US3375179A - Method of anodizing beryllium and product thereof - Google Patents

Method of anodizing beryllium and product thereof Download PDF

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Publication number
US3375179A
US3375179A US407454A US40745464A US3375179A US 3375179 A US3375179 A US 3375179A US 407454 A US407454 A US 407454A US 40745464 A US40745464 A US 40745464A US 3375179 A US3375179 A US 3375179A
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United States
Prior art keywords
beryllium
coating
bath
metal
anodizing
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
Application number
US407454A
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English (en)
Inventor
Richard D Pittman
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.)
Northrop Grumman Guidance and Electronics Co Inc
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Litton Systems Inc
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 Litton Systems Inc filed Critical Litton Systems Inc
Priority to US407454A priority Critical patent/US3375179A/en
Priority to GB34029/65A priority patent/GB1078165A/en
Priority to GB45395/65A priority patent/GB1102899A/en
Priority to DE19651496885 priority patent/DE1496885A1/de
Priority to DE1496886A priority patent/DE1496886C3/de
Priority to CH1566765A priority patent/CH473902A/de
Priority to FR38599A priority patent/FR1462508A/fr
Application granted granted Critical
Publication of US3375179A publication Critical patent/US3375179A/en
Priority to US797327*A priority patent/US3481851A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00—Compounds of chromium
    • C01G37/02—Oxides or hydrates thereof
    • C01G37/033—Chromium trioxide; Chromic acid
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2684—Electrochemical processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16—Use of chemical agents
    • B01D2321/168—Use of other chemical agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • This invention relates to the treatment of metals and, more particularly, to methods, products, and processes for producing anodic films on beryllium metal.
  • lberyllium would be a very valuable metal if it could be properly worked and handled in various manufacturing processes.
  • the metal is especially light and strong; it has the most favorable strengthto-weight ratio of all light metals.
  • Its conductivity is approximately forty percent that of copper.
  • Beryllium melts -at 1285 C., a temperature higher than the melting point of copper. It has an unusually high modulus of elasticity. It has substantially no tendency to warp, exhibits very little change in dimensions with temperature, is an especially good thermal conductor, and has various other attributes which are desirable. Such characteristics make beryllium especially useful in situations where weight, strength, and resistance to dimensional change are important, e.g., in precision instruments.
  • beryllium has a very low atomic number and a low absorption characteristic which make it penetrable by X-rays so the pure metal has been used as windows in X-ray tubes for selective ltration of sof v X-rays, It has also been used in atomic reactors.
  • a number of useful alloys have been formed with copper, aluminum, nickel, gold, and iron. In general, these alloys are quite hard; for example, beryllium-copper is the hardest copper-'based alloy known.
  • a preferred form of the coating is hard, extremely heat conductive, of selectable color, and exhibits excellent dielectric properties.
  • My ⁇ method is especially useful because the coating may be formed evenly and consistently to provide the desired 'dimensionsl over almost any texture of surface of the beryllium metal.
  • a rough-textured beryllium surface, a smooth shiny beryllium surface, a striated beryllium surface, or substantially any other beryllium surface may be prepared.
  • the thickness may be limited so that it does not appreciably alfect dimensions of the coated part yet provides the desired characteristics. Bonding to the coating by commercial methods has .proven quite effective.
  • the method is very inexpensive, requires a short time, is substantially.insensitive to the looseness of controls practiced, and has many other desirable features.
  • Yet another object of my invention in a primary sense, is to anodize beryllium metal.
  • Another object of my invention is to cover beryllium metal evenly without changing its dimensions materially.
  • An additional object of my invention is to provide coatings for beryllium metal by easily controlled processes.
  • An additional object of my invention is to anodize beryllium with a coating of material having a thickness which may be accurately controlled to minimum dimensions.
  • Yet another object of my invention is to anodize beryllium with coatings to which other materials may be easily bonded by commercial methods.
  • the material may be cleaned by substantially any method desired.
  • the surface of the metal may be prepared in a manner such that it is dull, bright, or has almost any other desired characteristic.
  • the coating which forms may be made so thin that the nal surface is substantially identical to the original and exhibits its characteristics.
