US3634211A - Process for electroplating chromium and electrolytes therefor - Google Patents
Process for electroplating chromium and electrolytes therefor Download PDFInfo
- Publication number
- US3634211A US3634211A US864170A US3634211DA US3634211A US 3634211 A US3634211 A US 3634211A US 864170 A US864170 A US 864170A US 3634211D A US3634211D A US 3634211DA US 3634211 A US3634211 A US 3634211A
- Authority
- US
- United States
- Prior art keywords
- chromium
- electroplating
- ions
- chromic acid
- fluoride
- 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 64
- 239000011651 chromium Substances 0.000 title claims abstract description 64
- 238000009713 electroplating Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000003792 electrolyte Substances 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 238000007747 plating Methods 0.000 claims abstract description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 6
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 41
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 41
- 150000002500 ions Chemical class 0.000 claims description 31
- -1 fluoride ions Chemical class 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 229910020187 CeF3 Inorganic materials 0.000 claims 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 7
- 229910001430 chromium ion Inorganic materials 0.000 abstract description 5
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 13
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002222 fluorine compounds Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- SWURHZJFFJEBEE-UHFFFAOYSA-J tetrafluorocerium Chemical compound F[Ce](F)(F)F SWURHZJFFJEBEE-UHFFFAOYSA-J 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229940070337 ammonium silicofluoride Drugs 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
Definitions
- this invention relates to novel compositions and to a process for electroplating chromium plate onto a basis metal which comprises passing current from an anode to a cathode at least a portion of which contains a conductive metal layer through an aqueous acidic chromium-plating solution substantially free of nitric acid and other oxidative catalysts containing 1. at least one chromium compound providing hexavalent chromium ions for electroplating chromium; and
- chromium electroplate having a thickness of at least 1X10 mm.
- PROCESS FORELECTROPLATING CHROMIUM AND ELECTROLYTES THEREFOR This invention relates to novel compositions and to novel processes for the electrodeposition of chromium from an aqueous acidic chromium-plating bath.
- chromium may be plated onto various basis metals from aqueous bath solutions.
- aqueous bath solutions it has been found that the use of certain catalysts such as silicofluoride ions and-sulfate ions provide improved chromium electrodeposits especially insocalled low current density areas.
- catalysts such as silicofluoride ions and-sulfate ions provide improved chromium electrodeposits especially insocalled low current density areas.
- the effect of such catalyst systems has been found to vary with the concentration of the chromic acid and the ratio of the catalysts to the total chromic acid'content.
- the concentration of the chromium-plating bath continually varies during operation due to the removal of chromium in the form of deposited metal and due-to the addition of impurities arising from the electrodes as well as decomposition products, it has been difficult to control and maintain the proper catalyst and chromic acid concentrations throughout the life of a typical aqueous acidic chromium-electroplating bath.
- a further object of the invention is to provide stabilized chromium-plating bath compositions which have good throwing power and extended useful life.
- Other object of the invention will be apparent to those skilled in the art upon inspection of the following detailed description of the invention.
- this invention relates to novel compositions and to a process for electroplating chromium plate onto a basis metal which comprises passing current from an anode to a cathode at least a portion of which contains a conductive metal layer through an aqueous acidic chromium-plating solution substantially free of nitric acid and other oxidative catalysts containing 1. at least one chromium compound providing hexavalent chromium ions for electroplating chromium; and
- cerous ions in combination with fluoride ions and sulfate ions as catalysts for a time sufficient to deposit a chromium electroplate having a thickness of at least I Xl' mm.
- the chromium electroplating bath compositions of the invention may contain about 100-600 g./l. of chromic acid (expressed as CrO and preferably about 200-350 g./l. of chromic acid.
- the fluoride ions may be added to the chromium electroplating bath in the form of compounds such as sodium silicofluoride (Na SiF fluosilicic acid (H SiF strontium silicofluoride (SrSiF ammonium silicofluoride [(Nl-l Sif magnesium silicofluoride (MgSif calcium silicofluoride (CaSiF etc.
- fluoride compounds which may be used in the bath according to the invention include sodium fluoride, potassium fluoride, calcium fluoride, hydrofluoric acid, ceric fluoride, cerous fluoride, etc.
- fluoride ions including complex fluoride ions
- fluoaluminates fluoborates, fluotitanates, and fluozirconates.
- the sulfate ions may be added to the chromium-electroplating bath in the form of suitable sulfate compounds such as strontium sulfate (S180 sulfuric acid (H S0 lithium sulfate (Li SO ammonium sulfate [(NH.,) 80 calcium sulfate (CaSo etc.
- suitable sulfate compounds such as strontium sulfate (S180 sulfuric acid (H S0 lithium sulfate (Li SO ammonium sulfate [(NH.,) 80 calcium sulfate (CaSo etc.
- the chromium electroplating process may use temperatures of 30-I0 C. with a chromic acid bath containing 100-600 gJl. of chromic'acid (as CrO).
- CrO chromic'acid
- the ratio of chromic acid to sulfate ion (Cr0 :SO may be maintained at l00-500: l ically l50-300:l and preferably about 200:1.
