US3917517A - Chromium plating electrolyte and method - Google Patents

Chromium plating electrolyte and method Download PDF

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US3917517A
US3917517A US508866A US50886674A US3917517A US 3917517 A US3917517 A US 3917517A US 508866 A US508866 A US 508866A US 50886674 A US50886674 A US 50886674A US 3917517 A US3917517 A US 3917517A
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chromium
concentration
ions
electrolyte
hypophosphite
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Joseph Thomas Jordan
John Joseph Bernard Ward
Clive Barnes
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International Lead Zinc Research Organization Inc
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International Lead Zinc Research Organization Inc
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    • 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
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium

Definitions

  • the present invention relates to electroplating baths containing trivalent chromium ions and -to methods of electrodepositing chromium from such baths.
  • the buffers used tend to be rather expensive and thus improved performance has to be offset against higher material costs. Furthermore being preferably aprotic the buffers may cause a reduction in the conductivity of the bath. Also since many of the common ion supplying materials (added, among other reasons, to increase the conductivity) are less soluble in buffer/water mixtures than in buffer free systems, the conductivity increase afforded by the inclusion of these materials may be limited. Decreased conductivity leads to increased heat production. At high buffer concentrations the bath may need to be cooled under operating conditions. In addition the buffered trivalent chromium electrolytes may suffer from a relatively restricted plating range and have a relatively low covering power. These deficiencies are associated with the pH at which the buffered solutions are operable. It is known that to obtain a good plating range it is preferable to have the pH as high as possible. Unfortunately, unless the pH is kept relatively low the chromium precipitates out.
  • hypophosphite ion to trivalent chromium plating baths, either as a supplement to an organic buffer or as a replacement for it, provides an electrolyte which mitigates or overcomes manyof these disadvantages.
  • the present invention accordingly provides an aqueous chromium electroplating bath containing dissolved trivalent chromium ions and hypophosphite ions, preferably in a concentration of at least about 0.08 molar. it is also preferred that ammonium ions be present in a concentration of at least 0.2 molar.
  • the invention also provides a method of electrodepositing chromium-containing deposits onto a substrate which process comprises providing an anode and a cathode in a chromium electroplating bath according to the invention and passing an electric current between the anode and .cathode so as to deposit chromium upon the cathode.
  • hypophosphite ion concentration of hypophosphite ion which are useful have not yet been evaluated but up to about 2 molar, improvements are noticeable. At higher concentrations the improvement with increasing concentration is small and also normal hypophosphite salts are not usually sufficiently soluble; The preferred range is from 0.5 to 2.0 molar in respect of hypophosphite ion.
  • the source of hypophosphiteion is not bei lieved to be critical provided the ion is not associated with materials which would have a deleterious effect on the performance of the plating bath.
  • Sodium hypophosphite e.g. as the monohydrate (NaH PO .H O) and hypophosphorous acid are possible sources. When using sodium hypophosphite the molar concentration limits on the hypophosphite ion represent from about 10 to 200 g/l with a preferred range of about 50 to 150 g/l.
  • hypophosphite ion in trivalent chromium electrolytes results in a remarkable increase in 'the plating range and particularly the bright plating range of the electrolyte.
  • Previous DMF buffered trivalent chromium plating baths have typical bright plating ranges of 125 to 3000 Amps/meter?
  • the use of hypophosphite either additionally to, or as a replacement for the DMF or other organic buffer can produce electrolytes with bright plating ranges of from 30 to 10,000 Amps/meter".
  • the extension of plating range is a sub-. stantial advance over prior trivalent chromium baths.
  • a further effect on the electrolyte is that in the presence of hypophosphite ion the: deposition of chromium at low current densities takes place at relatively high efficiency and at high current densities at relatively low efficiency.
  • This effect can be such that in the electrolytic plating of chromium onto objects shaped so as to produce a wide range of current densities, the deposition rate may be very nearly uniform and independent of current density.
  • the actual deposition efficiency is a complex function of many parameters both of the electrolyte and of the operating conditions.
  • hypophosphite electrolytes overall efficiencies typically in the range from 3 to 16% based on the trivalent chromium ion can be obtained. These efficiencies produce plating rates as good as those obtainable from the best available hexavalent chromium systems.