  • the part to be coated is connected to a positive source of DC potential; the negative terminal of the DC source is connected to an inert cathode material, eg., the container holding the coating bath.
  • the part is immersed in the coating solution; and the circuit is energized, either before or after the immersion.
  • a coating is formed on the beryllium having a particular color, a particular thickness, and others of the aforementioned characteristics, as desired.
  • anodizing baths are capable of turning beryllium black.
  • the baths do not produce coatings to which commercial high strength adhesives such as epoxy bond well.
  • the conventional bath Ifor blackening the exterior of beryllium metal is a chromic-acid/nitric-'acid solution which may contain as much as 701 Baum nitric acid (concentrated) and various other additives.
  • the coating produced is black, but slick and uneven.
  • the epoxy adhesives used in commercial bonding processes do not adhere well to the coat due to its slickness.
  • the coating does adhere well to the beryllium metal which it protects.
  • the coating is quite uneven. In order to provide appropriate overall protection of the beryllium nretal, the coating must be made so thick that general -dimensions of the material are changed. This is due to the fact that these coatings build up to cover the vsurface of the metal.
  • the coating abraded quite easily and had the wrong color for the planned use.
  • Postulating that beryllium oxide formed by the anodization lent the gray to the coating the sodium hydroxide concentration was increased and the boric acid concentration was decreased. This lessened the borate ion in solution and increased the beryllium oxide in the coating.
  • concentration of the bath reached four gram-moles of sodium hydroxide and three gram-moles of boric acid, the coating turned black. This was the second success in the experiments. Thereafter, I found that by lowering the boric acid content of the solution a thinner film was possible. After considering the bathV content, I decided to use sodium borate instead of boric yacid and to adjust the solution to fgive different pH concentrations. This arrangement proved the key to success in anodizing beryllium metal to obtain the desired properties.
  • the process of this invention amounts to an electrochemical formation of an oxide film of beryllium through the combination of ions from the bath solution with the beryllium metal anode.
  • a direct 5 current source is provided for biasing l'he beryllium metal anode to a positive potential.
  • the other terminal of the biasing source is connected to another electrode to define a cathode.
  • the cathode is the stainless steel tank used to hold the bath solution.
  • Vr Initial voltage.
  • Tg Thickness of coated sample.
  • V2 Final voltage.
  • T3 Thickness of coating in mils.
  • A1 Initial amperage.
  • A Area in square inches.
  • A2 Final amperage.
  • V.B. Voltage breakdown.
  • T1 Thickness of bare sample.
  • ASF Amperes per square foot.
  • Tgnlip. V1 V1 A1 A.; T1 T2 T3 A ASF V.B. Color 7. 0 13. 7 3. 2 245 2502 2503 .1 3. 87 9. 07 0 Tan. 7. 0 14.5 4. 8 455 2496 2497 .1 4. 51 15. 6 0 Dark Tan. 7. 0 14. 0 4. 0 305 2488 2438 .1 Ta 3. 2 13. 7 0 Golden Brown. 7. 0 13. 5 4. 5 620 2493 2493 .1 Ta 4. 03 22. 2 0 Black Violet. 7. 0 14.5 5. 6 720 2429 2429 .1 T3 4.03 25. 6 0 Metallic Blue. 7. 0 13. 7 6. 0 l. 120 2459 2459 .1 Ta 4. 28 37.
  • V1 Initial voltage.
  • T2 Thickness of coated sample.
  • V2 Final voltage.
  • Ts Thickness of coating in mils.
  • Ai 1nitial amperage.
  • A Area in square inches.
  • A2 Final amperage.
  • V.B. Voltage breakdown.
  • Tr Thickness of bare sample.
  • ASF AInperes per square foot.
  • the initial voltage is maintained at five or six volts.
  • higher voltages may be used.
  • the temperature of the bath need only be maintained between 70 and 180 Fahrenheit. Current is applied until the required thickness of coating is formed (e.g., from fifteen minutes-one hour).
  • a neutral solution of sodium borate is mixed with a small amount of sodium hydroxide to provide an excess of hydroxyl ions.
  • An especially useful solution contains sodium borate and sodium hydroxide in a ratio of 2.69 gram-moles to 0.77 gram-moles. As a potential is applied, oxygen is produced at the anodes, forming an oxide coating on the beryllium metal.
  • the coating actually comprises beryllium oxide held in a covalent bond with boron.
  • the structure of the beryllium is such that it may form a n-umber of diierent covalent bonds when different electrons are shared with oxygen thereby providing the different characteristics.
  • the bath comprises sodium b'ora'te having a consistency of 177 grams per liter and sodium hydroxide having a consistency of 30 grams per liter.
  • the bath is used at an operational tempera-ture of .to 120 Fahrenheit. An initial voltage of six volts is applied. The process continues for a period of yone hour. No particular preparation is necessary for this preferred bath though normally one of the chemicals is dissolved in solution and the bath brought to tempera-ture before the other is added.
  • no special cleaning techniques are required for this bath. This is in contrast ⁇ to the cleaning techniques necessary for anodizing aluminum in the standard chromic acid bath.
  • the material to be anodized is placed in the lbath solution as t-he anode.