- Cerous ions may be added to the bath in the form of salts such as cerium carbonate, cerium fluoride, cerium sulfate, etc.
- cerium fluoride CeF
- the chromium plating bath composition containing -600 g./l. of Cr0 may be saturated with can, Such saturation is provided to obtain self-regulation of the catalyst content of the bath.
- CeF Cerous salts including complex fluoride salts
- CeF or other cerous salts including complex fluoride salts
- a chromic acid solution which contains excess undissolved cerium fluoride (CeF Excess cerous ion concentrations derived from other cerium salts maybe utilized to suppress and further control the fluoride ion concentration.
- chromic acid concentration of less than 100-600 g./l. may be used, the preferred range is 100-600 g./l/, and the most preferred range is 200-400 g./l.
- the chromic acid:fluoride ratio remains relatively constant leading to uniformity of operation
- the concentration of the fluoride ion may be further suppressed by the use of an excess of cerous ion as supplied, for example, by cerous carbonate or soluble cerous oxide.
- the cerous ion-containing baths must be essentially free of substantial quantities of oxidative catalysts (such as nitric acid, perchloric acid, etc.) to prevent excessive oxidation of the cerous ion to the eerie ion on electrolysis. Because the solubility of ceric fluoride is substantially greater than the solubility of cerous fluoride, the presence of ceric ions in the bath compositions of the invention is undesirable.
- oxidative catalysts such as nitric acid, perchloric acid, etc.
- control solution showed the slight darkening expected from the formation of trivalent chromium by electrolysis.
- the experimental solution containing the nitric acid was virtually black thus indicating that much trivalent chromium and tetravalent cerium had been formed.
- the oxidation tivity is not directly proportional to the total fluoride because the complex fluorides may modify this activity.
- the unexpected stability of operation ofthe plating baths of the invention may be illustrated by the use of an aqueous bath was confirmed by analyzing the solutions for fluoride.
- the 5 made up originally to contain 300 g./l. chromic acid, 6.6 g./l. control solution contained 0.36 g./l. of fluoride. This was the strontium sulfate, 5.8 g./l. strontium chromate, and 3.5 cerous amount expected from the equilibrium solubility of cerous fluoride.
- the bath was allowed to equilibrate at 46 C. for fluoride.
- the experimental solution contained considerably three days with preelectrolysis of 4 amp-hr./liter (4 AH/L). more fluoride, 6.68 g./l.
- the aqueous acid chromium plating bath compositions of the invention may be employed TABLE at temperatures of about 3070 C. to prepare improved chromium plated articles by passing current from an anode to l5 Example m Hum k '6 a basis metal cathode through said aqueous acidic chromium (4.l AH/l.) ($51 :i-i/Ll plating solution at a temperature of 3070 C. for a time sufflcient to deposit a chromium electroplate having a thickness of Crq1 300 265 at least l l0 mm.
- the baths Standard test stl'lps m a Hull Cell Chrolmum coveroage are characterized by excellent stability and uniformity of the was measured by Platlng at 2 amperesfor 3 minutes a! 46 fluoride: sulfate ratios in the presence of chromic acid which is T coverage resllhs m ofchromlum measured fr Om the saturated with cerous fluoride. The ratios have been found to fi current denslty end of the test panels are Show" In table remain fairly uniform over wide concentrations of chromic TABLE III The following examples are submitted for the purpose of 11- lustration only and are not to be construed as limiting the Scope of the mvenuon in any I Example No. Days AH/LITER Coverage (mm.)
- an excess of cerous ion may be utilized to reduce or suppress the concentration of the fluoride ion as desired.
- Table I also illustrates that use of the complex fluoride provides a greater total fluoride content than the simple fluoride. It is to be noted that the catalytic acover long periods of use and show that the oxidation of cerous ion to ceric ion apparently does not occur even after electrolysis for extended time periods as long as the bath is free of nitric ion or other catalytic oxidative ions.
