US3827140A - Method of surface treating steel products with metal powder - Google Patents

Method of surface treating steel products with metal powder Download PDF

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Publication number
US3827140A
US3827140A US00294898A US29489872A US3827140A US 3827140 A US3827140 A US 3827140A US 00294898 A US00294898 A US 00294898A US 29489872 A US29489872 A US 29489872A US 3827140 A US3827140 A US 3827140A
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US
United States
Prior art keywords
metal
aluminum
slurry
powder
particle size
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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
Application number
US00294898A
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English (en)
Inventor
H Yamagishi
F Yokoi
T Kutino
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.)
JFE Engineering Corp
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Nippon Kokan Ltd
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Publication date
Priority claimed from JP4920769A external-priority patent/JPS4931182B1/ja
Application filed by Nippon Kokan Ltd filed Critical Nippon Kokan Ltd
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    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • C23C24/085—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/087—Coating with metal alloys or metal elements only
    • 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
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/4998—Combined manufacture including applying or shaping of fluent material
    • Y10T29/49982—Coating

Definitions

  • SHEET 2 (IF 2 IO/ IOO.
  • This invention relates to a method of surface treatment wherein a powder of metal is suspended in water and the suspension is applied upon the surface of steel products.
  • the invention is characterized by the utilization of fine metal powder capable of suspending in water.
  • a stabilizer may be incorporated into the suspension.
  • coated layer applied by the molten metal spray method is thin, numerous pin holes are formed in the coated layer to decrease the corrosion resistant property of the products.
  • thick coated layers decrease adhesion of the coated layers to the substrate.
  • Further object of this invention is to provide a novel method of forming protective coatings on steel products without utilizing any special atmosphere and heat treatment apparatus.
  • the invention provides a method of forming on a steel plate a homogenous and beautiful coating layer of excellent formability by the steps of suspending fine metal powder, aluminum powder for example in water, incorporating a slurry stabilizer which also acts as a corrosion preventing agent into the suspension, applying the mixture on the surface of the steel plate, thereafter heating, rolling and reheating.
  • a steel strip is payed off from a pay off reel, passed successively through an electrolytic degreasing bath, a pickling bath, scrubber and drier and is then applied with an aluminum coating by a roll coater.
  • the invention is characterized in that the grain size of the aluminum powder supplied to the roll coater is selected to be smaller than 325 mesh. Where aluminum powder of larger grain size is admixed with water and the mixture is applied on the surface of the steel strip by means of the roll coater, the aluminum powder will not be coated uniformly by forming local lumps for example, thus making it difficult to form beautiful and uniform coating. For this reason, it was necessary to use a viscosity increasing agent or a binder. However, such agents adversely affect the adhesion of the coating.
  • incorporation of an aluminum powder of less than 325 mesh eliminates all defects described above and uniformly disperses the aluminum powder in water to provide a slurry mixture having a constituent sufficient to be applied smoothly and readily on the steel surface with a roll coater.
  • a suitable ratio of water to aluminum is selected, it is possible to select any desired quality of aluminum to be coated and to precisely adjust the thickness of the coated layer to form continuous coating on the steel surface without utilizing any viscosity increasing agent.
  • phytinic acid is incorporated in an amount of about 10 to 1,000 ppm.
  • phytinic acid is added into water which undergoes reaction within several hours, the slurry becomes stable over hours.
  • phytinic acid In corporation of phytinic acid not only improves the stability of aluminum powder but aldo prevents rusting of the surface of the steel plate even when it takes a long time before the surface is dried after coating, thus improving process control. It should be understood that the stabilizer utilized in this invention is not limited to phytinic acid alone and that any other equivalent organic acid may be used.
  • Further object of this invention is to admix metal powders of the same metal but having different mean particle sizes to prepare a slurry to be applied on the surface of steel products in order to provide uniform coating layer and uniform adhesion of the dried metal powder before compaction as well as improved dispersion of metal particles in the slurry.
