US3111434A - Surface hardening of metal body consisting of or containing titanium or zirconium - Google Patents

Surface hardening of metal body consisting of or containing titanium or zirconium Download PDF

Info

Publication number
US3111434A
US3111434A US4635160A US3111434A US 3111434 A US3111434 A US 3111434A US 4635160 A US4635160 A US 4635160A US 3111434 A US3111434 A US 3111434A
Authority
US
United States
Prior art keywords
zirconium
titanium
gas
inert gas
metal
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
Inventor
Takao Zenichiro
Inomata Shigeo
Nakano Koichi
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.)
Kobe Steel Ltd
Original Assignee
Kobe Steel Ltd
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
Priority to CA713159A priority Critical patent/CA713159A/en
Application filed by Kobe Steel Ltd filed Critical Kobe Steel Ltd
Priority to US4635160 priority patent/US3111434A/en
Priority to FR840300A priority patent/FR1271837A/en
Priority to DEK41851A priority patent/DE1182016B/en
Priority to GB3655660A priority patent/GB906895A/en
Priority to CH134961A priority patent/CH414302A/en
Application granted granted Critical
Publication of US3111434A publication Critical patent/US3111434A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
    • B23K35/325—Ti as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
    • 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
    • Y10T70/00—Locks
    • Y10T70/70—Operating mechanism
    • Y10T70/7441—Key
    • Y10T70/7486—Single key
    • Y10T70/7508—Tumbler type
    • Y10T70/7559—Cylinder type
    • Y10T70/7588—Rotary plug
    • Y10T70/7593—Sliding tumblers
    • Y10T70/7599—Transverse of plug
    • Y10T70/7605—Pin tumblers

Definitions

  • the present invention relates to surface hardened metal bodies or articles consisting of or containing titanium or zirconium, and also to a process for surface hardening metal bodies or articlesconsisting of or containing titanium or zirconium.
  • the metals belonging to the titanium group of the periodic system particularly titanium, zirconium and alloys containing the same have relatively low specific gravities and are excellent in tensile strength and anticorrosive properties, and therefore have extensively been used as materials for various articles, structures, apparatus, etc. including chemical apparatus and appliances.
  • titanium and zirconium are low in hardness and are poor in wear resistance and furthermore have rawbacks that they are damaged particularly when applied to those which are subjected to friction. For these reasons, these materials are not fully satisfactory in spite of their various excellent properties.
  • an improved metal body or article consists of a base metal consisting of or containing titanium or zirconium and a surface hardened coating or layer which consists of the nitride and/ or oxide of the metal or alloy of the said base, or consists of a dispersed layer of the nitride and/ or oxide.
  • the hardened surface coating or layer is formed by reacting the surface layer of the base metal or alloy with oxygen and/ or nitrogen. It is preferable to use gaseous oxygen and gaseous nitrogen as oxidizing and nitridation agents respectively. More particularly, according to the present invention, the nitride and/ or oxide are formed by utilizing the so-called inert gas shielded arc welding arrangement with or without a filler metal rod consisting of the same material as the base metal or alloy. Oxygen and/ or nitrogen gas are mixed with the inert gas so that the nitridation and/or oxidation occur While the surface is being covered by the inert gas.
  • the surface of the base is reacted with oxygen and/or nitrogen to integrally form the oxide and/ or nitride thereon, while when the filler metal is used the molten filler metal itself forms the oxide and/or nitride layer or coating on the base.
  • Titanium is chemically stable below 500 C. but becomes very active at higher temperatures and reacts with oxygen at temperatures higher than the red heat (500 C.) to form titanium oxide as a solid solution or dispersion layer consisting mainly of titanium dioxide, and reacts with nitrogen at temperatures higher than 800 C. to form a solid solution or dispersion layer of titanium nitride.
  • solubility of oxygen and nitrogen in titanium is appreciably higher than in other practical metals.
  • zirconium reacts with oxygen and nitrogen at elevated temperatures (500 C.). The same is true in respect to titanium or zirconium base alloys. In any case, the oxide and/ or nitride forms very hard surface layer or coating on the base metal or alloy.
  • the formation of the desired oxide and/or nitride is effected by shielding the surface of the base metal body or article with an inert gas such as argon or helium and the surface is are molten or coated with additional molten metal (by using a filler metal rod) while introducing a predetermined amount of oxygen and/or nitrogen in the inert gas.
