US2440715A - Continuous method for electropolishing nickel and nickel-containing alloys - Google Patents

Continuous method for electropolishing nickel and nickel-containing alloys Download PDF

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Publication number
US2440715A
US2440715A US495842A US49584243A US2440715A US 2440715 A US2440715 A US 2440715A US 495842 A US495842 A US 495842A US 49584243 A US49584243 A US 49584243A US 2440715 A US2440715 A US 2440715A
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Prior art keywords
nickel
bath
electropolishing
dissolved
area
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Expired - Lifetime
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US495842A
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English (en)
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Charles L Faust
Paul D Miller
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Battelle Development Corp
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Battelle Development Corp
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Priority to NL69990D priority Critical patent/NL69990C/xx
Priority to BE478067D priority patent/BE478067A/xx
Priority to LU28772D priority patent/LU28772A1/xx
Application filed by Battelle Development Corp filed Critical Battelle Development Corp
Priority to US495842A priority patent/US2440715A/en
Priority to GB15550/44A priority patent/GB607680A/en
Priority to CH277326D priority patent/CH277326A/fr
Application granted granted Critical
Publication of US2440715A publication Critical patent/US2440715A/en
Priority to DES19569A priority patent/DE855188C/de
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Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/22—Polishing of heavy metals

Definitions

  • This invention relates to an improved electrolytic bath for anodically polishing nickel and nickel-containing alloys. More particularly, the invention pertains to a method of continuously electropolishing nickel by means of an electrolyte from which excess nickel dissolved during the electropolishing step is continuously plated out on the cathode as metallic nickel.
  • Nickel and its alloysthat are rich in nickel may be anodically polished in an electrolyte containing, as an essential active ingredient, sulfuric acid or a mixture of sulfuric and phosphoric acids.
  • concentration of the sulfuric acid, when used alone, as well as the combined concentration of the mixed sulfuric and phosphoric acids should be at least 50% by weight of the solution and preferably not more than 95% by weight of the solution, the balance being largely water. For practical purposes, about 90% is the upper limit for the total acid concentration.
  • a mirror-like ilnish .hay be produced by anodically polishing nickel in aqueous solutions containing 15% H2SO4 and 63% H3PO4, using a current density of amperes per square foot and a bath temperature of 115 to 130 F.
  • the time required to produce the polish is determined by the original physical character of the nickel being polished.
  • a nickel compound is formed which breaks up at higher temperatures to form nickel sulfate. Consequently, a used bath precipitates nickel sulfate on the hot surfaces of the heating coils and the cathodes.
  • Reconditioning consists of heating at high temperature to precipitate nickel sulfate, l'tering, adjusting the bath composition, and cleaning the cathodes. The bath can then be operated until reconditioning again becomes necessary. Since such reconditioning is not commercially feasible in the production tank, separate tanks and the attendant auxiliary equipment are needed. Thus, reconditioning adds to the operating cost.
  • Another object of this invention is to provide an electrolyte and a method for electropolishing nickel capable of being operated continuously without a progressive rise in operating voltages.
  • a further object of this invention is to provide an electrolyte and a. method for electropolishing nickel capable of continuous operation at low temperatures.
  • Still a further object of this invention is to provide an electrolyte and a method for electropolishing nickel by the use of which excess nickel dissolved from the anode in the electropolishing step is continuously plated out as metallic nickel on the cathode of a degree of purity and in a physical state suitable for recovery and use as nickel.
  • Figure 1 illustrates areas representing bath compositions which, by the addition of between 0.04 and 2.5% of hydrochloric acid (HC1), are operative at temperatures between 80 and 140 F. for effecting the electropolishing of nickel and nickel alloys with simultaneous plating out of excess dissolved nickel.
