GB2218109A - Semi-bright plating of ornamental articles - Google Patents
Semi-bright plating of ornamental articles Download PDFInfo
- Publication number
- GB2218109A GB2218109A GB8909435A GB8909435A GB2218109A GB 2218109 A GB2218109 A GB 2218109A GB 8909435 A GB8909435 A GB 8909435A GB 8909435 A GB8909435 A GB 8909435A GB 2218109 A GB2218109 A GB 2218109A
- Authority
- GB
- United Kingdom
- Prior art keywords
- layer
- plating
- bright
- underplating
- semi
- 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
Links
- 238000007747 plating Methods 0.000 title claims abstract description 97
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 238000005282 brightening Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- 238000002310 reflectometry Methods 0.000 claims abstract description 11
- 229910001020 Au alloy Inorganic materials 0.000 claims abstract description 9
- 238000009713 electroplating Methods 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 8
- 239000010931 gold Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 239000010948 rhodium Substances 0.000 claims abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000009472 formulation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003353 gold alloy Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940075566 naphthalene Drugs 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical compound [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- VQOGKPQTGUIHFL-UHFFFAOYSA-N [Au]=S.[Na] Chemical compound [Au]=S.[Na] VQOGKPQTGUIHFL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical compound OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- YGSZNSDQUQYJCY-UHFFFAOYSA-L disodium;naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1S([O-])(=O)=O YGSZNSDQUQYJCY-UHFFFAOYSA-L 0.000 description 1
- -1 guinoline Chemical compound 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/005—Jewels; Clockworks; Coins
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B37/00—Cases
- G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
A metal-made ornamental article, e.g. a watchcase, of a copper alloy or zinc is provided with a semi-bright surface finish having a relative reflectivity of 4 to 7 [by plating] to give an old-fashioned or antique impression is produced by (a) providing a watchcase base body made of a copper alloy or zinc on the surface thereof with an underplating layer of nickel formed in a first electrolytic bath; and (b) forming a finishing plating layer of a noble metal selected from the group consisting of palladium, rhodium and gold or an alloy of gold on the surface of the underplating layer in a second electrolytic plating bath, either one or both of the first and second electrolytic plating baths containing a brightening agent in a concentration which is about a half of the concentration thereof conventionally used and the total thickness of the underplating layer and the finishing plating layer being in the range from 2 mu m to 5 mu m.
Description
Semi-Bright Watchcåse and t1d for the the-Preparation thereof.
The present invention relates to a metal-made ornamental article such as a watchcase of improved semi-bright surface finish and a method for the preparation thereof.
In the prior art, it is usual that the surface of a metal made ornamental article such as a watchcase or an accessory thereof, e.g. a watchstrap, is finished by providing one or more plating layers with the object of imparting increased decorativeness and resistance to atmospheric influences.When a bright silvery surface finish with brilliant lustre is desired of a watchcase, a watchcase body for example (referred to hereinafter as the substrate) made of brass or stainless steel is first provided with a plating layer of nickel and then with a plating layer of palladium. When a bright golden finish with brilliant lustre is desired, a watchcase body made of brass is first provided with a plating layer of nickel and then with a plating layer of an alloy mainly composed of gold.
In contrast to the aboveimentioned bright surface finishing with a noble metal, it is a trend of fashion in recent years that some people prefer watchcases end watchstraps with a dull-finished or semi-bright surface capable of giving an old-fashioned or antique impression or looking like a wo m vout surface of stainless steel or gold after many years of use.It is almost impossible to obtain such a seni-bright surface finish by a conventional plating method so that according to one usual method the surface of the base body of a watchcase is subjected to a honing treatment to
impart a deliberately unevenly roughened surface, before the surface is provided with an underplating layer of nickel and a finishing plating layer of palladium or of an alloy of gold.
This method of uneven honing, however, is not wholly satisfactory from the aesthetic point of view due to the appearance of the honed marks on the surface and is unable to reproduce the somewhat dull surface of stainless steel or gold which may be obtained when innumerable scratches are formed at random on a Fm-out surface.
It has also been proposed to apply the uneven honing treatment to a surface with an underplating layer of nickel but this method is economically unacceptable because the thickness of the underplating layer must at least be doubled, since otherwise the underplating layer is readily destroyed by the honing treatment.
