US2774696A - Method of forming oxalate coating on chromium alloys - Google Patents
Method of forming oxalate coating on chromium alloys Download PDFInfo
- Publication number
- US2774696A US2774696A US190895A US19089550A US2774696A US 2774696 A US2774696 A US 2774696A US 190895 A US190895 A US 190895A US 19089550 A US19089550 A US 19089550A US 2774696 A US2774696 A US 2774696A
- Authority
- US
- United States
- Prior art keywords
- percent
- chromium
- iron
- coating
- ferrous
- 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
- 238000000576 coating method Methods 0.000 title claims description 29
- 239000011248 coating agent Substances 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title description 22
- 229910000599 Cr alloy Inorganic materials 0.000 title description 7
- 239000000788 chromium alloy Substances 0.000 title description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 31
- 239000011651 chromium Substances 0.000 claims description 31
- 229910052804 chromium Inorganic materials 0.000 claims description 31
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 19
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 18
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 3
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229940062993 ferrous oxalate Drugs 0.000 description 6
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910001026 inconel Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical group [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- -1 oxalate ions Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical group OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
Definitions
- This invention relates to a method for the coating of chromium and certain chromium alloys for the protection of the metals during mechanical working operations which result in extensive plastic deformation of the metal and also relates to the coated article.
- Oxalate compositions have been suggested as a base for paints to increase the corrosion resistance of the coating metal and other oxalate compositions have been suggested as so-called drawing compositions. in this latter connection it has been discovered thatjwhere the metal is to be drawn or otherwise subjected to deformation, an oxalate coating on the surface aids materially in protecting the surface against injury.
- the bath includes at least about 0.5 percent total iron and includes at least enoughferric iron to increase the solubility of ferrous iron to the extent that the sum of the ferrous and ferric iron ,isequal to at least .5%.
- the iron can be all ferric iron but cannot be all ferrous and can be in any proportion from 0.5 percent to saturation.
- a preferred percentage of total iron is l-6 percent.
- the preferred range of ferrous iron is about 00.8 percent.
- the iron oxalate is added as ferrous oxalate which is oxidized by oxidizing agents in the bath to ferric oxalate.
- the preferred oxidizing agent is chlorate but other oxidizing agents may be used. Such oxidizing agents as sodium chlorate and hydrogen peroxide are preferred for the practical reason that they leave no undesirable residue on reduction. It is preferred that the amount of chlorate or other oxidizing agent used be insufiicient to oxidize all the ferrous iron but rather to leave up to about 0.8 percent ferrous ion in the bath.
- Satisfactory coatings with the solutions of the present invention may be obtained at coating temperatures in the range of about 85 -l90 F. over a time of about 2-15. minutes. 7 N
- the oxalate ions for the coating bath are preferably derived from either ferrous oxalate, ferric oxalate, or oxalic acid.
- I oxalate salts can be used in combination with an iron salt or an acid to give the equivalent of an iron oxalate solution or the equivalent of a solution comprising iron oxalate and oxalic acid. In any event, however, the
- coating solution will include oxalate ions, ferric. ions and preferably some ferrous ions. Oxalic acid maybe added to increase the acidity Without limitation since extremely acid solutions with pH values too low for practical measurement have been used successfully.
- the concentration of acid as free acid which as used hereinafter and in the appended claims is defined as the ml. of N/ 10 alkali required to neutralize to a phenolphthalein endpoint 1 ml. of the coating composition to which has been added 10 ml. of 25 percent KF.2H2O.
- a free acid of 10 means that a 1 ml. sample of the Coating solution, after the addition of 10 ml. of 25 percent KF. ZHZO, would require 10 ml. of N/ 10 NaOH for neutralization with phenolphthalein indicator.
- 1 prefer to use a solution wherein the free acid is in the range of about 420 and particularly prefer a free acid content near the high end of the preferred range; that is, about 20.
- Inconel containing 14 percent chromium can be coated with compositions of the invention comprising about 0.5 percent chloride ion if the Inconel is annealed.
- Inconel which has been cold rolled and not annealed requires at least about 1.5 percent chloride ion.
- the lower limit of chloride for Inconel varies from about 0.5 to about 1.5 percent depending on the nature of the surface of the metal.
- a lower limit of about 1 percent may be given for Inconel, it being understood that this lower limit will vary plus or minus about 0.5 percent depending on.
- the chromium alloys of the invention which comprise about 4 percent and may be used as a reference point.
- Pure chromium plate requires a minimum chloride ion concentration of about 11 percent and this percentage 7 may be used as a referencelpoint in determining the mini- Patented Dec. 18,1956
- a metal of the present invention If it is desired to coat a metal of the present invention with a coating composition having a chloride proportion near the absolute minimum permissible, it is only a'matter of a few simple tests to establishlthis minimum. In this particular case the only criterion for a successful coating is that the solution react chemically with the surface of the metal and therefore it is merely necessary to raise the chloride percentage to the point where chemical reaction sets in.
- the lower limit of chloride ion concentration may be further characterized as that proportion which causes the solution to react chemically with the surface of the metal.