  • HC1 hydrochloric acid
  • Figure 2 illustrates areas representing bath compositions which, by the addition of between 0.3 and 1.0% of hydrochloric acid (HC1), are operative at a temperature of 115 F. for effecting the electropolishing of nickel and nickel alloys with simultaneous plating out of excess dissolved nickel.
  • HC1 hydrochloric acid
  • Figure 3 is similar to Figure 2 except that it represents bath compositions operative at 90 F.
  • Figure 4 is similar to Figures 2 and 3, except it represents bath compositions operative at 135 F.
  • the phosphoric acid can be maintained in practically its original electropolishing condition because the nickel deposits out on the cathode during the operation of electropolishing.
  • the straight phosphoric acid bath does not have so good throwing power as the H2SO4- HaPOi combination. Therefore, the phosphoric acid bath is included only in the broad range of operable bath compositions.
  • the manner of introducing the chloride apparently is immaterial, but the simplest and most expedient method is to use hydrochloric acid. If a metal chloride were to be used, the quantity would be selected on the basis of equivalency to the chloride content of HCl specified in the opchloric acid to straight "phosphoric acid and to erative ranges that are disclosed herein. Since the specified purpose of this invention is to remove metals from the electropolishing bath, it is preferred to use hydrochloric acid, for the metal chlorides introduce a metal into the bath. We have also found that the desired effect of chloride additions can be achieved by introducing small concentrations of chlorinated organic acids, such as monochloroacetic acid,
  • the electropolishing bath as freshly made up with an addition of a chloroacetic acid gives no 6 tained.
  • the HC1 was maintained at the proper value by periodicadditions of concentrated hydrochloric acid.
  • the amount to be added was determined by chemical chemical test for a chloride. However, after a 5 analysis for chloride in the bath. short period oi' use for electropolishing, the bath While HCl additions tend to facilitate the platgives a positive test for chloride.
  • Such a material water content which also determines the soluis particularly well suited for use as anodes in bility limit If the minimum concentration of nickel electroplating tanks. nickel for a suitable deposition rate is greater Only minor percentages of chlorides are rethan the solubility limit, precipitation will be quired to produce the desired effect. There is 2o unavoidable. no practical way to add chloride ions, per se We .have found that upon addition of HCl withto the bath, or to determine what is the necesin the disclosed range, certain bath compositions sary chloride ion concentration.
  • H3PO422% H2O electropolishing bath Similar data for a H2SO4-38% H3PO427% H2O bath are shown in Table II.
  • the criterion for satisfactory bath operation is the eicient plating of nickel at the cathodes and the absence of an objectionable precipitate of nickel salts.
  • Table I shows some fluctuation in per cent nickel plated out in baths containing 0.04% or more HC1. This small variation is considered to be caused by changes in water and HC1 concentration. Periods of operation below 100% deposition are oiset by periods of more than 100% so that no operational difliculties are encountered when water and HC1 contents are suitably main- TABLE II Per cent nickel plated at the cathode 1 For various HCl additions to the 35 H2SO438% H3PO427% H2O bath for electropolz'shing nickel l Values based on amount of nickel dissolved from the anode for the interval of electro olishing shown.
  • I Ppt. indicates formation of a precipitate of nickel salt.
  • the larger area defined by the lines AC, CD, DE, EF, FG, GH and HA represents bath compositions as regards percentages of HsPOi, or of HaPOi and H2804, which, when containing minor additions of HC1, are suitable for el-ectropolishing nickel and nickel alloys at some or all temperatures within the broad temperature range of from 80 to 140 F. Within part or all of this temperature range. baths of a composition falling within the designated area and containing chloride additions within the limits above given, are operative to impart a. bright polish to nickel and its alloys, while at the same time most of the dissolved nickel coming out of solution' plates out at the cathode to permit continuous operation with only a slight precipitation of nickel salts, if any.
  • the broad operative range lies between 21 and 85% H3P04, 0 and 45% H2804, and 15 and 34% H2O.
  • the total acid concentration within this broad operative range has a minimum value of 66% and a maximum value of 85%.
