US3824134A - Metalliding process - Google Patents

Metalliding process Download PDF

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Publication number
US3824134A
US3824134A US00188524A US18852471A US3824134A US 3824134 A US3824134 A US 3824134A US 00188524 A US00188524 A US 00188524A US 18852471 A US18852471 A US 18852471A US 3824134 A US3824134 A US 3824134A
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United States
Prior art keywords
metallic
layer
work piece
chromium
steel
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Expired - Lifetime
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US00188524A
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M Chance
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Cooper Industries LLC
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Thornhill Craver Co
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Priority to US00188524A priority Critical patent/US3824134A/en
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Assigned to JOY MANUFACTURING COMPANY reassignment JOY MANUFACTURING COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: THORNHILL-CRAVER COMPANY
Assigned to COOPER INDUSTRIES, INC., 1001 FANNIN, SUITE 4000, HOUSTON, TEXAS 77002, A CORP. OF OHIO reassignment COOPER INDUSTRIES, INC., 1001 FANNIN, SUITE 4000, HOUSTON, TEXAS 77002, A CORP. OF OHIO ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: JOY MANUFACTURING COMPANY
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    • 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C12/00Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12542More than one such component
    • Y10T428/12549Adjacent to each other

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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)
  • Electroplating Methods And Accessories (AREA)

Abstract

THE DISCLOSURE TEACHES NOVEL COPPER BASE ALLOYS HAVING IMPROVED TOUGHNESS AND OUTSTANDING RESISTANCE TO STRESS CORROSION. THE COPPER ALLOYS CONTAIN, IN WEIGHT PERCENTPRODUCE A BARRIER LAYER OF METALLIC CARBIDE AND BORONIZED TO PRODUCE A BARRIER LAYER OF METALLIC BORIDES. THIS ABSTRACT IS NEITHER INTENDED TO DEFINE THE INVENTION OF THE APPLICATION, WICH, OF COURSE, IS MEASURED BY THE CLAIMS, NOR IS IT INTENDED TO BE LIMITING AS TO THE SCOPE OF THE INVENTION IN ANY WAY.