- Example 1 A series of solutions were made up containing 94 grams ferrous oxalate dihydrate, 54 grams oxalic acid dihydrate, and 9.4 grams sodium chlorate, and sufficient water to make a volume of 2 liters.
- the chloride content of the baths was varied from percentages as low as 0.15 percent up to saturation.
- Each of the mixtures was heated to about 160 F. to permit the sodium chlorate to oxidize the ferrous oxalate to ferric oxalate, the amount of sodium chlorate being just suflicient to completely oxidize all the ferrous oxalate without leaving any chlorate residue in the bath.
- Clean chromium plated panels were immersed in each of the baths at 160 F. for 5 minutes.
- the example was repeated using 4 times the quantity of ferrous oxalate specified above and using a series of solutions with chloride contents varying from 12 to 15 percent. Some of the clean chromium plated panels were immersed in these baths at 130 F. for 15 minutes and others at 150 F. for 5 minutes. In every case an excellent, heavy coating was obtained.
- Example 2 Example 1 was repeated using Alloy C (60 Ni, 15 Cr, Fe) as the substrate metal. In the case of Alloy C no coatings were obtained with chloride ion concentrations below about 5 percent, whereas above about 5 percent good coatings were obtained up to saturation of the chloride ion.
- Alloy C 60 Ni, 15 Cr, Fe
- the method of coating a metal of the class consisting of chromium and chromium-nickel-iron alloys in which the major content is a non-ferrous metal selected from the group consisting of nickel and chromium comprising the step of contacting at a coating temperature the metal surface with an aqueous solution comprising as the essential coating-producing ingredients iron oxalate and the chloride ion wherein ferrous iron is in the range of about 0-0.8 percent, wherein the total iron is at least about 0.5 percent and includes at least enough ferric iron to increase the solubility of ferrous iron so that the sum of the ferrous and ferric iron is equal to at least .5 wherein the solution is at least substantially as acid as that produced by an aqueous solution of iron oxalate alone, and wherein the proportion of chloride ion is at least that proportion which is substantially proportional to the percentage of chromium in the metal with reference points as follows:
- the method of coating a metal of the class consisting of chromium and chromium-nickel-iron alloys in which the major content is a non-ferrous metal selected from the group consisting of nickel and chromium comprising the step of contacting at a coating temperature the metal surface with an aqueous solution comprising as the essential coating-producing ingredients oxalic acid, iron oxalate, and the chloride ion wherein ferrous iron is in the range of about 00.8 percent, whereing the total iron is at least about 0.5 percent and includes at least enough ferric iron to increase the solubility of ferrous iron so that the sum of the ferrous and ferric iron is equal to at least .5 wherein the solution is at least substantially as acid as that produced by an aqueous solution of iron oxalate alone, wherein the solution contains a proportion of free acid up to about 20, and wherein the proportion of chloride ions is at least that proportion which is substantially proportional to the percentage of chromium in the metal with reference points
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)
- Electroplating And Plating Baths Therefor (AREA)
- Chemical Treatment Of Metals (AREA)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE506526D BE506526A (enrdf_load_html_response) | 1950-10-19 | ||
| US190895A US2774696A (en) | 1950-10-19 | 1950-10-19 | Method of forming oxalate coating on chromium alloys |
| DEP6157A DE891171C (de) | 1950-10-19 | 1951-09-05 | Verfahren zur Aufbringung von UEberzuegen auf Chrom und Legierungen des Chroms |
| FR1043904D FR1043904A (fr) | 1950-10-19 | 1951-10-16 | Alliages de chrome à revêtement d'oxalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US190895A US2774696A (en) | 1950-10-19 | 1950-10-19 | Method of forming oxalate coating on chromium alloys |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2774696A true US2774696A (en) | 1956-12-18 |
Family
ID=22703236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US190895A Expired - Lifetime US2774696A (en) | 1950-10-19 | 1950-10-19 | Method of forming oxalate coating on chromium alloys |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2774696A (enrdf_load_html_response) |
| BE (1) | BE506526A (enrdf_load_html_response) |
| DE (1) | DE891171C (enrdf_load_html_response) |
| FR (1) | FR1043904A (enrdf_load_html_response) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723183A (en) * | 1996-09-16 | 1998-03-03 | Birchwood Laboratories, Inc. | Metal coloring process |
