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US2371725A - Lead-coated steel - Google Patents

Lead-coated steel Download PDF

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Publication number
US2371725A
US2371725A US429771A US42977142A US2371725A US 2371725 A US2371725 A US 2371725A US 429771 A US429771 A US 429771A US 42977142 A US42977142 A US 42977142A US 2371725 A US2371725 A US 2371725A
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US
United States
Prior art keywords
lead
copper
bath
coating
cyanide
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
US429771A
Inventor
James H Young
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US429771A priority Critical patent/US2371725A/en
Application granted granted Critical
Publication of US2371725A publication Critical patent/US2371725A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/10Lead or alloys based thereon

Definitions

  • Lead-coated steel articles for example leadcoated steel sheet
  • corrosion resistance is important.
  • Such lead-coated sheet is used, for example, for roofing.
  • Another important example is in .the'chemical industry where lead-coated sheet is used in contact with corrosive materials.
  • considerable difiiculty is com-- coatings such as those exemplified by terne plate are not satisfactory; and heretofore no suitable cheap method has been available for coating ferrous metals with lead of 95% or higher purity.
  • An object of the present invention is to provide an improved process for coating ferrous metal articles with lead. Another object is an improved, simple and cheap process for coating ferrous metalsurfaces with substantially pure lead.
  • My invention also includes the novel, leadcoated, ferrous metal articles as hereinafter described. Still other objects will be apparent from the following description of my invention.
  • substantially pure lead coatings or coatings containing about 95% or more by weight of lead can be produced on ferrous metal objects by first giving such objects a coating of copper and then immersing them in a bath of the molten lead.
  • the preliminary copper coating may be applied by any known method, for example by immersion plating or by electroplating.
  • I first coat the steel article with copper by giving it a copper strike coating by plating in a conventional copper cyanide plating bath, e. g., for 0.5 to 5 minutes.
  • I then provide a bath of molten lead and floatthereon a layer of an alkaline flux, consisting of amolten mixture of sodium cyanide and caustic soda.
  • the temperature of the bath Since pure lead may be maintained at, for example about 325- 400 C.
  • the coppered steel article to be coated is then dipped through the molten cyanide caustic flux layer, and thence into the molten lead bath. On removal of the steel article and cooling, a dense, adherent, uniform coating of lead is found on the steel article.
  • the cyanidecaustic flux may be kept in a conventional flux box so that the article to be'coated passes through the flux on its way into the lead bath but does not pass through the flux on removal from the bath.
  • the surface of the lead bath at the point the article is removed may be covered with a layer of suitable vegetable oil such as palm oil. or a hydrocarbon oil, for the purpose of smoothing and protecting the lead coating until ithas cooled.
  • an alkaline flux containing a metal cyanide.
  • I may use an alkali metal cyanide or mix-* tures of alkali metal cyanides with or without the addition of other alkaline materials such as alkali metal hydroxide, alkali metal carbonate, borax or the like.
  • a cyanide-free alkaline flux may be used, for example, molten caustic soda or mixtures of caustic soda and caustic potash.
  • the flux at least contains an appreciable amount, such as 10% or more, of an alkali metal cyanide.
  • the flux if desired, also may contain a small amount of a heavy metal cyanide, for example a cyanide of copper, lead, zinc or the like, which may be dissolved in the molten alkali metal cyanide present.
  • the metal article may be first immersed in the flux bath in aseparate container so as to I have further found that the preliminary cop-,
  • the per coating on the steel article may be obtained by contacting the ferrous metal surface with a molten bath comprising alkali metal cyanide having copper cyanide dissolved therein.
  • a temperature not lower than about 400 C. temperatures in the range of 400-500 C. are suitable.
  • the concentration-of copper cyanide in the cyanide melt should be at least about 20% byweight.
  • the copper cyanide-alkali metal cyanide bath may be utilized as the flux floating on the surface of the lead bath, or the steel article first may .be
  • the copper coating at a temperature of about 400-500 C. in a bath'separate from the lead bath and thendip the copper-coated article through an alkaline flux-which may or may not contain coppercyanide, the lead bath being maintained at a temperature not higher than 400 C.
  • the temperature of the lead hath not higher than about 400 C. While higher temperatures may be utilized if desired, and while baths at temperatures above 400 C. will produce lead coatingson steel, in general the most uniform andmost adherent lead coatings are obtained at temperatures not above 400 C. I have discovered that at higher temperatures there is some tendency for the copper coating to be removed from the steel, with the result that when such removal occurs the high degree of adherence of the lead, which is an object of this invention, is not attained. This tendency may be offset to some degree by utilizing a heavier copper .coating to begin with. However, for economical'reasons, it is preferable to utilize a light copper coating and keep the temperature of the lead bath not higher than 400 C., preferably at about 325-375 C.
  • the invention is not restricted thereto.
  • small amounts of other elements may be alloyed with the lead to modify its physical properties, for example, small amounts, not exceeding about 5% by weight, of tin, antimony, bismuth, magnesium, sodium, lithium, calcium, or the like.
  • the term "lead is used to mean any grade of lead or lead alloy containing not less than about 95% by weight of elemental lead.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)