  • the efficiencies are rather lower than those which can be obtained with the addition of high levels of DMF (or other organic buffer), but this is more than offset by the improvement in plating performance obtained. It should be noted in this regard that when comparing current efficiencies it is important to correct for the valency of the ion being deposited to obtain a true comparison.
  • the degree to which the improved plating performance is realized depends inter alia on the concentration of hypophosphite ion. As indicated above at concentrations less than about 0 .08 molar the improvements are scarcely noticeable, at concentrations up to about 0.5 molar a shift of the chromium threshold current density to lower values (from a zero concentration figure of about 125 Ampslmeter to about Amps/- meter is observed. Further increases of the hypophosphite concentration extend the plating range to even lower current densities (optimally as low as 30 Amps/- meter As a result of reduced efficiency at high current densities, and a subsequent reduction of the deleterious high deposition rate at high current densities, the tendency of the deposit to burn is also reduced.
  • hypophosphite produces so significant an improvement-in the deposition of chromium. At present it is thought probable thatthree separate but inter-related effects are present. Hypophosphorous acid is a weak acid and so the presence of hypophosphite ion increases the pH of the electrolyte. Increasing electrolyte pH. is known from previous experience to be beneficial. However, previously, with DMF baths, such an increase of pH would have resulted in the precipitation of chromium, as complex hydroxides, from the solution. The presence of hypophosphite ion very surprisingly prevents this.
  • the third way in which it seems that hypophosphite may be affecting chromium deposition is concerned with the actual electrode processes which are thought to be involved in the electrolytic deposition of chromium.
  • the deposition of chromium metal from trivalent chromium solutions is thought to be a two stage process.
  • the trivalent chromium ion is first reduced to the divalent state and subsequently to metallic chromium.
  • the rate and ease of chromium deposition is thought to be determined by concentration of divalent chromium ions. In normal circumstances there is atendency for divalent chromium to revert by oxidation to trivalent chromium thus slowing the overall reaction.
  • hypophosphite seems to stabilize divalent chromium in relation to trivalent chromium and also to make the formation of divalent chromium from trivalent chromium by electrons in the solution more rapid. It is thought that this is associated with the activity of hypophospite as a reducing agent although it seems that there is no net consumption of hypophosphite during electrolysis. It seems from this that not only does the hypophosphite ion stabilize trivalent chromium against high ph and divalent chromium against oxidative reversion, butalso that in the presumptive trivalent chromiumhypophosphite complex the trivalent chromium is also acting to stabilize the hypophosphite against against oxidation.
  • hypophosphite-containing trivalent chromium electrolytes can be employed at rather higher pHs than were previously possible with DMF baths.
  • the electrolytes of the present invention are operable to give electrodeposits of chromium or chromium alloys within the pH range of from 0.5 to 7, the preferred range being for chromium from 1.5. to 3.5.
  • Previous baths were substantially restricted to a pH of from 1 to 3. This improvement in the operable pH range is important because it allows an increase in the plating range and also it can be useful in reducing the acidic attack on the substrate at the start of electroplat- 4
  • the concentration of trivalent chromium ions in the electrolyte is lesscritical than in previous system s.
  • the chromium ion concentration will be from 0.5 to 1.75 molar, preferably from 0.7 to 1.3 molar.
  • the chromium may be used in the form ofits chloride, other halide salts, sulphate, phosphorous oxy acid salts, salts with organic acids or salts orcomplexes with other anions.
  • the salts may be normal, complex or basic, noting that pH adjustment may be necessary.
  • the trivalent chromium ions may be generated in situ by the action of acid (e.g. hydrochloric, sulphuric or phosphoric acids) on the metal, its oxides (other than CrO or hydroxides.
  • chromic ion examples include (I) chromic acid reduced by hydrogen peroxide, (2) a 57% basic solid salt (i.e. a solid salt containing 57% by weight Cr O and the remainder a neutral salt such as CrCl or (3) a basic salt such as a 57% basic solid salt in a sufficient amount of acid to yield a solution of the neutral salt (e.g. a 57% basic solid salt in sufficient hydrochloric acid to yield a solution of CrCl
  • basic salts can contain from 0% to 57% basic solids.
  • hypophosphite v and trivalent chromium concentrations generally correspond so that for a relatively small concentration of trivalent chromium ions a low level of hypophosphite is desirable and similarly for large concentrations of trivalent chromium ions a high level of hypophosphite isappropriate.