  • the major portion of the metal powder has a particle size of less than microns but larger particles are incorporated to improve adhesiveness of the coated metal layer after the final heat treatment.
  • the quantity of larger particles is selected to be in a range not to degrade the stability of the slurry.
  • metal powder having a mean particle size of less than 10 micron is utilize as the base and a portion thereof is substituted by metal powder having mean particle size of from 10 to 100 microns by a factor of 4/9 x 104.5 percent, where x represents the particle size of the latter metal powder having mean particle size ranging from 10 to 100 microns.
  • the slurry mixture is then applied on the steel surface and heat treatment, compaction and postcompaction heat treatment are carried out.
  • the metal particles are uniformly dispersed in the slurry and the slurry has excellent adhesion without decreasing easiness of coating operation.
  • particles having a grain size of less than 10 microns preferably of about 6 microns.
  • a slurry utilizing metal powder of about 13 microns can also be readily coated with a roll coater.
  • the metal powder is loosened from the surface of the steel plate by shock and vibration.
  • the adhesion in terms of reverse bend value (R.B.V.) of coating layers after a series of treating steps is as follows.
  • the R.B.V. of the coating layer consisting of only powder of 6 microns is about 80, whereas that of the coating consisting of powder of 13 microns increases to about 94.
  • a powder of larger particle size for example of 63 microns is mixed with water to form a slurry which is then applied by means of a roll coater the quantity of the powder that can be applied is very small and the powder is not firmly bonded to the surface after drying so that the powder falls off due to small shock or vibration.
  • a suitable quantity of larger particles are incorporated to the powder of 6 microns, the adhesion of the coated layer can be greatly improved over the coating containing only the powder of 6 microns.
  • a steel plate coated with aluminum powder is preheated in a preheating furnace in order to increase the rolling speed.
  • the preheating temperature is prescribed dependent upon the thickness of the plates, thickness of the coated layer and the heating time, temperatures ranging from 400 to 700 C generally give good results. More particularly, temperatures below 400 C result in blue brittleness causing a brittle plate whereas temperatures above 700 C cause vigorous oxidation of the metal powder thus making it difficult to obtain satisfactory coated layers.
  • such preheating can be performed in the atmosphere.
  • the rolling operation succeeding to the preheating step may be of such extent sufficient to elongate the plate by 2 to 5 percent. This is because that, with elongation of less than 2 percent, the aluminum powder will not be compacted sufficiently, thus forming porous coatings whereas elongation of more than 5 percent increases the brittleness of the plate.
  • FIG. 1 is a graph to show increase in the weight by oxidation which is obtained by the heat resistance test made on the product of example 1;
  • FIG. 2 shows the structure of aluminum coated steel of example 2 magnified 200 times
  • FIG. 3 shows a range in which larger particles can be added to powder of 6 microns.
  • FIG. 4 is a graph to show the improvement of the adhesion of the coated layer.
  • EXAMPLE 1 An aqueous suspension was prepared by admixing a finely divided aluminum powder having a particle size of less than 325 mesh, percent by weight of water and 200 ppm of phytinic acid. The suspension was coated by means of a roll coater upon a cold rolled steel plate of 1.2 mm thick which has been degreased and pickled. The coated steel plate was heated in the atmosphere at a temperature of 650 C for 45 seconds and was then rolled to elongate 5 percent at a rolling speed of 40m/min. After rolling, the plate was heat treated at a temperature of 700 C for seconds.
  • the aluminum coated steel plate obtained by this method has a uniform and beautiful coating, excellent formability and corrosion resistance.
  • the product showed excellent heat resistance as shown in FIG. 1.
  • EXAMPLE 2 The same aqueous suspension as that utilized in example l was coated upon a degreased and pickled cold rolled steel plate having a thickness of 0.8 mm at a rate of 80g/m by means of a roll coater. The coated steel plate was heated in the atmosphere at a temperature of 700 C for 20 seconds and was then cold rolled to elongate 3 percent at a rolling speed of 40m/min. The rolled plate was further heated in the atmosphere at a temperature of 400 C for 3 hours.
  • the aluminum coated layer formed in this manner on the steel plate had a thickness of 30 microns and no brittle alloy layer was formed as can be noted from a micrograph shown in FIG. 2. Thus the product has excellent deep drawability and corrosion resistance.
  • the invention is not limited to steel plate or sheet alone but may equally be applicable to other forms of steel products such as pipes, rods or beams of various cross-sectional configurations.