  • an inert gas such as argon or helium
  • the amount and proportions of oxygen and/or nitrogen can be controlled quite easily as desired to stabilize the oxidation and/or nitridation reaction and form the desired and uniform hardened surface.
  • an inert gas shielded arc welding arrangement which, so well known to those skilled in the art as requiring no detailed explanation, is a shield arc welding carried out in an inert gaseous atmosphere.
  • an electrode of material having a high melting point such as tungsten is employed.
  • the hardened layer to be formed is relatively thin A mm. or less
  • no filler metal rod is used and the surface to be hardened is are molten and reacted with oxygen and/or nitrogen While shielded with the inert gas to form the hard oxide and/or nitride.
  • the hardened layer to be formed is relatively thick (up to 5 mm. or thicker), it is preferable to use a filler metal in the usual manner.
  • the filler metal which is the same material as the base metal to be coated is similarly arc molten and reacted with oxygen and/ or nitrogen while shielded with the inert gas to form the hard oxide and/ or nitride which are deposited on the said surface.
  • the amount of oxygen and/ or nitrogen to be supplied in the inert gas will largely control the hardness of the formed layer or coating.
  • the amount of the reactive gas is less than that required no sufiicient hardness would be obtained, while if the amount of the reactive gas is excessive fragility of the oxide and/ or nitride is unduly increased so that the surface would become brittle.
  • the amount of the reactive gas is selected depending upon the desired hardness to be accomplished, the particular metal or alloy from which the body or article is formed, and the thickness of the hardened layer or coating. This amount can be selected easily by those skilled in the art by means of a small scale pretesting.
  • the amount of the reactive gas (oxygen and/ or nitrogen) is determined by the proportion occupying in the inert gas. Generally, when the metal surface itself is molten and hardened without using a metal deposition from the filler met-a1 rod it has been found that the amount of the reactive gas is preferable to be selected less than 15% by volume of the inert gas, while when the metal deposition is used the amount of the reactive gas is preferable to be less than 10% by volume of the inert gas. In the latter case the said less amount is caused by the use of 45 cording to gas analysis. In any case, the Welding conditions were equally' as follows:
  • the Weld or are current is f bl to be
  • the depositioncoa-tlng or layer was formed controlled within the range from 60 to 130 amp., alh thickness of 5 and lts hardhes rt*Thhrkahly though not absolutely necessary to be limited to this parhlghef than that of the base mhtal tltahlu'mticul ar range.
  • the arc length usually is about 2-10 mm.
  • Example 2 7 l 0 I v 2 3 .5; z 3 2 2 3 dhehum s f:
  • bodies of titan um, trtanlum base ale 1 6 gas a or e aroun e loys, zirconium, and zirconium base alloys were surface portion to be wgelded or molten may, 1n most cases, be hardened by amploying an oxygen and/o1.
  • g ifii i coatmg zf 0n results were as indicated in the fol-lowing table.
  • the surface hardness was measured by Vickers hardhas hardness of from 250 to 550 as measured by V1cxers t k 1 n ness meter (load 30 gs.). hardness meter (load 30 rigs).
  • the reactive gas (oxy- W 1d A A a R W m gen and/ or nitrogen) is introduced in the inert gas which Body g @33 gg f Speeed su face creates an inert gas shield the stability and uniformity of ng (mm) (In /hr.) percent g'liglj/ hardness the reaction are assured, the control of the reaction is (a easy so that there 1s obtained a umform hard layer or Ti H50 H0 1O 30 (02) 10mm 2504300 coating.
  • the filler metal rod for deposiuon a Ti al10y 00-150 2-10 10-g0 30 282) 100-150 25 -200 r .1 t z.
  • Zr 00-180 2-10 10- 0 0 00-150 25 00 tlnch coatmg, if desired, can be obta ned.
  • Zr H80 H0 10 30 g 100450 25mm controlling the amount of the deposition, the thickness of the hard coating may be varied as desired.
  • Example 3 since the definite or calculated amount of oxygen and/ or T I d an b a nitrogen can be introduced, and undesired intrusion of b a 15 i fi g i i atmospheric air (which would cause nonuniformity of the 165 ace ar e e y W 051.1 g a 1 minim formed 1a er or 60min is v revented b the inert as oxide and n1tr1de layer thereon.