  • the electrical connection to this material is normally insulated from the -bath solution to prevent an inappropriate anodizing from occurring at the connection itself.
  • the 4conductor 4to t-he ⁇ anode may be coated with a plastic material which is unaffected -by the anodzing bath; or an electrical connection of the same material, beryllium, may be used.
  • the particular operation is substantially insensitive to minor variations in parameters and produces a coating which is black, dielectric (measures 30G-500K ohms resistance), thin, bondable, and has a selectable surface and dimensions.
  • the thickness and nish of the coating is the fact that dimensions need not be programmed for the coating to allow corrections for add on during the process.
  • the coating is actually formed with the surface beryllium and is so thin thatV essentially the same dimensions and surface remain after the coating as those of the original material. The same surface remains though its constituency has changed. This is especially important in manufacturing precise instruments.
  • the multi-colored aspect of the coating allows a selection .for decorative, industrial, or other purposes.
  • the original black coating was chosen because a heat emissive exterior was desired for the particular instrument.
  • the coloring is accomplished in the bath without the necessity of a dyeing process, as is usual 'm aluminum anodizing.
  • another step is eliminated from ⁇ conventional processes.
  • the entire coating is of the selected color rather than just the surface portion so that the abrasion of the material is not so likely to cause flaws in the color as with aluminum anodized material.
  • the conductivity of the coating may be varied as desired.
  • a dielectric coating was desired.
  • Such a dielectric coating is especially useful in preventing electrical shorts and leakage in precision instruments and substantially eliminates galvanic corrosion which may tend to effect rapid deterioration of precision instruments using some prior art coatings.
  • the bondibility of the surface produced by the preferred process is also especially desirable.
  • the prior art techniques for producing a black coating on beryllium evidently were not gauged with modern production processes in mind, and the slick coating formed by some of the prior art techniques limited the techniques by which beryllium parts could be made to adhere to other elements.
  • Commercial epoxy adhesives designated FAS and LCA 4/ 9 a minimum block shear strength of 6100 p.s.i. was obtained.
  • the coating may be made both abrasion and corrosion resistant. For example, when subjected to a 5% salt water solution and to like vapors, the coating showed no effect after 120 hours though beryllium metal was severely etched after the same period.
  • a method of coating beryllium comprising the steps of immersing a piece of beryllium in an aqueous alkaline bath having a free hydroxyl ions and borate ions, placing a potential between said piece and a second terminal sufficient to generate a current in saidV bath wherein said piece is anodic, and anodizing said piece to produce a coating thereon.
  • a process of anodizing beryllium comprising the steps of preparing a desired surface on the beryllium metal by a selected cleaning technique, immersing the beryllium metal in an aqueous alkaline bath of an alkali metal borate solution containing free hydroxyl ions, connecting a source of potential between the beryllium metal as anode and a cathode, and passing current through the electrolyte bath by means of the source for a selected time.
  • a method for selectively coloring beryllium comprising the steps of preparing an aqueous alkaline bath comprising sodium hydroxide and boric acid having free hydroxyl ions, immersing the beryllium in the bath, connecting the beryllium to a positive terminal of an electrical source, applying a selected voltage between the beryllium and another point in the bath sufficient to pass current through the bath, and maintaining the current for a selected period.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Surface Treatment Of Glass (AREA)
US407454A 1964-10-29 1964-10-29 Method of anodizing beryllium and product thereof Expired - Lifetime US3375179A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US407454A US3375179A (en) 1964-10-29 1964-10-29 Method of anodizing beryllium and product thereof
GB34029/65A GB1078165A (en) 1964-10-29 1965-08-09 Improvements in or relating to method for producing anodic films on beryllium
GB45395/65A GB1102899A (en) 1964-10-29 1965-10-27 Apparatus and process for reconditioning metal treating solutions electrolytically
DE19651496885 DE1496885A1 (de) 1964-10-29 1965-10-29 Verfahren zum anodischen Oxydieren von Beryllium
DE1496886A DE1496886C3 (de) 1964-10-29 1965-11-12 Verfahren zum kontinuierlichen Regenerieren von chromsäurehaltigen elektrolytischen Behandlungslösungen mittels Dialyse
CH1566765A CH473902A (de) 1964-10-29 1965-11-13 Verfahren und Vorrichtung zum Regenerieren einer chromsäurehaltigen elektrolytischen Behandlungslösung
FR38599A FR1462508A (fr) 1964-10-29 1965-11-16 Procédé de régénération de solutions pour le traitement des métaux
US797327*A US3481851A (en) 1964-10-29 1969-01-10 Apparatus and procedure for reconditioning metal treating solutions