The inventors have continued extensive investigations to provide a watchcase and accessories thereof having a surface finished to give an old-fashioned or antique impression of a high aesthetic value to surpass conventional bright finishing and have
arrived at a discovery on the basis of which the present invention has been completed.
Thus, the semi-bright metalnade ornamental article according to the invention comprises:
(a) a base body of the article as a substrate made of a copper alloy or zinc, optionally having a corrosion-resistant plating layer; (b) an underplating layer of nickel formed on the surface of the substrate; and (c) a finishing plating layer of a noble metal selected from the group consisting of palladium, rhodium and gold or an alloy of gold formed on the surface of the underplating layer, the total thickness of the underplating layer and the finishing plating layer being in the range from 2 pm to 5 pm and the relative reflectivity of the surface of the finishing plating layer being in the range from 4 to 7.
Such a controlled surface condition of the plating layer can be obtained by a method in which the underplating layer and the finishing plating layer are formed each by a wet-process plating procedure in a plating bath and either one or both of the plating -baths in the wet-process plating procedure for the underplating and finishing platings contain a brightening agent in an amount which is about a half 6f the amount conventionally in use.
The base body of the watchcase or the like as the substrate is necessarily made of a copper alloy, such as brass, nickel silver or the like, or zinc. Optionally the substrate surface of zinc is provided with a corrosion-resistant plating layer of, for example, copper and/or nickel. The substrate surface, with or without the corrosion-resistant plating layer, is first provided with an under-plating layer of nickel and then with a finishing plating layer of a noble metal which may be palladium, rhodium, gold or an alloy of gold. Optionally t > n or trore plating layers of different noble metals are formed to provide together a finishing plating layer. These noble metals can be of a c3nuenticnal grade used in plating treatment.
The thickness of the plating layers is an important factor for achieving the object of the invention. Namely, the total thickness of the underplating layer and the finishing plating layer must be in the range from 2 pm to 5 pm. This limitation must be observed even when the finishing plating layer is formed of tWD or irore plating layers of different noble metals. When the total thickness of the plating layers is outside this range, the appearance of the plated surface may not satisfy the require brent for the semi-bright surface condition as desired.
Various mDdifications are possible in the actual procedures for forming the plating layers. When semi-bright silvery finishing is desired, for example, a brassinade substrate may be first provided with a semi-bright plating layer of nickel and then with a bright plating layer or palladium. When semi-bright golden finishing is desired, on the other hand, a brass-made substrate may be first provided with a dull-surface plating layer of nickel and then with a bright plating layer of a gold alloy as the finishing plating layer. Alternatively, the finishing plating layer in this case may be composed of a bright palladium plating layer and a bright gold plating layer thereon. In short, it is not always necessary that all of the plating layers have a semi-bright surface. The semi-bright surface plating layer of nickel here inplied is a plating layer obtained by a wet-process plating process in which the plating bath contains a brightening agent in an amount which is about a half of the amount conven- tionally used for forming a bright plating layer.
The brightening agents usable in the process according to the invention include primary brightening agents such as a compound having a -C-S02- linkage, e.g. saccharin, sodium 1,5-naphthalene disulphonate, 1,3,6 -naphthal ene trisulphonate and the like, and secondary brightening agents such as coumarine, 2-butyne, 2-butyn-1,4-diol, ethylene cyanhydrin., thiourea, guinoline, pyridine and the like.
When the finishing plating layer of a noble metal is desired to have a semi-bright surface, the amount of the brightening agents added to this plating bath also should be about a half of that added to a plating bath for forming a bright plating layer of the same noble metal.
According to the invention the total thickness of the underplating layer and the finishing plating layer is controlled in a range from 2 um to 5 pm and the wet-process plating procedure is conducted in a plating bath containing a controlled arrpunt of a brightening agent so as to limit the relative reflectivity of the finished surface to a value in the range from 4 to 7.The relative reflectivity here implied is a value obtained from a goniophoto- metric curve for the light incident at the plated surface with an angle of 60 and regularly reflected by the measurement with an automatic goniopDbometer such as that manufactured by Murakami Shikisai Gijutsu Kenkyusho. ab. Semi-bright plated surfaces of watchcases after a honing treatment usually have a relative reflectivity of 9 or larger as measured with the same instrument.