  • a usual mert gw shieldd th a n 35 ed arc Welding apparatus with tungsten elec rode was S 1 Z e ayel or coa Hg mime 18 i an y employed together with a filler metal rod as indicated for form in hardness and structure or composruon.
  • the Tesuh was as follows:
  • a method of surface-hardening a metal body selected from the group consisting of titanium and zirconium which comprises the steps of: forming a layer on the surface of the body by reacting said body with a reactive gaseous element in an inert gas-shielded arc welding arrangement by heating the body surface to a temperate at which it is molten, and introducing in the inert gas the reactive gaseous element so that said surface of the body while being arc-welded and shielded by the inert gas, is reacted with said reactive gaseous element to form the layer.
  • a method of surface hardening a metal body selected from the group consisting of titanium, zirconium, and titanium base alloys comprising the steps of: shielding the body with an inert gas having mixed therewith a measured amount of reactive gas for reacting with the body and simultaneously arc welding the body in the gas shield at a temperature which provides a molten surface on said body so that the molten portion of the body reacts with the reactive gas to form a hard layer on the surface of said body.
  • a method as defined in claim 3 comprising depositing metal from a filler metal rod onto the body during arc welding.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Arc Welding In General (AREA)
  • Nonmetallic Welding Materials (AREA)

Description

United States Patent SURFACE HARDENING 0F METAL BODY (ISN- SlSTlNG OF OR CONTAINENG TITANIUM 0R ZKRCONIUM Zenichiro Takao, Nishinomiya, and Shigeo Inomata and Koiehi Nakano, Higashinada-ku, Kobe, Japan, assignors to Kobe Steel Works, Ltd, Kobe, Japan No Drawing. Filed Aug. 1, 1966, Ser. No. 46,351
4 Claims. (Cl. 148-131) The present invention relates to surface hardened metal bodies or articles consisting of or containing titanium or zirconium, and also to a process for surface hardening metal bodies or articlesconsisting of or containing titanium or zirconium.
The metals belonging to the titanium group of the periodic system, particularly titanium, zirconium and alloys containing the same have relatively low specific gravities and are excellent in tensile strength and anticorrosive properties, and therefore have extensively been used as materials for various articles, structures, apparatus, etc. including chemical apparatus and appliances. However,. titanium and zirconium are low in hardness and are poor in wear resistance and furthermore have rawbacks that they are damaged particularly when applied to those which are subjected to friction. For these reasons, these materials are not fully satisfactory in spite of their various excellent properties.
It is an object of the present invention to provide surface hardened metal bodies or articles consisting of or containing titanium or zirconium which show excellent wear resistance and antifriction due to the hardened surface layer.
It is another object of the present invention to provide a process for surface hardening metal bodies or articles consisting of or containing titanium or zirconium to render them wear resistant and antifrictive to make them more useful.
In accordance with the invention, an improved metal body or article consists of a base metal consisting of or containing titanium or zirconium and a surface hardened coating or layer which consists of the nitride and/ or oxide of the metal or alloy of the said base, or consists of a dispersed layer of the nitride and/ or oxide.
The hardened surface coating or layer is formed by reacting the surface layer of the base metal or alloy with oxygen and/ or nitrogen. It is preferable to use gaseous oxygen and gaseous nitrogen as oxidizing and nitridation agents respectively. More particularly, according to the present invention, the nitride and/ or oxide are formed by utilizing the so-called inert gas shielded arc welding arrangement with or without a filler metal rod consisting of the same material as the base metal or alloy. Oxygen and/ or nitrogen gas are mixed with the inert gas so that the nitridation and/or oxidation occur While the surface is being covered by the inert gas. When the filler metal is not used the surface of the base is reacted with oxygen and/or nitrogen to integrally form the oxide and/ or nitride thereon, while when the filler metal is used the molten filler metal itself forms the oxide and/or nitride layer or coating on the base.