  • Molar ratios oftrivalent chromium to hypophosphite in the range of from 0.16 to 5 are useful but ratios in the range of 0.7 to 1.7 are preferred.
  • the anions present in the electrolyte are not critical- Since the bath does not require DMF or similar buffers the range of anions possible is widened somewhat. However, because hypophosphite is a moderately powerful reducing agent, anions with strongly oxidizing properties are thought to have deleterious effects. Thus among common anions nitrate and nitrite are not preferred anions. Among preferred anions are halide, expecially chloride, bromide and iodide, sulphate and phosphate anions of varr ious types. Minor proportions of other anions may also be present as a result of the inclusion of various additives as is discussed below.
  • hypophosphite baths can .tolerate mixtures of anions easily. It is believed that use of a common anion in hypophosphite baths does, not giveany substantial advantage from a technical point of view.
  • the hypophosphite baths of the present invention 7 can advantageously include organic buffersfAs is the case in prior trivalent chromium. platingbaths, the preferred organic buffers arethose with a highly electronegative oxygen atom and are also preferably aprotic. The most preferred in dimethylformamide.
  • the organic buffers usable in the present invention are those described and defined in US. Pat. No. 3,772,170.
  • DMF or other buffer
  • Chromic sulphate is available at the present time in a form sufficiently pure that no organic buffer may be necessary in the electrolyte to make operation feasible. However, such buffers are optional components of sulphate baths.
  • the electrolytes of this invention tend to produce rather larger quantities of gaseous hydrogen than the previous DMF type systems. This is particularly true in electrolytes containing little or no organic buffer. Inclusion of atnmoniumion improves the stabilityand conductivity of the electrolyte. Inorder'to have a significant effect a concentration of about 0.2 molar ammonium ion is necessary. The concentration can be increased up to about 6 molar to increase the effect and a preferred range of concentration is from 1 -to 4 molar.
  • Su ch additives improve bath performance with re- .spect to plating range, current efficiency and covering surfactants employed in trivalent chromium baths were of the cationic type, other types not being preferred because of the tendency to produce dull'deposits or black specks.
  • the present electrolytes are much less sensitive in this respect and cationic, amphoteric and non-ionic types of surfactant are applicable.
  • Present indications are that the former disadvantage of anionic agents may well be overcome in the present invention. This increased tolerance is believed to be a result of the higher possible pI-Is available with the present invention.
  • Suitable surfactants are:
  • Non-ionic type higher fatty alcohols ethers and epoxide s.
  • Typical levels of addition of surfactants are from 5 to 50 ppm.
  • a possible further benefit which can be obtained from the inclusion of a suitable surfactant is that itmay be useful in reducing spray from the bath resulting from the increased evolution of hydrogen mentioned above.
  • levellers and brighteners can be included in the electrolyte of the present invention but their presence is not critical and the benefits obtained are rather less than with previous systems.
  • di-n-alkyl phthalates e.g. di-n-pentyl phthalate and di-n-butyl phthalate improve the current density range over which chromium alloys
  • the ammonium ion may be added as a halide or sulphate salt or as a mixture of salts orby. reaction of ammonia with acid in situ.
  • phthalate esters The role of phthalate esters is uncertain but in the deposition ofchromium/iron co-deposits they increase the non-rusting rangeof deposits. There does not seem to be a particular lower limit of concentration effective in the electrolytes of the present invention andimprovements are found up to saturation. It is convenient to use a saturated solution in the presence of a small quantity of liquid phthalate ester to ensure continuing saturation. Various other additives such as cetyltrimethylammonium bromide can also be beneficial when used together with hypophosphite.
  • the temperature range over which the present invention. is operable is similar to that for previous trivalent chromium electrolytes Operation is preferred at or near ambient temperature, say in the range 25 i 5C.
  • the practical maximum temperature depends upon the anions present in the bath. With chloride baths about 35C is the operational maximum but with sulphate baths operation up to 55C is possible.
  • organic buffer (DMF) free systems are operable athigher temperatures than those including organic buffers
  • the electrolytes of the present invention typically have substantially higher conductivities than the prior (DMF) type electrolytes and this has the dual advantage of reducing the voltage requirements and reducing the heating due to electrical resistance for a given overall current level.