  • the metal powder is not limited to aluminum alone but may be used powders of zinc, lead, tin, titanium and the like having a particle size of less than 325 mesh. Of course, suitable method of suspending these powders in water and suitable preheating conditions are used.
  • EXAMPLE 3 This example illustrates the use of a zinc powder. Finely divided zinc powder having a particle size of less than 325 mesh was admixed with water at a ratio of 50 to 400 and 200 ppm of phytinic acid was added to the mixture. The resulted mixture was coated upon a pickled steel plate at a ratio of lg/m of the zinc powder. After being heated in the atmosphere at a temperatyre of 400 C for 10 seconds, the steel plate was rolled at a reduction rate of 3 percent. The rolled plate was then heat treated for 1 hour at a temperature of 300 C to obtain a steel plate having a homogenous zinc coating.
  • EXAMPLE 4 Aluminum powder having a particle size of 6 microns lOg Aluminum powder having a particle size of l3 microns g Water 50g Iron plate thickness 0.8mm
  • FIG. 3 shows an appropriate range of the percentage of admixing a powder of 6 microns and powders of larger particle size, with due consideration of uniform dispersion of the particles in the slurry and the adhesion of the powder layer before compaction.
  • FIG. 4 shows the formability of the coating layer from which it will be noted that the formability is improved in proportion to the quantity of incorporation of larger particles.
  • preheating before compaction can be performed in the oxidizing atmosphere.
  • a method of surface treatment of a steel product with a metal powder characterized by the steps of applying an aqueous slurry on the surface of said steel product, said slurry consisting of water and a metal powder having a particle size of less than 325 mesh suspended therein, prehating the coated steel product at a temperature of 400 to 700 C., rolling the coated steel product at a reduction rate of 2 to 5 percent to cause said metal powder to adhere to the surface of said steel product, and post-heating the resulting steel product at a temperature ranging from 300 to 700 C., said metal being selected from the group consisting of aluminum, zinc, lead, tin and titanium.
  • a method of surface treatment of a steel stock characterized by the steps of applying an aqueous slurry on the surface of said steel stock, said slurry consisting of water and a mixture of metal particles suspended therein, the mixture consisting of metal particles (i) having a mean particle size of less than microns and metal particles (ii) having a mean particle size of from 10 to 100 microns and the maximum percentage of said particles (ii) in said mixture being represented by the factor 4/9X [04.5 percent wherein X represents the particle size of said particles (ii), preheating the coated steel stock at a temperature of 400 to 700 C., rolling the coated steel stock at a reduction rate of 2 to 5 percent to cause said metal powder to adhere to the surface of steel stock and postheating said coated steel stock at a temperature ranging from 300 to 700 C., to form a stel product coated with an adhered layer of said metal powder, said metal being selected from the group consisting of aluminum, zinc, lead, tin and titanium.
  • a method of surface treatment of a steel product with a metal powder characterized by the steps of applying an aqueous slurry on the surface of said steel product, said slurry consisting of water, a metal powder having a particle size of less than 325 mesh suspended therein and a small quantity, sufficient to stabilize said slurry and to inhibit corrosion, of phytic acid, preheating the coated steel product at a temperature of 400 to 700 C., rolling the coated steel product at a reduction rate of 2 to 5 percent to cause said metal powder to adhere to the surface of said steel product, and postheating the resulting steel product at a temperature ranging from 300 to 700 C., said metal being selected from the group consisting of aluminum, zinc, lead, tin and titanium.
  • a method of surface treatment of a steel stock characterized by the steps of applying an aqueous slurry on the surface of said steel stock, said slurry consisting of water, a mixture of metal particles suspended therein, and a small quantity, sufficient to stabilize said slurry and to inhibit corrosion, of phytic acid, the mixture consisting of metal particles (i) having a mean par ticle size of less than 10 microns and metal particles (ii) having a mean particle size of from 10 to microns and the maximum percentage of said particles (ii) in said mixture being represented by the factor 4/9X 104.5 percent wherein X represents the particle size of said particles (ii), preheating the coated steel stock at a temperature of 400 to 700 C., rolling the coated steel stock at a reduction rate of 2 to 5 percent to cause said metal powder to adhere to the surface of steel stock and postheating said coated steel stock at a temperature ranging from 300 to 700 C., to form a steel product coated with an adhered layer of said metal powder, said metal being selected from the group