In this regard, the relative reflectivity of 4 to 7 according to the invention is unique.
The accompanying Figures la, ib and ic each illustrate a goniophotometric curve obtained with a goniophotoitter model GP 1HR for the surfaces obtained in the following Examples 1, 2 and 3, raspectively, of the invention while Figure id, the peak head of which reaches the measurement ceiling, is for a conventional bright-plated surface described for comparative purposes in Example 1. These figures clearly show the matt or semi-bright condition of the surfaces according to the invention, which give an Impression of high-class goods with reduced brightness.When the relative reflectivity of the plated surface is controlled within a range of 4 to 7 and the total thickness of the plating layers is controlled within a relatively narrow range, the light passing through one layer is subject to interference with the light passing through another layer to give a high aesthetic value of an old-fashioned or antique impression of the watchcase which could not be obtained by the prior art products and processes.
The invention is further described in greater detail by means of the following non-limiting Examples.
Example 1.
A brass-made base body of a watchcase was first provided with a dull-surface plating layer of nickel having a thickness of 3 by an electrolytic plating method in a plating bath at a temperature of 40 to 550C with a current density of 2 to 10 A/dm2 on the cathode.The fonrulation of the plating bath, which had a pH of 3.5 to 4.5, was as follows:
Nickel sulphate 250 g/litre
Nickel chloride 45 g/litre
Boric acid 40 g/litre
Sodium 1,5-naphthalene disulphonate 5 g/litre 1,4 -Butyndiol 0.1 g/litre
Formalin 1.2 g/litre
The thus-formed underplating layer of nickel was further provided thereon with a bright finishing plating layer of palladium having a thickness of 2 pin by an electrolytic plating method in a plating bath at a temperature of 25 to 350C with a current density of 0.2 to 1.5 A/dm2 on the cathode.The formulation of the plating bath, which has a pH of 8.5 to 9.5, was as follows:
Palladium chloride 5 g/litre
Nickel chloride 30 g/litre Ammonium chloride 50 g/litre
Brightening agent 3-5 g/litre
The brightening agent was a corrrrerical product sold under the trade name of Eugilite No. 61 manufactured by Ebara Eugilite Co. of which the principal ingredient was O-hydrDxy coumaric anhydride.
For comparison, the same plating procedures as above were
Undertaken except that the underplating of nickel was performed using a conventional plating bath for a bright nickel plating.
The relative reflectivity of the surface of the thus-finished watchcase was at least 9 and no semi-bright surface could be obtained.
Example 2.
A brass-made base body of a watchcase was first provided with a bright plating layer of nickel having a thickness of
I jin by an electrolytic plating method in a plating bath at a temperature of 50 to 700C with a current density of 0.5 to 6 A/dm2 on the cathode. The e formulation of the plating bath, which had a pH of 4 to 4.5, was as follows:
Nickel sulphate 280 g/litre
Nickel chloride 40 g/litre
Boric acid 40 g/litre
Brightening agent 3 g/litre
Pit inhibitor 5 g/litre
The brightening agent used above was the same as in the plating bath for palladium plating in Example 1.
Thereafter, the nickel-plated substrate was provided with a dull-surface plating layer of palladium having a thickness of 2 pm by an electrolytic plating method in a plating bath at a temperature of 25 to 350C with a current density of 0.2 to 1.5 A/dm2 on the cathode. The formulation of the plating bath, which had a pH of 8.5 to 9.5, was as follows. The brightening agent was the same one as used in the nickel plating.
Palladium chloride 8 g/litre
Nickel chloride 40 g/litre Ammonium chloride 8.8 g/litre
Brightening agent 1.2 g/litre
Further, the thus palladium-plated surface was provided with a bright plating layer of a gold alloy having a thickness of 1 pm by an electrolytic plating method in a plating bath at a temperature of 45 to 500C with a current density of 0.2 to 1.0 A/dm2 on the cathode. The formulation of the plating bath, which had a pH of 9 to 9.5, was as follows:
Sodium gold sulphide 0.5 litre Palladium (as metal) 3.0 g/litre EDr-zn 1.0 g/litre
Arsenious acid 1.0 g/litre EDTA-2Na 100 g/litre
EXample 3.