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US407454A US3375179A (en) 1964-10-29 1964-10-29 Method of anodizing beryllium and product thereof
US41130564A 1964-11-16 1964-11-16
US79732769A 1969-01-10 1969-01-10

Publications (1)

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US3375179A true US3375179A (en) 1968-03-26

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US407454A Expired - Lifetime US3375179A (en) 1964-10-29 1964-10-29 Method of anodizing beryllium and product thereof
US797327*A Expired - Lifetime US3481851A (en) 1964-10-29 1969-01-10 Apparatus and procedure for reconditioning metal treating solutions

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Application Number Title Priority Date Filing Date
US797327*A Expired - Lifetime US3481851A (en) 1964-10-29 1969-01-10 Apparatus and procedure for reconditioning metal treating solutions

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US (2) US3375179A (de)
CH (1) CH473902A (de)
DE (2) DE1496885A1 (de)
FR (1) FR1462508A (de)
GB (2) GB1078165A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140592A (en) * 1978-03-30 1979-02-20 The United States Of America As Represented By The Secretary Of The Air Force Gas bearing surface coating
CN103866371A (zh) * 2014-02-27 2014-06-18 北京航天控制仪器研究所 一种铍材电化学绝缘阳极氧化处理方法
CN106521605A (zh) * 2016-11-01 2017-03-22 中国工程物理研究院材料研究所 一种金属铍的微弧氧化电解液及工艺方法

Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674669A (en) * 1970-04-01 1972-07-04 Rai Res Corp Concentration of electrolyte from dilute washings by electrodialysis in a closed system
US3766049A (en) * 1971-08-26 1973-10-16 Process Res Inc Recovery of metal from rinse solutions
US4006067A (en) * 1973-03-05 1977-02-01 Gussack Mark C Oxidation-reduction process
US3933605A (en) * 1973-11-12 1976-01-20 United States Steel Corporation Non-polluting pickling method
US3983016A (en) * 1974-07-19 1976-09-28 Ppg Industries, Inc. Method of preparing chromium
US3909381A (en) * 1974-11-18 1975-09-30 Raymond John L Purification of chromium plating solutions by electrodialysis
US3926759A (en) * 1975-02-06 1975-12-16 Pitt Metals And Chemicals Inc Process for recovering tin salts from the waste rinse water of a halogen tin plating process
FR2314900A1 (fr) * 1975-06-18 1977-01-14 Niso Ste Civile Etud Rech Procede et installation de traitement des solutions de decapage de metaux
US4118295A (en) * 1976-04-20 1978-10-03 Dart Industries Inc. Regeneration of plastic etchants
US4149951A (en) * 1978-05-22 1979-04-17 Eddleman William L Frame filter press and apparatus
US4326935A (en) * 1978-11-06 1982-04-27 Innova, Inc. Electrochemical processes utilizing a layered membrane
US4243501A (en) * 1979-03-30 1981-01-06 Michael Ladney, Jr. Process and apparatus for the regeneration of chromic acid baths
US4188272A (en) * 1979-05-07 1980-02-12 Eastman Kodak Company Electrical chemical process for the removal of hexavalent chromium from aqueous medium
US4337129A (en) * 1979-05-08 1982-06-29 The United States Of America As Represented By The Secretary Of The Interior Regeneration of waste metallurgical process liquor
US4290864A (en) * 1979-05-29 1981-09-22 Diamond Shamrock Corporation Chromic acid production process using a three-compartment cell
US4325792A (en) * 1981-03-09 1982-04-20 Vaughan Daniel J Purification process
US4636288A (en) * 1984-01-06 1987-01-13 Vaughan Daniel J Electrodialytic conversion of multivalent metal salts
US4752373A (en) * 1985-01-14 1988-06-21 Morton Thiokol, Inc. Electrodialysis apparatus for the chemical maintenance of electroless copper plating baths
US4600493A (en) * 1985-01-14 1986-07-15 Morton Thiokol, Inc. Electrodialysis apparatus for the chemical maintenance of electroless copper plating baths
GB2248070A (en) * 1990-09-20 1992-03-25 Huang Yun Fu An apparatus for removing impurities contained in chrome plating bath
FR2668468B1 (fr) * 1990-10-26 1993-02-19 Electricite De France Cellule electrochimique, notamment pour recyclage d'acide chromique.
DE4109434C2 (de) * 1991-03-22 1993-12-23 Ludwig Mechler Gmbh Verfahren zum Aufarbeiten von chromathaltigen Abwässern und/oder Prozeßlösungen
DE4137377A1 (de) * 1991-11-13 1993-05-19 Jatzke Rudolf Fa Verfahren, mittel und vorrichtung zum elektrodialytischen regenerieren des elektrolyten eines galvanischen bades oder dergl.
US5246559A (en) * 1991-11-29 1993-09-21 Eltech Systems Corporation Electrolytic cell apparatus
EP0613862A3 (de) * 1993-02-03 1994-12-28 Metallgesellschaft Ag Verfahren zur Reduzierung der Schadstoffkonzentration von aus industriellen Prozessen stammenden Abwässern.
DE4407448C2 (de) * 1994-03-07 1998-02-05 Mib Metallurg Und Oberflaechen Elektrolyseverfahren zum Regenerieren einer Eisen-III-Chlorid- oder Eisen-III-Sulfatlösung, insbesondere zum Sprühätzen von Stahl
GB2293390A (en) * 1994-09-20 1996-03-27 British Tech Group Simultaneous etchant regeneration and metal deposition by electrodialysis
JP2918832B2 (ja) * 1995-12-15 1999-07-12 日英ハードクローム工業株式会社 クロムめっきにおけるクロムめっき液、クロムめっき廃液、クロム酸洗浄水用クローズド・リサイクル・システム
US6063252A (en) * 1997-08-08 2000-05-16 Raymond; John L. Method and apparatus for enriching the chromium in a chromium plating bath
DE19804534C1 (de) * 1998-02-05 1999-06-24 Otb Oberflaechentechnik Berlin Verfahren zur elektrolytischen Regeneration verunreinigter Rhodiumlösungen
US20040035696A1 (en) * 2002-08-21 2004-02-26 Reinhard Fred P. Apparatus and method for membrane electrolysis for process chemical recycling
AU2003902048A0 (en) * 2003-04-29 2003-05-15 M.I.M. Holdings Limited Method & apparatus for cathode plate production
US20100133097A1 (en) * 2008-12-01 2010-06-03 Hydrogen Technology Applications, Inc. Hydrogen rich gas generator
US10472723B2 (en) * 2015-01-06 2019-11-12 Thyssenkrupp Uhde Chlorine Engineers (Japan) Ltd. Method of preventing reverse current flow through an ion exchange membrane electrolyzer
KR102572078B1 (ko) * 2018-01-04 2023-08-30 삼성전자주식회사 스테인레스강의 부동태 표면 처리방법
JP7300820B2 (ja) * 2018-02-26 2023-06-30 三菱重工業株式会社 酸性処理液処理装置、酸性処理液処理方法、表面処理システム及び表面処理方法
CN114477573B (zh) * 2022-03-07 2023-05-16 盛隆资源再生（无锡）有限公司 一种硫酸铝溶液中三价铬和铝的分离方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2373273A (en) * 1942-10-28 1945-04-10 Rca Corp Signal recording and reproducing method
US2871425A (en) * 1954-09-16 1959-01-27 Fansteel Metallurgical Corp Capacitor
GB813994A (en) * 1955-10-21 1959-05-27 British Non Ferrous Metals Res Protective treatment of zinc surfaces
US3180807A (en) * 1961-10-23 1965-04-27 Lockheed Aircraft Corp Method for making film resistors
US3276974A (en) * 1963-01-18 1966-10-04 Ii Richard C Tyson Anodizing process for the metal beryllium