  • the wholly enclosed smaller area lying within the straight dotted lines BI, IJ, JK, KG (full line), GL, LM and MB, represents the preferred ranges of bath compositions within which practically no precipitation of nickel sulfate occurs when the chloride content is within the limits given above and a proper temperature, within the range of from 90 to 125 F., is used for the composition selected.
  • nickel and its alloys can be satisfactorily polished anodically, while, at the same time, dissolved nickel is plated out at the cathode at a rate suiiicient to maintain the dissolved nickel content below its saturation point, and thus prevent any substantial precipitation of nickel salts.
  • the percentages of HaPOi lie between the limits of 38% and 77%, of H2804 between the limits of 2% and 28, and of water between 15% and 34%.
  • the combined HaP04 and H2804 concentration withln this same area lies between a minimum value of 66% and a maximum value of the same as in the larger composition area.
  • compositions within the larger area in Figure 1 defined by the lines AC, CD, DE, EF, FG, GH and HA
  • compositions within the smaller area in Figure l defined by the straight dotted lines BI, IJ', JK, the full line KG and the straight dotted lines GL, LM and MB
  • the compositions within the smaller area are yall operative within part or all of the temperature range of I-rom 90 to 125 F. However, other compositions outside the smaller area but inside the larger area may also be operative at a temperature between 90 and 125 F.
  • the dissolved nickel remains at a concentration within th'e range of about 0.5 to 2.5%, calculated as Ni. Since the H2804:H3P04:H20 values shown in the diagram are based on of the bath consisting only of the three mentioned components, the dissolved nickel and hydrochloric acid, or chloride content, alter all components to the same relative amount and to a degree that has nosigniilcant effect on the bath composition and.
  • Additions of chlorides may also be used eifectively to cause dissolved nickel to be continuously deposited as metallic nickel at the cathode during electropolishing in the high temperature baths containing additions of trivalent aluminum, or of trivalent aluminum and trivalent chromiuml as has been mentioned previously.
  • the advantages of both high temperature operation say, 180 F. to nearly boiling temperature, and continuous deposition of the dissolved nickel as metallic nickel on the cathode may be obtained.
  • the eil'ect of HC1 concentration on these baths is illustrated by the data in Table VII. ⁇
  • the baths of the present invention are opera.- tive for the electropolishing of nickel and nickel alloys containing at least 90% nickel together with alloying ingredients in amounts (generally less than 10%) such as will not materially affect the behavior of the nickel for electrolytic treatment purposes.
  • alloying ingredients in amounts (generally less than 10%) such as will not materially affect the behavior of the nickel for electrolytic treatment purposes.
  • 'I'he principles of the invention include broadly electropolishing nickel in baths containing a minor chloride addition furnished o by any compound selected from the group consisting of hydrochloric acid, metal (including ammonium) chlorides, and chlorinated organic acids.
  • polishing and electrodeposition of nickel can be satisfactorily carried out.
  • a siisht amount of precipitation of nickel salts may occur. but
  • the preferred bath compositions lie within the area delineated by the straight lines joining the points I, I, 0, I3, I4 and vl. in the order named. Within this area. both electropolishing and pickel electrodepositlon can be most satisfactorily performed.
  • the broader bath'composition limits for simultaneous polishing and plating are thoselying within the area defined by the straight lines joining the points I, l, l, Il, Il,
  • the preferred bath compositions lie within the limits of from to '17% H1PO4, 3 to 20% H1804 andA 15 to 30% H10, and within the area defined by the straight lines I-i, 0-0. O-IS, Il-II and II-l. In the broader bath composition range. the limits are from 31 to 85% HaPO4, 0 to 39% H2804. and 15 to 30% HzO'and lie within the area. defined by the straight lines l-l. l-I, 0--I
  • the preferred bath ⁇ compositions when containing from 0.3 to 1.0% HCl and operated at 90 F. lie within the area delineated by the straight lines joining the points 22, 23, 24, I9, 21 and 22, in the order named. Within this area, both electropol- .ishing and nickel electrodeposition can be most satisfactorily performed.
