013A (en) * 1978-10-20 1980-05-20 Oxy Metal Industries Corporation Method for treating polymeric substrates prior to plating employing accelerating composition containing an alkyl amine

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0067257B1 (fr) * 1981-06-15 1986-02-05 Asahi Glass Company Ltd. Verre réfléchissant la radiation de chaleur et procédé pour sa fabrication
EP0102874B1 (fr) * 1982-07-30 1986-12-03 Office National d'Etudes et de Recherches Aérospatiales (O.N.E.R.A.) Bain pour le dépôt chimique de nickel et/ou de cobalt utilisant un réducteur à base de bore ou de phosphore

Also Published As

Publication number Publication date
DE3172414D1 (en) 1985-10-31
EP0066656B1 (fr) 1985-09-25

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