Description

Patented Mar. 20, 1945 LEAD-COATED STEEL James H. Young Niagara Falls, N. Y., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del, a corporation of Delaware No Drawing. Application February 6, 1942, Serial No. 429,771
3 Claims. (Cl. 11771) @UNITED STATES PATENT OFFICE This invention relates to the production of corrosion-resistant coatings v(m iron and steel and more particularly to and improved method of coating steel with lead.
Lead-coated steel articles, for example leadcoated steel sheet, is utilized where corrosion resistance is important. Such lead-coated sheet is used, for example, for roofing. Another important example is in .the'chemical industry where lead-coated sheet is used in contact with corrosive materials. In making lead-coated articles of this sort, considerable difiiculty is com-- coatings such as those exemplified by terne plate are not satisfactory; and heretofore no suitable cheap method has been available for coating ferrous metals with lead of 95% or higher purity.
An object of the present invention is to provide an improved process for coating ferrous metal articles with lead. Another object is an improved, simple and cheap process for coating ferrous metalsurfaces with substantially pure lead. My invention also includes the novel, leadcoated, ferrous metal articles as hereinafter described. Still other objects will be apparent from the following description of my invention.
I have discovered that substantially pure lead coatings or coatings containing about 95% or more by weight of lead can be produced on ferrous metal objects by first giving such objects a coating of copper and then immersing them in a bath of the molten lead. The preliminary copper coating may be applied by any known method, for example by immersion plating or by electroplating. I
In one method of. practicing my process, which is described by way of illustration, Ifirst coat the steel article with copper by giving it a copper strike coating by plating in a conventional copper cyanide plating bath, e. g., for 0.5 to 5 minutes. I then provide a bath of molten lead and floatthereon a layer of an alkaline flux, consisting of amolten mixture of sodium cyanide and caustic soda. The temperature of the bath Since pure lead may be maintained at, for example about 325- 400 C. The coppered steel article to be coated is then dipped through the molten cyanide caustic flux layer, and thence into the molten lead bath. On removal of the steel article and cooling, a dense, adherent, uniform coating of lead is found on the steel article.
In carrying out the above described operation, conventional apparatus for hot 'dip coating of steel may be utilized. If desired, the cyanidecaustic flux may be kept in a conventional flux box so that the article to be'coated passes through the flux on its way into the lead bath but does not pass through the flux on removal from the bath. Likewise, if desired, the surface of the lead bath at the point the article is removed may be covered with a layer of suitable vegetable oil such as palm oil. or a hydrocarbon oil, for the purpose of smoothing and protecting the lead coating until ithas cooled.
In practicing this invention, as distinguished from the conventional method of making terne plate, I have found it is essential to utilize an alkaline flux. Preferably I utilize an alkaline flux containing a metal cyanide. For this purpose I may use an alkali metal cyanide or mix-* tures of alkali metal cyanides with or without the addition of other alkaline materials such as alkali metal hydroxide, alkali metal carbonate, borax or the like. A cyanide-free alkaline flux may be used, for example, molten caustic soda or mixtures of caustic soda and caustic potash. However the best results usually are obtained when the flux at least contains an appreciable amount, such as 10% or more, of an alkali metal cyanide. The flux, if desired, also may contain a small amount of a heavy metal cyanide, for example a cyanide of copper, lead, zinc or the like, which may be dissolved in the molten alkali metal cyanide present.
It is not always necessary to locate the flux bath on the surface of the molten lead bath. If desired, the metal article may be first immersed in the flux bath in aseparate container so as to I have further found that the preliminary cop-,