  • the best electrolytes of the present invention can operate substantially at thermal equilibrium at ambient or near ambient temperatures. Thus, to a large extent there is no longer any requirement for deliberate external cooling of the system.
  • the p'resent'electrolyte also permits the direct chromium plating on reactive substrates such as zinc, aluminum and brass without first plating the substrate with copper or nickel as is required with conventional hexavalent chromium baths. Because of their higher typical operating pH, hypophosphite baths are superior to prior trivalent chromium direct plating systems in that the substrate is less subject to acidic attack. However, some acidic attack will take place unless a thin protective layer of chromium is struck on the substrate. This can be ensured by immersing the substrate live in the bath, and/or by using a high initial current density.
  • An important subsidiary feature of the present invention is the possibility of forming co-deposits or alloys by employing a suitable mixture of cations in the electrolyte.
  • chromium-iron, chromium-nickel and chromium-iron-nickel systems are chromium-iron, chromium-nickel and chromium-iron-nickel systems.
  • the dynamics of such binary and ternary systems are complex and are not fully understood. However, insofar as they affect the composition of the deposit formed on the cathode, the following factors appear to be relevant.
  • the rate of deposition of chromium from an electrolyte of constant composition is virtually independent of current density and also of any other cations which may be being co-deposited on the cathode.
  • the actual amount of chromium metal deposited on the cathode is constant. This is not true of either iron or nickel, the rate of deposition of both metals being a function of concentration.
  • the functions connecting concentration and rate of deposition are direct but not linear.
  • hypophosphite baths With hypophosphite baths the dependency of the rate of deposition of iron and/or nickel upon current density is considerably reduced compared with previous systems. Thus, it is possible to plate approximately constant composition irrespective of current density. This leveling effect is not, however, so prominent with iron and nickel as it is withchromium and thus there is some variation of deposit composition with current density.
  • Non-rusting plate has been produced at current densities as low as 50 Amps/- meter but it is expected that this range will be extended with further work. The precise reasons for this improvement are not known but may bea result of the evening'up of the deposition rate vs. current density function in the presence of hypophosphite.
  • the improvement in non-rusting plating range can be augmented by the inclusion of phthalate esters particularly DPP.
  • any iron supplied to the electroplating bath of the invention be in a lower valency state. Usually the iron will be supplied as a ferrous salt.
  • the concentration ofiron if present, will be from 0.05 M to 2.5 M, preferably 0.1 M to 1 M, and the concentration of nickel, if present, from 0.05 M to 1 M, preferably 0.1 M to 0.5 M.
  • concentration of iron and/or nickel is dependent upon the desired composition of the alloy to be' deposited.
  • the present electrolyte can be used to produce coatings containing inert particulate material.
  • the material in the form of particles usually 5 pm diameter or smaller or whiskers usually from 3 to 6 mm. long and up to pm in diameter is suspended in the electrolyte during electroplating by air agitation or the like.
  • the cathode is thus provided with a chromium deposit (or codeposit with other metal) in which the particles or whiskers are embedded.
  • the sizes of particles or whiskers used can be larger than the values indicated if suitably strong solution agitation is used.
  • Typical inert materials useful in this application include alumina,- yttria, zirconium diboride, molybdenum disulphide and tungsten carbide. Incorporation of such materials makes the electroplated layer much harder and wear resistant than would otherwise be the case.
  • the electrolytes of the invention can be madeby admixture of the components and then adjusting the pH.
  • Starting with normal chromic salts, sodium hypophosphite and preferably ammonium salts of mineral acids, together with, as desired, boric acid, a surfactant or other additive discussed above, and dissolving them in water or aqueous/organic buffer mixtures will in general produce an electrolyte whose natural pH is in the preferred range of pH for plating.
  • the pH of any mixture will depend upon the precise nature of the starting materials.
  • the pH may be adjusted simply by adding mineral acid or caustic alkali (or ammonia) as appropriate.
  • the invention also provides a composition comprising a mixture of the components of the electrolyte which, when dissolved in water, aqueous acid or alkali or in mixtures of these with an organic buffer, will produce a solution suitable for use as an electrolyte according to the invention.
