US3864221A - Coating of a steel or iron with a chromium containing surface layer - Google Patents

Coating of a steel or iron with a chromium containing surface layer Download PDF

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Publication number
US3864221A
US3864221A US372618A US37261873A US3864221A US 3864221 A US3864221 A US 3864221A US 372618 A US372618 A US 372618A US 37261873 A US37261873 A US 37261873A US 3864221 A US3864221 A US 3864221A
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United States
Prior art keywords
chromium
layer
steel
coating
iron
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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
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US372618A
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English (en)
Inventor
Lars Henry Ramqvist
Henrik Werme
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Rederi Nordstjernan AB
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Rederi Nordstjernan AB
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/917—Treatment of workpiece between coating steps
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating

Definitions

  • ABSTRACT A ductile chromium coatingis produced on a carboncontaining steel or iron substrate by first coating the substrate with at least one metal from the group consisting of Cu, Ag, Au, Pd, Pt, Rh, Ir, Ru, Os and CuNi alloy and then depositing a metal layer consisting essentially of chromium by electrolysis from a salt bath at a temperature in excess of 700C.
  • the present invention relates to a process for the preparation of a ductile surface coating of chromium on steel or iron.
  • chromium layer To coat steel and iron objects with a chromium layer is an old, well-known technique widely used. Normally the coating with chromium is carried out by means of electrolysis in an aqueous solution containing chromic acid. The temperature of the electrolyte is usually 5060C.
  • a chromium layer prepared by means of water electrolysis serves substantially only a decorative purpose, as the layer normally has bad corrosion properties. This is due to the fact that such a chromium layer is crisscrossed by a great number of microcracks, through which corrosive media may penetrate to the steel underlayer and corrode this. For this reason chromium coated objects exposed to atmospheric corrosion, e.g., car details, are coated with a corrosion protective layer of nickel or nickel and copper between the steel underlayer and the chromium layer. The chromium layer is not ductile, and therefore objects to be chromium coated must have the form intended for final use before the chromium coating, which is a great disadvantage for such details as piston rings and springs. The brittleness of chromium layers prepared by means of water electrolysis depends on a relatively high oxygen content.
  • chromizing it is also known to coat steel objects or substrates, preferably such having a low content of carbon, at high temperature with a coherent chromium layer according to the so-called pack-diffusion method (chromizing).
  • the chromium layers obtained are tight and have very good corrosion properties.
  • pack-diffusion methods There are several different pack-diffusion methods, and they are characterized in that the surface coating is obtained at a high temperature, often more than l000C, and that the chromium atoms are conveyed to the surface of the steel in the form of gaseous chromium halide, e.g. CrCl This reacts with the iron atoms of the underlayer forming chromium and gaseous iron halide.
  • the chromium layer to some extent reacts with the carbon in the steel underlayer, a very brittle layer of chromium carbide being obtained between the steel underlayer and the chromium layer.
  • the greatest disadvantages of the known methods are thus that they do not provide ductile and tight chromium layers on medium and high carbon steels or iron.
  • steel or iron substrates are coated with a metal layer, substantially consisting of chromium.
  • This chromium layer is in the ductile state. In this way the excellent corrosion properties of the chromium are utilized at the same time as the coated material is ductile.
  • a steel or iron coated according to the present invention can thus be used as constructional material, especially in corroding atmosphere, e.g. for piston rings, springs, mine hoisting ropes, bracing wires and fence wire.
  • the present process is characterized in that the steel or iron surface is coated with a layer substantially consisting of one or several of the metals Cu, Ag, Au, Pd, Pt, Rh, Ir, Ru or Os or of a CuNi-alloy and that a layer substantially consisting of chromium is then precipitated by electrolysis in a salt melt containing a chromium halide or by reduction of a gaseous chromium halide.
  • a layer of a metal is first precipitated on the steel or iron surface, acting as a barrier for a carbon diffusion from the iron, and then a layer is precipitated substantially consisting of chromium.
  • the precipitation of chromium either takes place electrolytically in a salt bath containing a chromium halide or by reduction of a chromium halide in gaseous phase. in both cases the precipitation must take place at a high temperature.