Titanium is chemically stable below 500 C. but becomes very active at higher temperatures and reacts with oxygen at temperatures higher than the red heat (500 C.) to form titanium oxide as a solid solution or dispersion layer consisting mainly of titanium dioxide, and reacts with nitrogen at temperatures higher than 800 C. to form a solid solution or dispersion layer of titanium nitride. In this connection it should be noted that solubility of oxygen and nitrogen in titanium is appreciably higher than in other practical metals. Similarly, zirconium reacts with oxygen and nitrogen at elevated temperatures (500 C.). The same is true in respect to titanium or zirconium base alloys. In any case, the oxide and/ or nitride forms very hard surface layer or coating on the base metal or alloy.
According to the present invention, the formation of the desired oxide and/or nitride is effected by shielding the surface of the base metal body or article with an inert gas such as argon or helium and the surface is are molten or coated with additional molten metal (by using a filler metal rod) while introducing a predetermined amount of oxygen and/or nitrogen in the inert gas.
As is known, atmospheric air is abundant with oxygen and nitrogen and it is apparent that when air is employed oxygen and nitrogen as contained therein serve as reactive gas to form the oxide and nitride. Simply considered, the use of atmospheric air may be convenient and economical. However, it has been found that the same is not true from the practical point of view. That is, the flow of air into the reaction zone is very unstable and nonuniform and in addition thereto are producing condition such as electric current is not constant at all times and usually varies from instant to instant, so that the formed oxide and nitride are nonuniform in the extent and structure.
Therefore, according to the invention it is preferable not to use atmospheric air but to introduce into the inert gas separately prepared oxygen and/or nitrogen. Thus, the amount and proportions of oxygen and/or nitrogen can be controlled quite easily as desired to stabilize the oxidation and/or nitridation reaction and form the desired and uniform hardened surface.
As mentioned hereinbefore, it is preferable to employ an inert gas shielded arc welding arrangement which, so well known to those skilled in the art as requiring no detailed explanation, is a shield arc welding carried out in an inert gaseous atmosphere. As is conventional, an electrode of material having a high melting point such as tungsten is employed. When the hardened layer to be formed is relatively thin A mm. or less), no filler metal rod is used and the surface to be hardened is are molten and reacted with oxygen and/or nitrogen While shielded with the inert gas to form the hard oxide and/or nitride. If the hardened layer to be formed is relatively thick (up to 5 mm. or thicker), it is preferable to use a filler metal in the usual manner. The filler metal which is the same material as the base metal to be coated is similarly arc molten and reacted with oxygen and/ or nitrogen while shielded with the inert gas to form the hard oxide and/ or nitride which are deposited on the said surface.
It is apparent that the amount of oxygen and/ or nitrogen to be supplied in the inert gas will largely control the hardness of the formed layer or coating. Thus, when the amount of the reactive gas is less than that required no sufiicient hardness would be obtained, while if the amount of the reactive gas is excessive fragility of the oxide and/ or nitride is unduly increased so that the surface would become brittle.
The amount of the reactive gas is selected depending upon the desired hardness to be accomplished, the particular metal or alloy from which the body or article is formed, and the thickness of the hardened layer or coating. This amount can be selected easily by those skilled in the art by means of a small scale pretesting. The amount of the reactive gas (oxygen and/ or nitrogen) is determined by the proportion occupying in the inert gas. Generally, when the metal surface itself is molten and hardened without using a metal deposition from the filler met-a1 rod it has been found that the amount of the reactive gas is preferable to be selected less than 15% by volume of the inert gas, while when the metal deposition is used the amount of the reactive gas is preferable to be less than 10% by volume of the inert gas. In the latter case the said less amount is caused by the use of 45 cording to gas analysis. In any case, the Welding conditions were equally' as follows:
the filler metal rod for the deposition coating. That is, Welding current 75 95 amp when such filler metal rod is employed atmospheric air Arc Voltage comes to get mixed in even if the inert gas shield is es- Arclength mm t'ablished, and oxygen and nitrogen contained in this air Gas HOW 15 ft s/hr.
would take part in the reaction so that this must be taken Welding speed 100430 {mm/mil into consideration beforehand.
