EP0066656B1 - Verfahren zur Herstellung einer Nickelschicht - Google Patents

Verfahren zur Herstellung einer Nickelschicht Download PDF

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Publication number
EP0066656B1
EP0066656B1 EP19810302442 EP81302442A EP0066656B1 EP 0066656 B1 EP0066656 B1 EP 0066656B1 EP 19810302442 EP19810302442 EP 19810302442 EP 81302442 A EP81302442 A EP 81302442A EP 0066656 B1 EP0066656 B1 EP 0066656B1
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EP
European Patent Office
Prior art keywords
nickel
glass plate
layer
nickel salt
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.)
Expired
Application number
EP19810302442
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English (en)
French (fr)
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EP0066656A1 (de
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 EP19810302442 priority Critical patent/EP0066656B1/de
Priority to DE8181302442T priority patent/DE3172414D1/de
Publication of EP0066656A1 publication Critical patent/EP0066656A1/de
Application granted granted Critical
Publication of EP0066656B1 publication Critical patent/EP0066656B1/de
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 containing 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 plates 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 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 uneveness is caused, and pinholes are caused and a uniform dense layer is not easily formed.
  • a process for depositing a nickel containing layer on a substrate in which the substrate is treated with a nickel salt and a reducing agent for reducing said nickel salt, characterized in that said treatment is carried out in the presence of diethylenetriamine and/or imidazole.
  • the nickel salt and reducing agents are applied successively in separate solutions and the diethylenetriamine and/or imidazole is present in the nickel salt solution in a concentration of 1 to 1000 ppm.
  • the diethylenetriamine or imidazole is utilised in an amount of 0.02 to 20 wt% based on the nickel salt.
  • 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 present during the chemical reduction of the nickel salt.
  • the diethylenetriamine and/or imidazole may be incorporated as an additive in a solution of a nickel salt, a solution of a reducing agent, or in a nickel plating solution containing both of a nickel salt and a reducing agent.
  • the diethylenetriamine, and/or imidazole may be applied separately during the chemical reduction process to deposit the nickel layer.
  • diethylenetriamine, and/or imidazole When diethylenetriamine, and/or imidazole is incorporated in the chemical reduction of the nickel salt, a nickel layer having high density, and a uniform thickness without pinhole can be formed. The reason is not clear, however, it is considered to result fine nickel grains deposited by the chemical reduction. Diethylenetriamine imparts especially superior effect.
  • a time for plating in the deposition of the nickel layer by the chemical plating process is usually in a range of 30 seconds to 10 minutes preferably about 1 minute to 5 minutes.
  • Atemperature 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 temperature 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 the 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 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 an 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 mmx300 mmx5 mm) was polished with ceria and rinsed with water.
  • An aqueous solution of stannous chloride (SnC12. 2H 2 0:1 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 (PdC12. nH 2 0:0.05 g/1 liter of water; 1.0 ml of 35% HCI/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.
  • PdC12. nH 2 0:0.05 g/1 liter of water 1.0 ml of 35% HCI/1 liter of water
  • 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/minute 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 longidutinal direction of the glass plate having nickel layer.
  • the optical characteristics of the glass plate are shown in Table 1.
  • a glass plate (300 mmx300 mmx5 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 ml of 35% HCI/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.
  • 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 ⁇ 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 ⁇ 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.
  • Figure 1 shows color distributions of nickel layers of the samples.
  • the nickel layer having the uniform color distribution and less pinhole can be obtained in accordance with the process of the present invention.

Claims (3)

1. Verfahren zur Abscheidung einer nickelhaltigen Schicht auf einem Substrat, wobei das Substrat behandelt wird mit einem Nickelsalz und einem Reduktionsmittel zur Reduzierung des Nickelsalzes, dadurch gekennzeichnet, daß die Behandlung durchgeführt wird in Gegenwart von Diäthylentriamin und/oder Imidazol.
2. Verfahren nach Anspruch 1, wobei das Nickelsalz und Reduktionsmittel aufeinander folgend in gesonderten Lösungen appliziert werden und das Diäthylentriamin und/oder Imidazol in der Nickels alz-Lösung in einer Konzentration von 1 bis 1000 ppm vorliegt.
3. Verfahren nach Anspruch 1 oder Anspruch 2, wobei man das Diäthylentriamin oder Imidazol in einer Menge von 0,02 bis 20 Gew.-%, bezogen auf das Nickelsalz, anwendet.
EP19810302442 1981-06-02 1981-06-02 Verfahren zur Herstellung einer Nickelschicht Expired EP0066656B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19810302442 EP0066656B1 (de) 1981-06-02 1981-06-02 Verfahren zur Herstellung einer Nickelschicht
DE8181302442T DE3172414D1 (en) 1981-06-02 1981-06-02 Process for preparing nickel layer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19810302442 EP0066656B1 (de) 1981-06-02 1981-06-02 Verfahren zur Herstellung einer Nickelschicht

Publications (2)

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

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19810302442 Expired EP0066656B1 (de) 1981-06-02 1981-06-02 Verfahren zur Herstellung einer Nickelschicht

Country Status (2)

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EP (1) EP0066656B1 (de)
DE (1) DE3172414D1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0067257B1 (de) * 1981-06-15 1986-02-05 Asahi Glass Company Ltd. Wärmestrahlungsreflektierendes Glas und dessen Herstellung
FR2531103B1 (fr) * 1982-07-30 1985-11-22 Onera (Off Nat Aerospatiale) Bain pour le depot chimique de nickel et/ou de cobalt utilisant un reducteur a base de bore ou de phosphore

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD125143A1 (de) * 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

Also Published As

Publication number Publication date
EP0066656A1 (de) 1982-12-15
DE3172414D1 (en) 1985-10-31

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