A zinc made watchcase was first provided with a corrosionresistant plating composed of a layer of copper of a bright surface having a thickness of 15 to 20 pm and a layer of nickel of bright surface having a thickness of 10 to 15 jin. The copper plating was performed in a plating bath of the formulation shown below at a -temperature of 500C with a current density of 0.5 to 5 A/dm2 on the cathode while the nickel plating was performed using the same plating bath and under the same conditions as in the bright nickel plating in Example 2.
Copper sulphate 200 g/litre
Sulphuric acid 50 g/litre
Phenol 1 g/litre
Thiourea 0.01 g/litre
Dextran 0.01 litre In the next place, a dull-surface plating layer of nickel having a thickness of 2 m was provided on the abovedescribed corrosion-resistant plating layer using the same plating bath and under the same conditions as in Example 1. Finally, a bright-surface palladium plating layer having a thickness of 2 was formed on the underplating layer of nickel using the same plating bath and under the same conditions as in Example 1. The thus-finished palladiumplated silvery surface had a relative reflectivity of 6.4.
When the aboveementioned bright-surface palladium plating was omitted and, instead, a bright-surface gold-alloy finishing plating was performed using the same plating bath and under the same conditions as in Example 2, a watchcase having a semi-bright golden surface could be obtained.
Claims (4)
1. A semi-bright mefalxmade ornamental article which comprises: ~(a) a base body of the article as a substrate made of a copper alloy or zinc;
(b) an underplating layer of nickel formed on the surface of the substrate; and
(c) a finishing plating layer of a noble metal selected from the group consisting of palladium, rhodium and gold or an alloy of gold formed on the surface of the underplating layer, the total thickness of the underplating layer and the finishing plating layer being in the range from 2 pm to 5 trim and the relative reflectivity of the surface of the finishing plating layer being in the range from 4 to 7.
2. A method for the preparation of a semi-bright metal-made ornamental article of which the relative reflectivity of the surface is in the range from 4 to 7, which method comprises the steps of:
(a) providing a base body of the article made of a copper alloy or zinc on the surface thereof with an underplating layer of nickel formed in a first electrolytic bath; and
(b) forming a finishing plating layer of a noble metal selected from the group consisting of palladium, rhodium and gold or an alloy of gold on the surface cf the underplating laier in a second electrolytic plating bath, either one or both of the first and second electrolytic plating baths containing a brightening agent in a concentration which is about a half of the concentration thereof conventionally in use and the total thickness of the underplating layer and the finishing plating layer being in the range from 2 ym to 5 pm.
3. A method for the preparation of a semi-bright metalemade ornamental article, said method being as claimed in claim 2 and substantially as hereinbefore described in any of the foregoing
Examples.
4. A semi-bright netalinade ornamental article when made by a method as claimed in claim 2 or claim 3.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63106786A JP2693480B2 (en) | 1988-04-28 | 1988-04-28 | Exterior parts for watch and manufacturing method thereof |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8909435D0 GB8909435D0 (en) | 1989-06-14 |
| GB2218109A true GB2218109A (en) | 1989-11-08 |
| GB2218109B GB2218109B (en) | 1992-10-07 |
Family
ID=14442584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8909435A Expired - Fee Related GB2218109B (en) | 1988-04-28 | 1989-04-25 | Semi-bright watchcase and method for the preparation thereof |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP2693480B2 (en) |
| KR (1) | KR930004560B1 (en) |
| CN (1) | CN1020355C (en) |
| GB (1) | GB2218109B (en) |
| HK (1) | HK27793A (en) |