  • the mixture will have the following composition:
  • trivalent chromium ion (CR 25 to 100, preferably 35 to 70, parts by weight.
  • hypophosphite ion H PO to 130, preferably 40 to 100, parts by weight.
  • ammonium ion (Ni-1 3 to 100, preferably 20 to 70, parts by weight.
  • the weight ratio of chromium ion to hypophosphite ion should be from 0.16 to 4, preferably from 0.6 to 1.4, and the weight ratio of chromium ion to ammonium ion should be from 0.5 to 7, preferably 1 to 4.
  • the chro mium hypophosphite and ammonium ion concentrations are here expressed in terms of the ions and not, of
  • the ratios of trivalent chromium ion to hypophosphite ion and trivalent chromium ion to ammonium ion should be within the ranges stated above.
  • the electrolytes of the invention seem to possess substantial operational stabilityover extended periods of time. Baths have been operating satisfactorily over30 Ampere hours/litre. The electrolytesolution s are not entirely stable under all storage conditions. At storage 10 pHs lower than 1.5 current efficiency tends to rise, and at pHs higher than 3.5 efficiency tends to fall. The solid formulations discussed above are believed to the stable over indefinite periods.
  • the long term operational stability of the electrolytes is a further indication that the hypophosphite is not either rapidly consumed during electrolysis or that the decomposition products of hypophosphite that may be produced are not deleterious.
  • the electrolytes of the present invention are operable over long periods'by simply providing more trivalent chromium ions (and other deposit forming species) to the electrolyte together with water as appropriate and, when necessary small quantities of acid or alkali to maintain the pH. Dragout losses are replaced by addition of bathconstituents.
  • the deposits produced from the electrolyte and by the process of the present invention are darker in hue than hexavalent chromium bath deposits. They appear to be slightly darker than is normal for prior trivalent chromium systems. Dupernell testing at 0.25 am has shown the deposit to be intensely microporous. Chromium and chromium-iron, chromium-nickel and chromium-iron-nickel deposits produced by the invention are extremely resistant to concentrated hydrochloric acid and the complete dissolution of even a 0.25 pm coating may take up to 1% hour. With alloy coatings, heating may be necessary to effect complete dissolution. Thicker deposits progressively darken in color as plating time increases and eventually become black.
  • the method of the invention can be used to plate chromium and chromium alloys onto all conventional substrates such as iron, steel nickel, as well as more difficult substrates such as aluminum, copper, brass and zinc.
  • Adhesion failure of chromium on overbrightened or imperfectly activated nickels has been observed. This sort of adhesion failure can be overcome, eg by a brief cathodic treatment at 1500 Amps/meter in 10% sodium cyanide followed by a good rinsing before deposition of the chromium.
  • the present electrolyte and method of electroplating avoid the difficulties previously associated with anodic chlorine production. There is now no need to select special anodes or separate anolyte or catholyte.
  • the anode can conveniently be made of graphite.
  • One feature which is more apparent with this bath than previous trivalent chromium systems is that more hydrogen is evolved at the cathode, especially at low or :zero organic buffer concentrations. This is an inconvenience rather than a disadvantage as the production of gaseous hydrogen does not seem to have any effect on plating characteristics or on the deposit formed.
  • the surface spray produced by the evolution of hydrogen can be overcome by including a surface active agent in the electrolyte as is indicated above.
  • the invention may be illustrated by the following Examples.
  • EXAMPLE 1 An electroplating bath having the following composition was made up:- t.
  • the electrolyte had the following properties:
  • pH 3 plating range 75 to 6000 Amps/meter Hull cell voltage 18V Hull cell current 10A Samples were plated in a bath containing the electrolyte for 2 minutes at 25C giving the following deposits:
  • the electrolyte had the following properties:
  • pH 2.5 plating range 50 to 10,000 Amps/meter Hull cell voltage 13V Hull cell current 10A Samples were plated for 2 minutes at 25C giving the following results:
  • EXAMPLE V An electrolyte having no boric acid was made up according to the invention as follows:
  • the thickness were determined coulormetrically by stripping the chromium to the nickel substrate.
  • the bath was adjusted with ammonia to pH 2.5 and possessed 'a'plating range on a nickel coated Hull cell plate of 60 to 4800 Amps/meter.
  • Hull cell voltage and I current were 10V and 10A coulormetrically.