per coating on the steel article may be obtained by contacting the ferrous metal surface with a molten bath comprising alkali metal cyanide having copper cyanide dissolved therein. In thus .producing the copper coating it is preferable to utilize a temperature not lower than about 400 C.; temperatures in the range of 400-500 C. are suitable. The concentration-of copper cyanide in the cyanide melt should be at least about 20% byweight. In thismodificatio'n of the invention, the copper cyanide-alkali metal cyanide bath may be utilized as the flux floating on the surface of the lead bath, or the steel article first may .be
dipped into the copper cyanide bath to produce the copper coating and then dipped into the lead bath in a separate container. In this modification, generally I prefer to obtain the copper coating at a temperature of about 400-500 C. in a bath'separate from the lead bath and thendip the copper-coated article through an alkaline flux-which may or may not contain coppercyanide, the lead bath being maintained at a temperature not higher than 400 C.
In all cases I prefer to maintain the temperature of the lead hath not higher than about 400 C. While higher temperatures may be utilized if desired, and while baths at temperatures above 400 C. will produce lead coatingson steel, in general the most uniform andmost adherent lead coatings are obtained at temperatures not above 400 C. I have discovered that at higher temperatures there is some tendency for the copper coating to be removed from the steel, with the result that when such removal occurs the high degree of adherence of the lead, which is an object of this invention, is not attained. This tendency may be offset to some degree by utilizing a heavier copper .coating to begin with. However, for economical'reasons, it is preferable to utilize a light copper coating and keep the temperature of the lead bath not higher than 400 C., preferably at about 325-375 C.
While a prime object of my invention is to coat iron or steel with substantially pure lead coatings,
. for example coatings of lead having a purity of 99% by weight or higher, the invention is not restricted thereto. If desired, small amounts of other elements may be alloyed with the lead to modify its physical properties, for example, small amounts, not exceeding about 5% by weight, of tin, antimony, bismuth, magnesium, sodium, lithium, calcium, or the like. In the appended claims, the term "lead is used to mean any grade of lead or lead alloy containing not less than about 95% by weight of elemental lead.
I claim:
1. The process which comprises coating a ferrous metal surface with copper and bringing the copper-coated surface into contact with molten lead in the presence of molten sodium cyanide.
2. The process which comprises contacting a ferrous metal surface with an alkaline melt comprising molten sodium cyanide having at least about 20% by weight of copper cyanide dissolved therein, maintaining said ferrous surface in contherein, maintaining said ferrous surface in contact with said melt at a temperature of about 400 to 500 C. until said surface has acquired a coating of copper, and then contacting the resulting coppered surface with molten lead at a temperature of about 325 to 400 C. in the presence of a molten alkaline flux consisting essentially of caustic containing at least 10% by weight of sodium cyanide.
JAMES H. YOUNG.
US429771A 1942-02-06 1942-02-06 Lead-coated steel Expired - Lifetime US2371725A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2657458A (en) * 1949-01-29 1953-11-03 Rca Corp Method of joining copper members
FR2235208A1 (en) * 1973-06-29 1975-01-24 Bundy Corp
US3957086A (en) * 1973-06-29 1976-05-18 Bundy Corporation Corrosion resistant tubing
FR2524007A1 (en) * 1982-03-26 1983-09-30 Usui Kokusai Sangyo Kk COATED FERROUS COATED MATERIALS RESISTANT TO CORROSION

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2657458A (en) * 1949-01-29 1953-11-03 Rca Corp Method of joining copper members
FR2235208A1 (en) * 1973-06-29 1975-01-24 Bundy Corp
US3875027A (en) * 1973-06-29 1975-04-01 Bundy Corp Method of electroplating tubing prior to terne alloy coating
US3957086A (en) * 1973-06-29 1976-05-18 Bundy Corporation Corrosion resistant tubing
FR2524007A1 (en) * 1982-03-26 1983-09-30 Usui Kokusai Sangyo Kk COATED FERROUS COATED MATERIALS RESISTANT TO CORROSION

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