US2371725A - Lead-coated steel - Google Patents
Lead-coated steel Download PDFInfo
- 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
- Authority
- 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
Links
- 229910000831 Steel Inorganic materials 0.000 title description 16
- 239000010959 steel Substances 0.000 title description 16
- 238000000576 coating method Methods 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 230000004907 flux Effects 0.000 description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 6
- -1 ferrous metals Chemical class 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 230000001464 adherent effect Effects 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000648 terne Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/10—Lead 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.
Landscapes
- 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US429771A US2371725A (en) | 1942-02-06 | 1942-02-06 | Lead-coated steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US429771A US2371725A (en) | 1942-02-06 | 1942-02-06 | Lead-coated steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2371725A true US2371725A (en) | 1945-03-20 |
Family
ID=23704687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US429771A Expired - Lifetime US2371725A (en) | 1942-02-06 | 1942-02-06 | Lead-coated steel |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2371725A (en) |
Cited By (4)
| 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 |
-
1942
- 1942-02-06 US US429771A patent/US2371725A/en not_active Expired - Lifetime
Cited By (5)
| 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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