Description

United States Patent 01 Lfice 3,824,134 Patented July 16, 1974 3,824,134 METALLIDING PROCESS Maynard R. Chance, Houston, Tex., assignor to Thornhill- Craver Company, Houston, Tex. No Drawing. Filed Oct. 12, 1971, Ser. No. 188,524 Int. Cl. C23c 11/12 US. Cl. 148-6 2 Claims ABSTRACT OF THE DISCLOSURE A metalliding process for producing extremely hard metallic boride surface layers on steel bodies wherein the steel is carburized and treated with a nonferrous metal to produce a barrier layer of metallic carbide and boronized to produce the surface layer of metallic borides. This abstract is neither intended to define the invention of the application, which, of course, is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
This invention relates to a metalliding process, and particularly to a process for forming an extremely hard surface layer of metallic borides on a steel work piece.
In certain cases it is desirous that steel bodies be given extremely hard surface layers so as to minimize abrasion, wear, deformation, etc. It is well known that certain of the metallic borides are extremely hard. However, their use as a coating for steel or other ferrous metals has heretofore been limited because of the well-known diffusion characteristic of ferrous ions. If a hard boride, such as chromium boride, is plated onto a steel surface, the ferrous ions from the steel quickly diffuse into the boride layer forming ferrous borides and destroying the desirable extreme hardness of the coating layer.
[It is, therefore, the principal object of the present invention to provide a method for the coating of steel surfaces with extremely hard metallic boride layers wherein means are provided for preventing the diffusion of iron from the steel body into the boride layer.
Another object is to produce on steel work pieces extremely hard metallic borides, the major metallic constituent of which is not iron boride (Fe B) and/or (FeB).
Another object is to provide such boride coatings by utilizing the iron diffusion blocking properties in metallic carbides.
In accordance with the present invention, it has been discovered that the imposition of a layerof certain of the metallic carbides, such as chromium carbide, between the steel work piece and the metallic boride layer has the effect of blocking diffusion of the ferrous ions into the metallic boride layer.
In the preferred form of the invention, the steel work piece is first carburized by any conventional process to diffuse carbon into the work piece to provide a surface layer of high carbon content. One conventional carburizing process, as disclosed in -U.S. Pat. 2,659,685, is by packing the work piece in finely divided charcoal and heating to a very high temperature.
After carburizing, the work piece is electrolytically plated with any of certain nonferrous metals to diffuse said metal into the carburized layer to react with the carbon to form metallic carbides which act as a barrier to diffusion of the ferrous ions. The preferred nonferrous metal is chromium to form a barrier layer of chromium carbide, but it is pointed out that other carbide layers, specifically those of tantalum, titanium, vanadium, zirconium and hafnium are also included in this disclosure as having sutficient iron diffusion retarding properties to obtain the desired end result.
The electroplating is preferably carried out in accordance with US. Pat. No. 3,232,853 which discloses a process for chromiding wherein a cathode of the metal to be treated and an anode of plating metal, in this case chromium, are immersed in a fluoride bath at high temperature and connected through an external electrical circuit. With a suitable temperature bath and suitable current passing in the system, the chromium from the anode is deposited on the cathode work piece and reacts therewith to form a surface layer of chromium carbides.
It will be noted that Pat. 3,232,853 teaches chromiding directly on a metallic base without previous carburizing. However, it is an important discovery in accordance with the present invention that the formation of a suitably impervious carbide layer, specifically chromium carbide, and more specifically CR C6 and CR C2 cannot be obtained using the patented metalliding process unless carbon is present in sufficient quantities in the base metal. Therefore, carburizing a chromided base metal work piece is not sufficient to produce this layer, but chromiding at approximately .65 amperes per square decimeter on a carburized surface at sufficiently high temperature (approximately 1000 to 1150 C.) will produce a dense, practically defect-free layer of chromium carbides. This layer is difii'cult to obtain in thicknesses greater than ap proximately 08 mils, because of the retarding effect of the layer on the diffusion of iron in the base metal. The diffusion of iron in the base metal is prerequisite to the formation of layers on the base metal, as those skilled in the art are aware.
After formation of the practically impervious layer of nonferrous metallic carbide on the work piece, the piece is then borided preferably by the same electrolytic process. The anode of chromium or other nonferrous metal is replaced with an anode of boron and current is again circulated through the fluoride bath at elevated temperature to deposit a layer of boron on the work piece which diffuses into and reacts with the chromium or other nonferrous metal to produce a layer of extremely hard metallic borides the major metallic constituent of which is not iron boride or Fe B. In the case of chromium carbide layers, the principal boride formed is CrB it being understood that other and more complex borides can be pres cut. The hardness of such surface layers has been found to be in the order of 4600 to 5500 DPH (diamond pyramid hardness).
In addition to electroplating, the boriding step can also be carried out by other conventional cementation processes such as are well known to those skilled in the art.
It has been found that this method can be applied to both stainless steel of the straight chromium type, and to low alloy steels such as 4615 and 8620, and also to the low and medium carbon plain steels such as 1040 and 1020.
The foregoing disclosure and description of the invention is illustrative and explanatory thereof, and various changes in materials and in details of the disclosed process may be made within the scope of the appended claims without departing from the spirit of the invention.
What is claimed is: l
1. A method for producing an extremely hard metallic boride layer on a steel work piece comprising the steps of (1) diffusing carbon into said work piece to provide thereon a layer of high carbon content,
(2) diffusing into the work piece a metal selected from: the group consisting of chromium, tantalum, titanium, vanadium, zirconium and hafnium to form thereon a layer of metallic carbide, and
(3) diffusing into the work piece boron to produce an extremely hard layer of borides of said metal.
2. The method of claim 1 wherein said work piece is of stainless steel and said metal is chromium.
4 References Cited UNITED STATES PATENTS 3,029,162 4/1962 Samuel et a1. 148-63 3,684,585 8/1972 Stroup et al 148l6.5 2,659,685 11/1953 Latferty 1483 1.5
DOUGLAS J. DRUMMOND, Primary Examiner M. G. WITYSHYN, Assistant Examiner US. Cl. X.R. l48.l6.5, 31.5
US00188524A 1971-10-12 1971-10-12 Metalliding process Expired - Lifetime US3824134A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4012238A (en) * 1973-08-10 1977-03-15 Hughes Tool Company Method of finishing a steel article having a boronized and carburized case
US4153483A (en) * 1975-06-19 1979-05-08 Chemetal Corporation Deposition method and products
EP0152471A1 (en) * 1983-08-15 1985-08-28 CLARK, Eugene V. Turbine components having increased life cycle and method
EP0188057A1 (en) * 1984-11-19 1986-07-23 Avco Corporation Erosion resistant coatings
US4979998A (en) * 1989-10-10 1990-12-25 Union Carbide Corporation Process for forming a metal boride coating on a carbonaceous substrate
US5190598A (en) * 1990-02-26 1993-03-02 Westinghouse Electric Corp. Steam turbine components having duplex coatings for improved erosion resistance
EP2058418A1 (en) * 2007-11-09 2009-05-13 Mustafa K. Ürgen Method for boriding of coatings using high speed electrolytic process
US20110132769A1 (en) * 2008-09-29 2011-06-09 Hurst William D Alloy Coating Apparatus and Metalliding Method
WO2014044418A1 (en) * 2012-09-21 2014-03-27 Schaeffler Technologies AG & Co. KG Chain element, chain pin and method for producing same
RU2618289C1 (en) * 2015-11-18 2017-05-03 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный технологический университет" (ФГБОУ ВО "КубГТУ") Method for hard alloy products durability increase