- a process for electroplating chromium plate onto a basis metal which comprises passing current from an anode to a cathode at least a portion of which contains a conductive metal layer through an aqueous acidic chromium plating solution substantially free of nitric acid or other oxidative catalyst containing 1. at least one chromium compound providing hexavalent chromium ions for electroplating chromium; and
- a composition for electroplating chromium plate onto a basis metal which is substantially free of oxidative catalyst which comprises 1. at least one chromium compound providing hexavalent chromium ions on aqueous media for electroplating chromium; and
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Catalysts (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86417069A | 1969-10-06 | 1969-10-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3634211A true US3634211A (en) | 1972-01-11 |
Family
ID=25342674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US864170A Expired - Lifetime US3634211A (en) | 1969-10-06 | 1969-10-06 | Process for electroplating chromium and electrolytes therefor |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US3634211A (nl) |
| JP (1) | JPS4911539B1 (nl) |
| CA (1) | CA975709A (nl) |
| DE (1) | DE2049038C3 (nl) |
| ES (1) | ES384095A1 (nl) |
| FR (1) | FR2064156B1 (nl) |
| GB (1) | GB1322939A (nl) |
| NL (1) | NL171074C (nl) |
| SE (1) | SE368723B (nl) |
| ZA (1) | ZA706489B (nl) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477315A (en) * | 1980-11-10 | 1984-10-16 | Omi International Corporation | Trivalent chromium electrolyte and process employing reducing agents |
| US4680099A (en) * | 1986-04-07 | 1987-07-14 | Raymund Singleton | Electroplating apparatus |
| WO2009044266A2 (en) * | 2007-10-05 | 2009-04-09 | Create New Technology S.R.L. | System and method of plating metal alloys by using galvanic technology |
| CN114076721A (zh) * | 2020-08-12 | 2022-02-22 | 宝山钢铁股份有限公司 | 钢板镀铬溶液使用寿命的检测方法 |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3758390A (en) * | 1971-06-18 | 1973-09-11 | M & T Chemicals Inc | Novel cromium plating compositions |
| JPS52125319U (nl) * | 1976-03-19 | 1977-09-22 | ||
| JPS5312245U (nl) * | 1976-07-15 | 1978-02-01 | ||
| JPS53132158A (en) * | 1977-04-21 | 1978-11-17 | Kouji Makimoto | Door |
| JPS53148545U (nl) * | 1977-04-27 | 1978-11-22 | ||
| JPS5521488U (nl) * | 1978-07-31 | 1980-02-12 | ||
| GB2071151B (en) * | 1980-03-10 | 1983-04-07 | Ibm | Trivalent chromium electroplating |
| JPS5960287U (ja) * | 1982-10-15 | 1984-04-19 | 星 三喜人 | 仕切用木製パネル |
| CA1244376A (en) * | 1983-05-12 | 1988-11-08 | Thaddeus W. Tomaszewski | Trivalent chromium electrolyte and process |
| JPS59190884U (ja) * | 1983-06-03 | 1984-12-18 | 不二サッシ株式会社 | フラツシユドアのコア材 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3334033A (en) * | 1964-09-11 | 1967-08-01 | Udylite Corp | Chromium plating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1864014A (en) * | 1927-01-03 | 1932-06-21 | Dwight T Ewing | Chromium plating process |
-
1969
- 1969-10-06 US US864170A patent/US3634211A/en not_active Expired - Lifetime
-
1970
- 1970-09-10 GB GB4337770A patent/GB1322939A/en not_active Expired
- 1970-09-22 ZA ZA706489A patent/ZA706489B/xx unknown
- 1970-09-28 JP JP45084917A patent/JPS4911539B1/ja active Pending
- 1970-09-29 ES ES384095A patent/ES384095A1/es not_active Expired
- 1970-10-01 CA CA094,545A patent/CA975709A/en not_active Expired
- 1970-10-02 SE SE13382/70A patent/SE368723B/xx unknown
- 1970-10-05 FR FR7035891A patent/FR2064156B1/fr not_active Expired
- 1970-10-05 NL NLAANVRAGE7014597,A patent/NL171074C/nl not_active IP Right Cessation
- 1970-10-06 DE DE2049038A patent/DE2049038C3/de not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3334033A (en) * | 1964-09-11 | 1967-08-01 | Udylite Corp | Chromium plating |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477315A (en) * | 1980-11-10 | 1984-10-16 | Omi International Corporation | Trivalent chromium electrolyte and process employing reducing agents |
| US4680099A (en) * | 1986-04-07 | 1987-07-14 | Raymund Singleton | Electroplating apparatus |
| WO2009044266A2 (en) * | 2007-10-05 | 2009-04-09 | Create New Technology S.R.L. | System and method of plating metal alloys by using galvanic technology |
| WO2009044266A3 (en) * | 2007-10-05 | 2010-01-21 | Create New Technology S.R.L. | System and method of plating metal alloys by using galvanic technology |
| US20100221571A1 (en) * | 2007-10-05 | 2010-09-02 | Create New Technology S.R.L. | System and method of plating metal alloys by using galvanic technology |
| US8668817B2 (en) | 2007-10-05 | 2014-03-11 | Creat New Technology S.R.L. | System and method of plating metal alloys by using galvanic technology |
| CN114076721A (zh) * | 2020-08-12 | 2022-02-22 | 宝山钢铁股份有限公司 | 钢板镀铬溶液使用寿命的检测方法 |
| CN114076721B (zh) * | 2020-08-12 | 2023-09-12 | 宝山钢铁股份有限公司 | 钢板镀铬溶液使用寿命的检测方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2049038C3 (de) | 1982-03-25 |
| DE2049038B2 (de) | 1981-06-11 |
| ES384095A1 (es) | 1972-12-16 |
| FR2064156A1 (nl) | 1971-07-16 |
| ZA706489B (en) | 1971-05-27 |
| FR2064156B1 (nl) | 1974-08-23 |
| NL7014597A (nl) | 1971-04-08 |
| JPS4911539B1 (nl) | 1974-03-18 |
| GB1322939A (en) | 1973-07-11 |
| DE2049038A1 (de) | 1971-04-29 |
| NL171074C (nl) | 1983-02-01 |
| CA975709A (en) | 1975-10-07 |
| SE368723B (nl) | 1974-07-15 |
| NL171074B (nl) | 1982-09-01 |
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