| SG (1) | SG1093G (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1249861A3 (en) * | 2001-03-23 | 2007-11-21 | Interuniversitair Micro-Elektronica Centrum | A multi-step method for metal deposition |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE68929253T2 (en) * | 1988-12-06 | 2001-02-22 | Idemitsu Kosan Co. Ltd., Tokio/Tokyo | Lubricating oil for a compressor cooling device |
| JP3935982B2 (en) * | 1995-10-19 | 2007-06-27 | 出光興産株式会社 | Hydraulic fluid composition |
| KR100553566B1 (en) * | 2003-10-22 | 2006-02-22 | 김명진 | How to process nail beauty tools |
| KR101250004B1 (en) * | 2010-07-02 | 2013-04-05 | 최영락 | Reflector by electroforming and method of fabrication the same |
| CN112941517A (en) * | 2019-12-11 | 2021-06-11 | 日本碍子株式会社 | Article having excellent design and method for producing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2086428A (en) * | 1980-10-31 | 1982-05-12 | Hooker Chemicals Plastics Corp | Hardened gold plating process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5848693A (en) * | 1981-09-18 | 1983-03-22 | Seiko Instr & Electronics Ltd | Armor parts for watch |
-
1988
- 1988-04-28 JP JP63106786A patent/JP2693480B2/en not_active Expired - Lifetime
-
1989
- 1989-02-24 KR KR1019890002195A patent/KR930004560B1/en not_active Expired - Fee Related
- 1989-03-23 CN CN89101716A patent/CN1020355C/en not_active Expired - Fee Related
- 1989-04-25 GB GB8909435A patent/GB2218109B/en not_active Expired - Fee Related
-
1993
- 1993-01-04 SG SG10/93A patent/SG1093G/en unknown
- 1993-03-25 HK HK277/93A patent/HK27793A/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2086428A (en) * | 1980-10-31 | 1982-05-12 | Hooker Chemicals Plastics Corp | Hardened gold plating process |
Non-Patent Citations (3)
| Title |
|---|
| "Electroplat * |
| "Gold Platin * |
| "Modern Elec * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1249861A3 (en) * | 2001-03-23 | 2007-11-21 | Interuniversitair Micro-Elektronica Centrum | A multi-step method for metal deposition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1037224A (en) | 1989-11-15 |
| JP2693480B2 (en) | 1997-12-24 |
| KR930004560B1 (en) | 1993-06-01 |
| HK27793A (en) | 1993-04-02 |
| SG1093G (en) | 1993-03-12 |
| JPH01275796A (en) | 1989-11-06 |
| GB2218109B (en) | 1992-10-07 |
| CN1020355C (en) | 1993-04-21 |
| KR890016208A (en) | 1989-11-28 |
| GB8909435D0 (en) | 1989-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100494820B1 (en) | Decorative article having white film and production method thereof | |
| JPWO2002000958A1 (en) | Decorative article with white coating and method for manufacturing the same | |
| US7867625B2 (en) | Copper-tin-oxygen alloy plating | |
| EP1553213B1 (en) | Copper-tin-oxygen based alloy plating | |
| EP1309741A2 (en) | Electroplated aluminum parts and process of production | |
| KR20110086631A (en) | Layered series containing precious metals for ornaments | |
| US4917967A (en) | Multiple-layered article and method of making same | |
| KR100366248B1 (en) | Accessory having colored coating and manufacturing method thereof | |
| GB2218109A (en) | Semi-bright plating of ornamental articles | |
| US4046644A (en) | Process for forming a gold-chromium alloy from an electrodeposited gold-chromium surface | |
| US3748712A (en) | Tarnish resistant plating for silver articles | |
| EP3540097A1 (en) | Electroplated products and electroplating bath for providing such products | |
| US3380814A (en) | Electrolyte and method for coating articles with a gold-copper-antimony alloy and article thereof | |
| JPS6187894A (en) | Method for plating titanium blank | |
| JP2003013282A (en) | Ornament and manufacturing method therefor | |
| JPS6358919B2 (en) | ||
| EP0229665A1 (en) | Specular product of golden tone and method for manufacturing same | |
| JPH0718484A (en) | Gold alloy plating solution | |
| JP3107419U (en) | Precious metal ornaments | |
| JP3480765B2 (en) | Manufacturing method of blue decorative member | |
| US4403016A (en) | Gold-colored silver-cadmium-nickel alloy for electrodeposited duplex coating | |
| CA1303802C (en) | Gold colored ware | |
| JPH09310166A (en) | Manufacturing method of plated body | |
| CN113638019A (en) | A copper-based workpiece electroplated with thick silver and method for making the same | |
| Wittle | Electrodeposited multilayer coating for titanium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19990425 |