  • Example V111 was repeated omitting DPP from the electrolyte and using 400 g DMF and 600 g H O. The pH was 1.5. The results are given in Table 2.
  • Electrolytes according to the present invention for the deposition of chromium-nickel and chromiumnickel-iron alloys were tested by formulating the following:
  • a Hull cell panel was plated.
  • the quality of the deposit was poor with numerous black streaks in the deposit and there were two distinct regions: at high current densities, a chromium rich region and at low current densities, a nickel rich region.
  • Table 3 also records the effect of adding 100 g/l of FeCl .41-I O to the electrolyte to produce a ternary system. Good quality deposits were obtained and the nonrusting range extended to Ampsimeter This elec- 5O trol te has metal de osition efficiencies a roachin NaH PO C D Time Corn osition Efficiency y p pp g 2 2 m g, p 50%.
  • the deposit is predominantly iron, it is g/l m t Fe Cr Fe Cr +C contemplated that by adjusting the formulation, a de- 0 300 300 gm 9D L0 posit of composition similar to 18/8 stainless steel 0 1500 150 68.5 31.5 20.0 12.0 32.0 ld b obtained.
  • An electrolyte solution for electrodeposition of chromium on a substrate comprising hypophosphite ions in a concentration of at least about 0.08 M, trivalent chromium ions in a concentration of at least about'0.5 M, and containing at least 1% dimethylformamide.
  • a method of electrodepositing a chromium coating on a substrate which comprises immersing said substrate in an electrolyte solution comprising water, hypophosphite ions in a concentration of at least about 0.8 M and trivalent chromium ions in a concentration of at least 0.5 M, maintaining the temperature below about 55C and passing an electric current through said 16 solution thereby to deposit said trivalent chromium ions on a substrate.
  • a method according to claim 6 including the step of maintaining the temperature below about 35C.
  • a method according to claim 6 including the step of maintaining the temperature between about 20C and 30C.

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US4107004A (en) * 1975-03-26 1978-08-15 International Lead Zinc Research Organization, Inc. Trivalent chromium electroplating baths and method
FR2382521A1 (fr) * 1977-03-04 1978-09-29 Int Lead Zinc Res Bains pour galvanoplastie au chrome trivalent
DE2818780A1 (de) * 1977-06-14 1978-12-21 Ibm Galvanisches bad zum elektroplattieren von chrom oder chromlegierungen
DE2847961A1 (de) * 1977-01-26 1979-05-17 Ibm Chromquelle fuer das elektroplattieren, ihre herstellung und verwendung
US4196063A (en) * 1978-06-02 1980-04-01 International Lead Zinc Research Organization, Inc. Electrodeposition of black chromium
WO1982003095A1 (en) * 1981-03-09 1982-09-16 Battelle Development Corp High-rate chromium alloy plating
US4569699A (en) * 1985-05-08 1986-02-11 The Dow Chemical Company Method for providing a corrosion resistant coating for magnesium containing materials
US4610763A (en) * 1984-04-07 1986-09-09 Inter Metals And Minerals, S.A. Electrodeposition of chromium and chromium bearing alloys
US4615773A (en) * 1984-05-07 1986-10-07 State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Portland State University Chromium-iron alloy plating from a solution containing both hexavalent and trivalent chromium
US4892628A (en) * 1989-04-14 1990-01-09 The United States Department Of Energy Electrodeposition of amorphous ternary nickel-chromium-phosphorus alloy
US5194100A (en) * 1991-02-08 1993-03-16 Blount, Inc. Heat treatable chromium
US5413646A (en) * 1991-02-08 1995-05-09 Blount, Inc. Heat-treatable chromium
US5868917A (en) * 1994-10-28 1999-02-09 Floquet Monopole Process for the electrodeposition of a chromium coating containing solid inclusions and plating solution employed in this process
FR2885370A1 (fr) * 2005-05-03 2006-11-10 Commissariat Energie Atomique Procede de depot electrochimique, source de rayonnements alpha et x, fabriquee par ce procede, et dispositif d'analyse pixe-xrf, utilisant cette source.