  • the first layer can thus according to the invention consist of one or several of the metals copper, silver, gold, palladium, platinum, rhodium, iridium, ruthenium or osmium or an alloy of one or several of these metals as main constituent. Copper has been found to be most suitable, and especially good results of the end product have been obtained, when this barrier layer of copper also contains some amount of nickel.
  • the barrier layer can be coated according to some known method, preferably electrolytically. It is an advantage if this layer is heat treated before the chromium layer is coated. in this way a stronger adhesion to the underlayer is obtained by diffusion in the boundary surface. If no special heat treatment is carried out before the chromium coating, the diffusion takes place during the chromium coating, as this must be carried out at a high temperature according to the invention.
  • the barrier layer will prevent diffusion of carbon from the iron to the chromium layer deposited on the barrier layer. This prevents the development of chromium carbides making the chromium layer brittle.
  • the thickness of the barrier layer must be adapted to the carbon content in the steel or iron to be coated. Thus a high carbon steel requires a thicker barrier layer than a low carbon steel.
  • the thickness of the barrier layer is also dependent on the temperature selected during the chromium coating. At temperatures within a higher temperature range, e.g. more than 1000C, a thicker barrier layer is required than if the chromium coating takes place at for instance 800C.
  • the chromium coating in salt melt is carried out at a temperature high enough for a metal diffusion occurring through the interfaces. To obtain a diffusion within the time of electrolysis the temperature should therefore exceed 700C.
  • the upper limit of the temperature depends on the composition of the salt melt, but for practical reasons 1l00C should not be exceeded.
  • the salt melt substantially consists of sodium chloride or potassium chloride or preferably a mixture thereof.
  • it must contain a chromium halide, preferably chromium (Il)chloride. It is also suitable that the melt is protected with a neutral atmosphere, e.g. argon gas, to avoid oxidation.
  • the chromium coating in gaseous phase is carried out through reduction of a chromium halide, preferably chromium(ll)chloride, in gaseous phase with hydrogen gas. This reduction must be carried out at a temperature higher than 1000C.
  • the chromium halide used can to a small extent be replaced with another metal halide, e.g., nickel halide, the coating being formed by an alloy substantially consisting of chromium.
  • the present invention the presents of high amounts of oxygen is avoided in the chromium layer.
  • the barrier layer prevents the formation of carbide in the chromium layer.
  • the relatively high temperatures at which the chromium coating is carried out result in good contact between the coating layers and the underlayer due to metal diffusion. All this leads to a product that after the coating with chromium can still be shaped or worked to some extent without the chromium layer breaking.
  • a steel wire, which at an analysis showed 0.12 percent C, 0.22 percent Si and 0.5 percent Mn was coated with a copper layer of 0.003 mm thickness by means of electrolysis at room temperature for 1.5 min.
  • the electrolyte consisted of an aqueous solution containing 25 g/l copper cyanide, 34 g/l sodium cyanide and g/l sodium carbonate.
  • the current density was 10 A/dm
  • a chromium layer of 0.007 mm thickness was applied to this copper layer by means of electrolysis in salt melt for 10 min. at 750C, the current density being 3.6 A/dm 2.
  • the electrolysis was carried out in argon atmosphere.
  • composition of the salt melt was 49.5 percent by weight of NaCl, 49.5 percent by weight of KCl and 1 percent by weight of CrCl
  • the chromium layer obtained was coherent, fine-granular and ductile.
  • the coated wire was wound around its own diameter without the chromium layer breaking or delaminating from the underlayer.
  • a high carbon flat wire which at analysis showed 0.81 percent C, 0.23 percent Si and 0.54 percent Mn, was coated with a nickel layer of 0.002 mm thickness by means of electrolysis at room temperature.
  • the current density was 5 A/dm and the time of electrolysis was 2 min.
  • the composition of the electrolyte was 300 g/l nickel sulphate, 30 g/l nickel chloride and 30 g/l boric acid.
  • a copper layer of 0.003 mm thickness was applied by means of electrolysis to a high carbon band steel.
  • the band steel showed at analysis 0.80 percent C, 0.23 percent Si and 0.54 percent Mn.
  • the electrolysis was carriedout in the same electrolyte and in other respects under the same conditions as in example 1.
  • the band steel was coated electrolytically with another layer of nickel.
  • the thickness of the nickel layer was 0.005 mm.
  • the nickel electrolyte consisted of an aqueous solution containing 300 g/l nickel sulphate, 45 g/l nickel chloride, g/l boric acid and a wetting agent, viz.
  • band steel was coated with a chromium layer of0.0l2 mm thickness by means of electrolysis in a salt melt of 47.5 percent by weight of NaCl, 47.5 percent by weight of KCl and 5.0 percent by weight of CrCl
  • the electrolysis was carried out at 900C in argon atmosphere.
  • the current density was 7.1 A/dm and the time of electrolysis was 10 min.
  • the band was bent 180 without the chromium layer breaking or delaminating.