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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)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Chemically Coating (AREA)
US00294898A 1968-10-17 1972-10-04 Method of surface treating steel products with metal powder Expired - Lifetime US3827140A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7546868 1968-10-17
JP4920769A JPS4931182B1 (enrdf_load_stackoverflow) 1969-06-23 1969-06-23

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US3827140A true US3827140A (en) 1974-08-06

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US (1) US3827140A (enrdf_load_stackoverflow)
FR (1) FR2020932A1 (enrdf_load_stackoverflow)
GB (1) GB1288600A (enrdf_load_stackoverflow)
SU (1) SU461514A3 (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3884729A (en) * 1972-11-03 1975-05-20 British Steel Corp Method of providing an aluminum coating on a steel substrate
US20040142162A1 (en) * 2000-11-13 2004-07-22 Etienne Maze Use Of Moo3 as corrosion inhibitor, and coating composition containing such an inhibitor
US20100028658A1 (en) * 2006-09-28 2010-02-04 Makoto Nagasawa Hihgly corrosion-resistant, rust-prevention coating material, highly corrosion-resistant steel, and steel structure

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4256810A (en) * 1978-12-04 1981-03-17 Gould Inc. High conductivity titanium electrode

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041206A (en) * 1960-02-16 1962-06-26 Solar Aircraft Co Method and composition for obtaining diffused aluminum coating layers on metal articles
US3076734A (en) * 1960-07-01 1963-02-05 Acme Steel Co Protective coatings on metals
US3142560A (en) * 1960-11-17 1964-07-28 Vitre Teja Ind Co De Process for strip cladding by hot rolling of particulate material
US3231971A (en) * 1961-01-19 1966-02-01 Inland Steel Co Method of producing fusion coated metal base
US3248251A (en) * 1963-06-28 1966-04-26 Teleflex Inc Inorganic coating and bonding composition
US3310870A (en) * 1967-03-28 Process for producing nickel-coated steel
US3316625A (en) * 1963-06-10 1967-05-02 Int Nickel Co Method for coating steel with nickel
US3325282A (en) * 1965-04-27 1967-06-13 Bethlehem Steel Corp Method of forming a zinc-aluminum coating on a ferrous base
US3453849A (en) * 1965-10-13 1969-07-08 Texas Instruments Inc Manufacture of clad metals
US3485654A (en) * 1966-03-15 1969-12-23 Nat Steel Corp Method of preparing metal coated metallic substrates
US3690940A (en) * 1969-11-21 1972-09-12 Nippon Kokan Kk Preventing rusting of steel sheets coated with aqueous slurry of metal powder

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3310870A (en) * 1967-03-28 Process for producing nickel-coated steel
US3041206A (en) * 1960-02-16 1962-06-26 Solar Aircraft Co Method and composition for obtaining diffused aluminum coating layers on metal articles
US3076734A (en) * 1960-07-01 1963-02-05 Acme Steel Co Protective coatings on metals
US3142560A (en) * 1960-11-17 1964-07-28 Vitre Teja Ind Co De Process for strip cladding by hot rolling of particulate material
US3231971A (en) * 1961-01-19 1966-02-01 Inland Steel Co Method of producing fusion coated metal base
US3316625A (en) * 1963-06-10 1967-05-02 Int Nickel Co Method for coating steel with nickel
US3248251A (en) * 1963-06-28 1966-04-26 Teleflex Inc Inorganic coating and bonding composition
US3325282A (en) * 1965-04-27 1967-06-13 Bethlehem Steel Corp Method of forming a zinc-aluminum coating on a ferrous base
US3453849A (en) * 1965-10-13 1969-07-08 Texas Instruments Inc Manufacture of clad metals
US3485654A (en) * 1966-03-15 1969-12-23 Nat Steel Corp Method of preparing metal coated metallic substrates
US3690940A (en) * 1969-11-21 1972-09-12 Nippon Kokan Kk Preventing rusting of steel sheets coated with aqueous slurry of metal powder

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3884729A (en) * 1972-11-03 1975-05-20 British Steel Corp Method of providing an aluminum coating on a steel substrate
US20040142162A1 (en) * 2000-11-13 2004-07-22 Etienne Maze Use Of Moo3 as corrosion inhibitor, and coating composition containing such an inhibitor
US20060112849A1 (en) * 2000-11-13 2006-06-01 Etienne Maze Use of MoO3 as corrosion inhibitor, and coating composition containing such as inhibitor
US7081157B2 (en) * 2000-11-13 2006-07-25 Dacral Use of MoO3 as corrosion inhibitor, and coating composition containing such an inhibitor
US20060188731A1 (en) * 2000-11-13 2006-08-24 Etienne Maze Use of moo3 as corrosion inhibitor, and coating composition containing such an inhibitor
US7118807B2 (en) * 2000-11-13 2006-10-10 Dacral, S.A. Use of MoO3 as corrosion inhibitor, and coating composition containing such an inhibitor
US7250076B2 (en) 2000-11-13 2007-07-31 Dacral Use of MoO3 as corrosion inhibitor, and coating composition containing such an inhibitor
US20100028658A1 (en) * 2006-09-28 2010-02-04 Makoto Nagasawa Hihgly corrosion-resistant, rust-prevention coating material, highly corrosion-resistant steel, and steel structure
US8114527B2 (en) * 2006-09-28 2012-02-14 Nippon Steel Corporation Highly corrosion-resistant, rust-prevention coating material, highly corrosion-resistant steel, and steel structure

Also Published As

Publication number Publication date
DE1952424B2 (de) 1977-01-27
SU461514A3 (ru) 1975-02-25
DE1952424A1 (de) 1970-12-03
GB1288600A (enrdf_load_stackoverflow) 1972-09-13
FR2020932A1 (enrdf_load_stackoverflow) 1970-07-17

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