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4012238A (en) * 1973-08-10 1977-03-15 Hughes Tool Company Method of finishing a steel article having a boronized and carburized case
US4153483A (en) * 1975-06-19 1979-05-08 Chemetal Corporation Deposition method and products
EP0152471A1 (en) * 1983-08-15 1985-08-28 CLARK, Eugene V. Turbine components having increased life cycle and method
EP0152471A4 (en) * 1983-08-15 1986-03-18 Eugene V Clark Turbine components having increased life cycle and method.
EP0188057A1 (en) * 1984-11-19 1986-07-23 Avco Corporation Erosion resistant coatings
US4979998A (en) * 1989-10-10 1990-12-25 Union Carbide Corporation Process for forming a metal boride coating on a carbonaceous substrate
US5190598A (en) * 1990-02-26 1993-03-02 Westinghouse Electric Corp. Steam turbine components having duplex coatings for improved erosion resistance
AU2008324152B2 (en) * 2007-11-09 2011-04-28 Guldem Kartal Method for boriding of coatings using high speed electrolytic process
WO2009060033A1 (en) * 2007-11-09 2009-05-14 Uergen Mustafa K Method for boriding of coatings using high speed electrolytic process
US20100224498A1 (en) * 2007-11-09 2010-09-09 Uergen Mustafa K Method for boriding of coatings using high speed electrolytic process
EP2058418A1 (en) * 2007-11-09 2009-05-13 Mustafa K. Ürgen Method for boriding of coatings using high speed electrolytic process
CN101910471B (en) * 2007-11-09 2012-07-04 穆斯塔法·K·乌尔根 Method for boriding of coatings using high speed electrolytic process
US10287700B2 (en) 2007-11-09 2019-05-14 Mustafa K. Ürgen Method for boriding of coatings using high speed electrolytic process
US20110132769A1 (en) * 2008-09-29 2011-06-09 Hurst William D Alloy Coating Apparatus and Metalliding Method
WO2014044418A1 (en) * 2012-09-21 2014-03-27 Schaeffler Technologies AG & Co. KG Chain element, chain pin and method for producing same
CN104662329A (en) * 2012-09-21 2015-05-27 舍弗勒技术股份两合公司 Chain element, chain pin and method for producing same
US9958030B2 (en) 2012-09-21 2018-05-01 Schaeffler Technologies AG & Co. KG Chain element, chain pin, and method for producing same
CN104662329B (en) * 2012-09-21 2019-02-12 舍弗勒技术股份两合公司 Chain member, chain pin and its manufacturing method
DE102012217020B4 (en) 2012-09-21 2022-02-17 Schaeffler Technologies AG & Co. KG Manufacturing process for a chain element with a surface layer containing boron and vanadium
RU2618289C1 (en) * 2015-11-18 2017-05-03 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный технологический университет" (ФГБОУ ВО "КубГТУ") Method for hard alloy products durability increase

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Owner name: JOY MANUFACTURING COMPANY 301 GRANT STREET PITTSBU

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Effective date: 19840831

Owner name: JOY MANUFACTURING COMPANY,PENNSYLVANIA

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Effective date: 19840831

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Owner name: COOPER INDUSTRIES, INC., 1001 FANNIN, SUITE 4000,

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:JOY MANUFACTURING COMPANY;REEL/FRAME:004679/0943

Effective date: 19870204