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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)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
US372618A 1972-07-07 1973-06-22 Coating of a steel or iron with a chromium containing surface layer Expired - Lifetime US3864221A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
SE7209011A SE372043B (cs) 1972-07-07 1972-07-07

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US3864221A true US3864221A (en) 1975-02-04

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4432839A (en) * 1981-06-18 1984-02-21 Diamond Shamrock Corporation Method for making metallided foils
US4840711A (en) * 1981-01-13 1989-06-20 Metafuse Limited Process for the fusion of one element into a second element
US6485026B1 (en) 2000-10-04 2002-11-26 Dana Corporation Non-stainless steel nitrided piston ring, and method of making the same
US20150176113A1 (en) * 2013-10-22 2015-06-25 Sam Rae Jung Partial heat treatment method in salt bath at low temperature

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1535339A (en) * 1924-05-10 1925-04-28 Peacock Samuel Process for electrolytically depositing elemental chromium upon metals
US1927773A (en) * 1931-06-02 1933-09-19 Purdue Research Foundation Electroplating chromium, etc., on iron, etc.
US2438013A (en) * 1940-07-22 1948-03-16 Patents Corp Treated steel sheet and process
US3232853A (en) * 1962-03-05 1966-02-01 Gen Electric Corrosion resistant chromide coating
US3585068A (en) * 1966-06-07 1971-06-15 Albright & Wilson Chromising of ferrous metal substrates

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1535339A (en) * 1924-05-10 1925-04-28 Peacock Samuel Process for electrolytically depositing elemental chromium upon metals
US1927773A (en) * 1931-06-02 1933-09-19 Purdue Research Foundation Electroplating chromium, etc., on iron, etc.
US2438013A (en) * 1940-07-22 1948-03-16 Patents Corp Treated steel sheet and process
US3232853A (en) * 1962-03-05 1966-02-01 Gen Electric Corrosion resistant chromide coating
US3585068A (en) * 1966-06-07 1971-06-15 Albright & Wilson Chromising of ferrous metal substrates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4840711A (en) * 1981-01-13 1989-06-20 Metafuse Limited Process for the fusion of one element into a second element
US4432839A (en) * 1981-06-18 1984-02-21 Diamond Shamrock Corporation Method for making metallided foils
US6485026B1 (en) 2000-10-04 2002-11-26 Dana Corporation Non-stainless steel nitrided piston ring, and method of making the same
US20150176113A1 (en) * 2013-10-22 2015-06-25 Sam Rae Jung Partial heat treatment method in salt bath at low temperature
CN105683404A (zh) * 2013-10-22 2016-06-15 Dk-Lok公司 低温盐浴局部热处理方法
US9534284B2 (en) * 2013-10-22 2017-01-03 Dk-Lok Corporation Partial heat treatment method in salt bath at low temperature

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Publication number Publication date
SE372043B (cs) 1974-12-09

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