| US20040250748A1 (en) * | 1999-05-24 | 2004-12-16 | Ravenscroft Keith N. | Composition and method for metal coloring process |
| US20060014042A1 (en) * | 2004-07-15 | 2006-01-19 | Block William V | Hybrid metal oxide/organometallic conversion coating for ferrous metals |
| US7964044B1 (en) | 2003-10-29 | 2011-06-21 | Birchwood Laboratories, Inc. | Ferrous metal magnetite coating processes and reagents |
| WO2019103067A1 (ja) * | 2017-11-24 | 2019-05-31 | 日本製鉄株式会社 | 化成処理合金材の製造方法及び化成処理合金材の製造方法に使用する化成処理液再生装置 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL197493A (enrdf_load_html_response) * | 1954-05-28 | |||
| GB823373A (en) * | 1955-05-24 | 1959-11-11 | Pyrene Co Ltd | Improvements relating to the formation of coatings on metal surfaces |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1895569A (en) * | 1932-02-09 | 1933-01-31 | Western Union Telegraph Co | Production of protective coatings on iron and steel articles |
| US1895568A (en) * | 1931-05-22 | 1933-01-31 | Western Union Telegraph Co | Rust proofing iron and steel articles |
| US1926846A (en) * | 1931-08-15 | 1933-09-12 | Cutler Hammer Inc | Electrode for electron discharge devices |
| US2060365A (en) * | 1933-01-31 | 1936-11-10 | Curtin Howe Corp | Oxalate coating on nonferrous metal |
| US2105015A (en) * | 1934-06-09 | 1938-01-11 | Tubus A G | Mechanically working metal article |
| US2273234A (en) * | 1933-03-27 | 1942-02-17 | Parker Rust Proof Co | Method of and solution for producing a coated iron article |
| US2434291A (en) * | 1942-09-04 | 1948-01-13 | Insl X Corp | Marine antifouling steel base |
| GB661385A (en) * | 1947-10-29 | 1951-11-21 | Pyrene Co Ltd | The production of oxalate coatings |
| US2577887A (en) * | 1949-02-12 | 1951-12-11 | Parker Rust Proof Co | Activation of oxalate metal coating compositions |
-
0
- BE BE506526D patent/BE506526A/xx unknown
-
1950
- 1950-10-19 US US190895A patent/US2774696A/en not_active Expired - Lifetime
-
1951
- 1951-09-05 DE DEP6157A patent/DE891171C/de not_active Expired
- 1951-10-16 FR FR1043904D patent/FR1043904A/fr not_active Expired
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1895568A (en) * | 1931-05-22 | 1933-01-31 | Western Union Telegraph Co | Rust proofing iron and steel articles |
| US1926846A (en) * | 1931-08-15 | 1933-09-12 | Cutler Hammer Inc | Electrode for electron discharge devices |
| US1895569A (en) * | 1932-02-09 | 1933-01-31 | Western Union Telegraph Co | Production of protective coatings on iron and steel articles |
| US2060365A (en) * | 1933-01-31 | 1936-11-10 | Curtin Howe Corp | Oxalate coating on nonferrous metal |
| US2273234A (en) * | 1933-03-27 | 1942-02-17 | Parker Rust Proof Co | Method of and solution for producing a coated iron article |
| US2105015A (en) * | 1934-06-09 | 1938-01-11 | Tubus A G | Mechanically working metal article |
| US2434291A (en) * | 1942-09-04 | 1948-01-13 | Insl X Corp | Marine antifouling steel base |
| GB661385A (en) * | 1947-10-29 | 1951-11-21 | Pyrene Co Ltd | The production of oxalate coatings |
| US2577887A (en) * | 1949-02-12 | 1951-12-11 | Parker Rust Proof Co | Activation of oxalate metal coating compositions |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723183A (en) * | 1996-09-16 | 1998-03-03 | Birchwood Laboratories, Inc. | Metal coloring process |
| US20040250748A1 (en) * | 1999-05-24 | 2004-12-16 | Ravenscroft Keith N. | Composition and method for metal coloring process |
| US7964044B1 (en) | 2003-10-29 | 2011-06-21 | Birchwood Laboratories, Inc. | Ferrous metal magnetite coating processes and reagents |
| US20060014042A1 (en) * | 2004-07-15 | 2006-01-19 | Block William V | Hybrid metal oxide/organometallic conversion coating for ferrous metals |
| US7144599B2 (en) | 2004-07-15 | 2006-12-05 | Birchwood Laboratories, Inc. | Hybrid metal oxide/organometallic conversion coating for ferrous metals |
| US7481872B1 (en) | 2004-07-15 | 2009-01-27 | Birchwood Laboratories, Inc. | Process for making bath composition for converting surface of ferrous metal to mixed oxides and organometallic compounds of aluminum and iron |
| US7625439B1 (en) | 2004-07-15 | 2009-12-01 | Birchwood Laboratories, Inc. | Bath composition for converting surface of ferrous metal to mixed oxides and organometallic compounds of aluminum and iron |
| WO2019103067A1 (ja) * | 2017-11-24 | 2019-05-31 | 日本製鉄株式会社 | 化成処理合金材の製造方法及び化成処理合金材の製造方法に使用する化成処理液再生装置 |
| CN111373074A (zh) * | 2017-11-24 | 2020-07-03 | 日本制铁株式会社 | 化学转化处理合金材料的制造方法和化学转化处理合金材料的制造方法中使用的化学转化处理液再生装置 |
| JPWO2019103067A1 (ja) * | 2017-11-24 | 2020-10-22 | 日本製鉄株式会社 | 化成処理合金材の製造方法及び化成処理合金材の製造方法に使用する化成処理液再生装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| BE506526A (enrdf_load_html_response) | |
| DE891171C (de) | 1953-09-24 |
| FR1043904A (fr) | 1953-11-12 |
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