  • the broader bath composition limits for simultaneous polishing and plating are those lying within the area defined by the straight lines joining the points I5, 2
  • the preferred bath compositions lie within the limits of from 38 to 73% H3PO4, 3 to 28% H2SO4, and 24 to 34% H2O, and Within the area defined by the straight lines 22-23, 2li- 24, 2I-
  • the limits are 38 to 85% H3PO4, 0 to 28% H2804 and to 34% H2O and lie within the area dened by the straight lines I5-2 i, 2I-22, 22-23, 23-25, 25-28, 26-
  • the preferred bath compositions when containing from 0.3 to 1.0% HCl and operated at 135 F., lie within the area delineated by the straight lines joining the points 39, 36,31, 38, 33, 34 and 39, in the orde/r named. Within this area, both electropolishing and nickel electrodepition can be most satisfactorily performed.
  • the broader bath composition limits for simultaneous polishing and plating are those lyingwithin the area defined by the straight lines joining the points 28, 36, 3l, 33, 33, 34, 35 and 28.
  • the limits are 40 to 85% H3PO4, 0 to 30% H2804 and 15 to 30% H2O and lle within the area defined by the straight lines 28-36, 36-31, 31-38, 38-33, 33-314, 34-35 and 35-28.
  • the method of electrolytically polishing metal selected from the group consisting of nickel and nickel alloys containing at least nickel, which comprises making the metal the anode in an aqueous bath having a dissolved chloride ion content calculated -as HC1 of from 0.04 to 2.5% by weight of said bath, the remainder of said bath consisting essentially of a composition ly- -ing within the closed area defined on the accompanying diagram by -the solid straight lines AC, CD, DE, EF, FG, GH and HA, passing through said solution while held within the temperature range of from 80 to 140 F. an electrical current of suiicient density and for a sufficient period of time to effect the polishing oi. said metal, and during said electropolishing maintaining said bath at that temperature within said range at which anodically dissolved nickel will be electrodeposited from said bath whereby the tendency of nickel salts to precipitate on continued operation of said bath is reduced.
  • the method of electrolytlcally polishing metal selected from the group consisting of nickel and nickel alloys containing at least 90% nickel, which comprises making the metal the anode in an aqueous bath having a dissolved chloride ion content calculated as lHC1 of froml 0.04 to 2.5% by weight of said bath, the remainder of said bath consisting essentially of a composition lying within the closed area defined on the accompanying diagram by the dotted straight lines BI. IJ, and JK, the solid straight lineKG and the dotted straight lines GL, LM and ,MB, passing through said solution while held within a temperature range of from 90 to 125 F.
  • an aqueous solution having a, dissolved chloride ion content calculated as HC1 of from about 0.04 to 2.5% by weight of said solution and containing up to saturation of dissolved nickeLthe dissolved nickel content calculated as Ni being at least equal' to 0.5% by weight of said solution, the remainder of said solution consisting essentially of a composition lying within the closed area on the accompanying diagram defined by the solid straight lines AC, CD, DE, EF, FG, GH and HA.
  • an aqueous solution having a dissolved chlorideion content calculated'as 4HC1 of from about 0.04 to 2.5% by weight of said solution and containing up to saturation of dissolved nickel, the dissolved nickel content calculated as Ni being atleast equal to 0.5% by weight of said solution.
  • the remainder of said solution Iconsisting essentially of a composition lyingwithin the closed area on the accompanying diagram dened by the dotted straight lines BI, IJ, and JK, the solid straight line'KG lines GL, LM and MB.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US495842A 1943-07-23 1943-07-23 Continuous method for electropolishing nickel and nickel-containing alloys Expired - Lifetime US2440715A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL69990D NL69990C (en)) 1943-07-23
BE478067D BE478067A (en)) 1943-07-23
LU28772D LU28772A1 (en)) 1943-07-23
US495842A US2440715A (en) 1943-07-23 1943-07-23 Continuous method for electropolishing nickel and nickel-containing alloys
GB15550/44A GB607680A (en) 1943-07-23 1944-08-15 Improvements in or relating to methods of anodically electropolishing nickel and nickel-containing alloys and electrolytes suitable for use in said method
CH277326D CH277326A (fr) 1943-07-23 1947-08-08 Procédé pour le polissage anodique.
DES19569A DE855188C (de) 1943-07-23 1950-09-26 Verfahren zum Elektropolieren von Nickel und nickelhaltigen Legierungen und hierzu geeigneter Elektrolyt