CN102352521A (zh) * 2011-11-09 2012-02-15 广东达志环保科技股份有限公司 一种环保滚镀型三价铬电镀液及其滚镀方法
US20120052319A1 (en) * 2009-02-13 2012-03-01 Atotech Deutschland Gmbh Chrome-plated part and manufacturing method of the same
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WO2012059473A1 (de) * 2010-11-04 2012-05-10 Technische Universität Wien Verfahren zur abscheidung von hartchrom aus cr(vi)-freien elektrolyten
WO2015088876A1 (en) * 2013-12-10 2015-06-18 Lei Chen Nickel-chromium-aluminum composite by electrodeposition
US20160116446A1 (en) * 2013-04-26 2016-04-28 Sumitomo Electric Industries, Ltd. Analysis method for organic substances in solution to be examined
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US10378118B2 (en) 2013-12-11 2019-08-13 United Technologies Corporation Electroformed nickel-chromium alloy
US10563316B2 (en) 2014-12-24 2020-02-18 Posco Fe—P—Cr alloy thin plate and method for manufacturing same
US10669867B2 (en) 2013-12-10 2020-06-02 Raytheon Technologies Corporation Electrodeposited nickel-chromium alloy
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FR2474538A1 (fr) * 1980-01-28 1981-07-31 Tardy Rene Procede de depot electrolytique de chrome au moyen d'un bain de chrome trivalent
JPS6156294A (ja) * 1984-08-27 1986-03-20 Nippon Kokan Kk <Nkk> クロム合金メツキ浴
DE102006025847A1 (de) * 2006-06-02 2007-12-06 Merck Patent Gmbh Verwendung von Phosphinsäure in der Galvanotechnik
CN102041529B (zh) * 2011-01-12 2012-07-04 山东轻工业学院 一种在环保型三价铬镀液中制备镍铬合金复合镀层的方法
FI129420B (en) 2020-04-23 2022-02-15 Savroc Ltd AQUATIC ELECTRIC COATING BATH
DE102021002197A1 (de) * 2021-04-27 2022-10-27 VDEh-Betriebsforschungsinstitut Gesellschaft mit beschränkter Haftung Vorrichtung und Verfahren zum Beschichten eines Bauteils oder Halbzeugs mit einer Chromschicht

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US4107004A (en) * 1975-03-26 1978-08-15 International Lead Zinc Research Organization, Inc. Trivalent chromium electroplating baths and method
DE2847961A1 (de) * 1977-01-26 1979-05-17 Ibm Chromquelle fuer das elektroplattieren, ihre herstellung und verwendung
FR2382521A1 (fr) * 1977-03-04 1978-09-29 Int Lead Zinc Res Bains pour galvanoplastie au chrome trivalent
DE2818780A1 (de) * 1977-06-14 1978-12-21 Ibm Galvanisches bad zum elektroplattieren von chrom oder chromlegierungen
US4196063A (en) * 1978-06-02 1980-04-01 International Lead Zinc Research Organization, Inc. Electrodeposition of black chromium
WO1982003095A1 (en) * 1981-03-09 1982-09-16 Battelle Development Corp High-rate chromium alloy plating
US4610763A (en) * 1984-04-07 1986-09-09 Inter Metals And Minerals, S.A. Electrodeposition of chromium and chromium bearing alloys
AU568432B2 (en) * 1984-04-07 1987-12-24 Inter Metals And Minerals S.A. Electrodeposition of chromium and chromium bearing alloys
US4615773A (en) * 1984-05-07 1986-10-07 State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Portland State University Chromium-iron alloy plating from a solution containing both hexavalent and trivalent chromium
US4569699A (en) * 1985-05-08 1986-02-11 The Dow Chemical Company Method for providing a corrosion resistant coating for magnesium containing materials
US4892628A (en) * 1989-04-14 1990-01-09 The United States Department Of Energy Electrodeposition of amorphous ternary nickel-chromium-phosphorus alloy
US5194100A (en) * 1991-02-08 1993-03-16 Blount, Inc. Heat treatable chromium
US5413646A (en) * 1991-02-08 1995-05-09 Blount, Inc. Heat-treatable chromium
US5868917A (en) * 1994-10-28 1999-02-09 Floquet Monopole Process for the electrodeposition of a chromium coating containing solid inclusions and plating solution employed in this process
FR2885370A1 (fr) * 2005-05-03 2006-11-10 Commissariat Energie Atomique Procede de depot electrochimique, source de rayonnements alpha et x, fabriquee par ce procede, et dispositif d'analyse pixe-xrf, utilisant cette source.