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US803543A (en) * 1905-02-16 1905-11-07 Anson Gardner Betts Electrolytic process using insoluble anodes.
US883651A (en) * 1906-01-31 1908-03-31 Basf Ag Electrolytic production of chromic acid.
US1851603A (en) * 1927-10-08 1932-03-29 Westinghouse Electric & Mfg Co Method for revitalizing chromium-plating solutions
US2865823A (en) * 1957-06-04 1958-12-23 United States Steel Corp Method of reclaiming waste pickle liquor
BE594986A (de) * 1959-09-28

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2373273A (en) * 1942-10-28 1945-04-10 Rca Corp Signal recording and reproducing method
US2871425A (en) * 1954-09-16 1959-01-27 Fansteel Metallurgical Corp Capacitor
GB813994A (en) * 1955-10-21 1959-05-27 British Non Ferrous Metals Res Protective treatment of zinc surfaces
US3180807A (en) * 1961-10-23 1965-04-27 Lockheed Aircraft Corp Method for making film resistors
US3276974A (en) * 1963-01-18 1966-10-04 Ii Richard C Tyson Anodizing process for the metal beryllium

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140592A (en) * 1978-03-30 1979-02-20 The United States Of America As Represented By The Secretary Of The Air Force Gas bearing surface coating
CN103866371A (zh) * 2014-02-27 2014-06-18 北京航天控制仪器研究所 一种铍材电化学绝缘阳极氧化处理方法
CN106521605A (zh) * 2016-11-01 2017-03-22 中国工程物理研究院材料研究所 一种金属铍的微弧氧化电解液及工艺方法
CN106521605B (zh) * 2016-11-01 2018-04-17 中国工程物理研究院材料研究所 一种金属铍的微弧氧化电解液及工艺方法

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DE1496885A1 (de) 1969-05-22
GB1102899A (en) 1968-02-14
CH473902A (de) 1969-06-15
FR1462508A (fr) 1966-04-15
DE1496886C3 (de) 1974-09-26
GB1078165A (en) 1967-08-02
DE1496886A1 (de) 1970-01-08
US3481851A (en) 1969-12-02
DE1496886B2 (de) 1974-02-14

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