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BE (1) BE478067A (en))
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GB (1) GB607680A (en))
LU (1) LU28772A1 (en))
NL (1) NL69990C (en))

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2861930A (en) * 1956-09-13 1958-11-25 Smith Corp A O Method of electropolishing and electrolytic solution therefor
US2874104A (en) * 1954-10-26 1959-02-17 Sylvania Electric Prod Electropolishing method
US3213008A (en) * 1961-06-14 1965-10-19 Ametek Inc Electrolytic polishing of stainless steel
US4038702A (en) * 1973-09-21 1977-08-02 Philip Nicholas Sawyer Electrochemical and chemical methods for production of non-thrombogenic metal heart valves
US5380408A (en) * 1991-05-15 1995-01-10 Sandvik Ab Etching process
CN103822817A (zh) * 2014-02-28 2014-05-28 金川集团股份有限公司 一种纯镍化学抛光浸蚀液及其使用方法
US12043915B2 (en) 2019-10-08 2024-07-23 Lake Region Manufacturing, Inc. Electropolishing of MP35N wire for fatigue life improvement of an implantable lead

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE225873C (en)) *
US1918477A (en) * 1933-07-18 Gesellschait
US2003051A (en) * 1933-07-05 1935-05-28 Victor Chemical Works Purification of strong phosphoric acid
GB504026A (en) * 1937-09-17 1939-04-17 Harold Robert Priston Improvements in or relating to the polishing of nickel applicable also to the production of decorative or other designs upon the surface
DE682248C (de) * 1937-05-20 1939-10-20 Hans Burkhardt Dr Ing Elektrolytisches Glaenzverfahren fuer rostfreie Stahllegierungen
GB526966A (en) * 1938-12-21 1940-09-30 Houdaille Hershey Corp Improvements in or relating to methods of electrobuffing nickel
US2315696A (en) * 1939-08-16 1943-04-06 Battelle Memorial Institute Polishing of metal surfaces
US2315695A (en) * 1938-11-23 1943-04-06 Battelle Memorial Institute Method of polishing metals
US2331721A (en) * 1939-08-12 1943-10-12 Rustless Iron & Steel Corp Polishing stainless iron and steel
US2366714A (en) * 1942-04-24 1945-01-09 Battelle Memorial Institute Electrolyte for and method of anodically polishing copper
US2366713A (en) * 1939-11-06 1945-01-09 Battelle Memorial Institute Method of anodically polishing nickel

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE225873C (en)) *
US1918477A (en) * 1933-07-18 Gesellschait
US2003051A (en) * 1933-07-05 1935-05-28 Victor Chemical Works Purification of strong phosphoric acid
DE682248C (de) * 1937-05-20 1939-10-20 Hans Burkhardt Dr Ing Elektrolytisches Glaenzverfahren fuer rostfreie Stahllegierungen
GB504026A (en) * 1937-09-17 1939-04-17 Harold Robert Priston Improvements in or relating to the polishing of nickel applicable also to the production of decorative or other designs upon the surface
US2315695A (en) * 1938-11-23 1943-04-06 Battelle Memorial Institute Method of polishing metals
GB526966A (en) * 1938-12-21 1940-09-30 Houdaille Hershey Corp Improvements in or relating to methods of electrobuffing nickel
US2331721A (en) * 1939-08-12 1943-10-12 Rustless Iron & Steel Corp Polishing stainless iron and steel
US2315696A (en) * 1939-08-16 1943-04-06 Battelle Memorial Institute Polishing of metal surfaces
US2366713A (en) * 1939-11-06 1945-01-09 Battelle Memorial Institute Method of anodically polishing nickel
US2366714A (en) * 1942-04-24 1945-01-09 Battelle Memorial Institute Electrolyte for and method of anodically polishing copper

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2874104A (en) * 1954-10-26 1959-02-17 Sylvania Electric Prod Electropolishing method
US2861930A (en) * 1956-09-13 1958-11-25 Smith Corp A O Method of electropolishing and electrolytic solution therefor
US3213008A (en) * 1961-06-14 1965-10-19 Ametek Inc Electrolytic polishing of stainless steel
US4038702A (en) * 1973-09-21 1977-08-02 Philip Nicholas Sawyer Electrochemical and chemical methods for production of non-thrombogenic metal heart valves
US5380408A (en) * 1991-05-15 1995-01-10 Sandvik Ab Etching process
CN103822817A (zh) * 2014-02-28 2014-05-28 金川集团股份有限公司 一种纯镍化学抛光浸蚀液及其使用方法
US12043915B2 (en) 2019-10-08 2024-07-23 Lake Region Manufacturing, Inc. Electropolishing of MP35N wire for fatigue life improvement of an implantable lead

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CH277326A (fr) 1951-08-31
LU28772A1 (en))
BE478067A (en))
DE855188C (de) 1952-11-10
GB607680A (en) 1948-09-03
NL69990C (en))

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