US20080152078A1 (en) * 2005-05-03 2008-06-26 Istituto Nazionale Di Fisica Nucleare Alpha and X Radiation Source, Pixe-Xrf Analysis Device Using this Source and Method for Making the Source
US11248300B2 (en) 2009-02-13 2022-02-15 Nissan Motor Co., Ltd. Chrome-plated part and manufacturing method of the same
US20120052319A1 (en) * 2009-02-13 2012-03-01 Atotech Deutschland Gmbh Chrome-plated part and manufacturing method of the same
US10266957B2 (en) * 2009-02-13 2019-04-23 Nissan Motor Co., Ltd. Chrome-plated part and manufacturing method of the same
WO2012059473A1 (de) * 2010-11-04 2012-05-10 Technische Universität Wien Verfahren zur abscheidung von hartchrom aus cr(vi)-freien elektrolyten
CN102383150A (zh) * 2011-11-09 2012-03-21 广东达志环保科技股份有限公司 一种高耐蚀环保三价铬电镀液及其电镀方法
CN102383150B (zh) * 2011-11-09 2014-08-20 广东达志环保科技股份有限公司 一种高耐蚀环保三价铬电镀液及其电镀方法
CN102352521A (zh) * 2011-11-09 2012-02-15 广东达志环保科技股份有限公司 一种环保滚镀型三价铬电镀液及其滚镀方法
CN102352521B (zh) * 2011-11-09 2015-03-11 广东达志环保科技股份有限公司 一种环保滚镀型三价铬电镀液及其滚镀方法
US20160116446A1 (en) * 2013-04-26 2016-04-28 Sumitomo Electric Industries, Ltd. Analysis method for organic substances in solution to be examined
US10669867B2 (en) 2013-12-10 2020-06-02 Raytheon Technologies Corporation Electrodeposited nickel-chromium alloy
US10669851B2 (en) 2013-12-10 2020-06-02 Raytheon Technologies Corporation Nickel-chromium-aluminum composite by electrodeposition
WO2015088876A1 (en) * 2013-12-10 2015-06-18 Lei Chen Nickel-chromium-aluminum composite by electrodeposition
US10378118B2 (en) 2013-12-11 2019-08-13 United Technologies Corporation Electroformed nickel-chromium alloy
US11732372B2 (en) 2013-12-11 2023-08-22 Raytheon Technologies Corporation Electroformed nickel-chromium alloy
US10563316B2 (en) 2014-12-24 2020-02-18 Posco Fe—P—Cr alloy thin plate and method for manufacturing same
CN108026654A (zh) * 2015-09-09 2018-05-11 萨夫罗克有限公司 基于铬的涂层，用于制备基于铬的涂层的方法以及涂覆的物体
CN108026654B (zh) * 2015-09-09 2020-11-27 萨夫罗克有限公司 基于铬的涂层，用于制备基于铬的涂层的方法以及涂覆的物体
US11371156B2 (en) 2015-09-09 2022-06-28 Savroc Ltd Chromium-based coating, a method for producing a chromium-based coating and a coated object
EP3744874A1 (en) * 2019-05-29 2020-12-02 Coventya SAS Electroplated product with corrosion-resistant coating
WO2020239932A1 (en) * 2019-05-29 2020-12-03 Coventya Sas Electroplated product with corrosion-resistant coating
US20210017659A1 (en) * 2019-07-18 2021-01-21 The Boeing Company Functional chromium alloy plating from trivalent chromium electrolytes

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GB1482747A (en) 1977-08-10
NL7413211A (nl) 1975-04-14
CA1030094A (en) 1978-04-25
FR2247550B1 (enrdf_load_stackoverflow) 1979-04-27
JPS5066442A (enrdf_load_stackoverflow) 1975-06-04
IT1020962B (it) 1977-12-30
FR2247550A1 (enrdf_load_stackoverflow) 1975-05-09
DE2447897A1 (de) 1975-04-17
SE7412152L (enrdf_load_stackoverflow) 1975-04-11
JPS5742713B2 (enrdf_load_stackoverflow) 1982-09-10
BE820802A (nl) 1975-02-03
AU7383874A (en) 1976-04-08

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