Generally the Weld or are current is f bl to be In each case the depositioncoa-tlng or layer was formed controlled within the range from 60 to 130 amp., alh thickness of 5 and lts hardhes rt*Thhrkahly though not absolutely necessary to be limited to this parhlghef than that of the base mhtal tltahlu'mticul ar range. The arc length usually is about 2-10 mm. Example 2 7 l 0 I v 2 3 .5; z 3 2 2 3 dhehum s f: In 'th1s example, bodies of titan um, trtanlum base ale 1 6 gas a or e aroun e loys, zirconium, and zirconium base alloys were surface portion to be wgelded or molten may, 1n most cases, be hardened by amploying an oxygen and/o1. nitmgm gas i g; g d 1 1 mixed inert gas shielded arc welding arrangement with- 1 a d ip 6 so ayer or if out using a filler metal, under various conditions. The $2 3? g ifii i coatmg zf 0n results were as indicated in the fol-lowing table. In any 6 me i o y or m e 15 very um Orm an i y case, the surface hardness was measured by Vickers hardhas hardness of from 250 to 550 as measured by V1cxers t k 1 n ness meter (load 30 gs.). hardness meter (load 30 rigs).
According to this invention, since the reactive gas (oxy- W 1d A A a R W m gen and/ or nitrogen) is introduced in the inert gas which Body g @33 gg f Speeed su face creates an inert gas shield the stability and uniformity of ng (mm) (In /hr.) percent g'liglj/ hardness the reaction are assured, the control of the reaction is (a easy so that there 1s obtained a umform hard layer or Ti H50 H0 1O 30 (02) 10mm 2504300 coating. By llSlIlg the filler metal rod for deposiuon a Ti al10y 00-150 2-10 10-g0 30 282) 100-150 25 -200 r .1 t z. Zr 00-180 2-10 10- 0 0 00-150 25 00 tlnch coatmg, if desired, can be obta ned. In th s case, by Zr (H80 H0 10 30 g 100450 25mm controlling the amount of the deposition, the thickness of the hard coating may be varied as desired. Furthermore, 30 Example 3 since the definite or calculated amount of oxygen and/ or T I d an b a nitrogen can be introduced, and undesired intrusion of b a 15 i fi g i i atmospheric air (which would cause nonuniformity of the 165 ace ar e e y W 051.1 g a 1 minim formed 1a er or 60min is v revented b the inert as oxide and n1tr1de layer thereon. A usual mert gw shieldd th a n 35 ed arc Welding apparatus with tungsten elec rode was S 1 Z e ayel or coa Hg mime 18 i an y employed together with a filler metal rod as indicated for form in hardness and structure or composruon. the deposition The Tesuh was as follows:
The invention will be further described with reference v a to the following examples. However, 1t should be under W61 d Are Argon Reactive stood that these examples are for illustration only and not 40 Body curlength g as gas, Filler Surface for limiting the invention in any way. 53 (mm) (ft/hr) percent metal hardness Example 1 Ti 00-150 g-io 10-3 (81) T T1i1 300-2 0 A titanium rod circular in cross section and 17 mm. gig 5;: 23328 :18 18:2 20 13 35 28: in diameter was surface hardened by depositing a tita- Tialloyn 69450 10-30 20 (O2) Timmy 3OO'5OO nium oxide layer thereon. A usual inert gas shielded are welding apparatus with tungsten electrode was employed In y Case, the Welthhg Speed was 109150 mill/mmtogether with a filler titanium rod for the deposition. In E m l 4 the first Weld deposmcn was earned out by using In this example, various titanium, zirconium and their usual or Common argon gas (Oxygen Fontent 0% N base alloy bodies listed below were surface hardened by the fiamfi Pfocfiddte Was ffipeated with the of stgma employing an oxygen and/ or nitrogen gas mixed inert gas grade argon gas y cohtil'lt 5% and finally 'Wlth a shielded arc welding with or without using a filler metal, mixture of equal amount of argon gas and sigma grade under various conditions indicated. The various condigas, the oxygen content in said mixture being 3.4% actions and results are given below.
Reactive Gas, Weld Shield Percent Current Gas flow Speed Length Exp. Body Filler Rod gas (amp.) (l./1nin.) (111111.! of arc min.) (mm.)
1 0 100-130 5-10 100-130 34 3 0 100-130 5-10 100-130 34 0 0 100-130 5-10 100-130 3-4 0 1 100-130 5-10 100-130 34 0 3 100-130 5-10 100-130 34 0 5 100-130 5-10 100-130 3-4 Ti 0 10 100-130 51-10 100-130 3-4 Ti alloy--- 2 0 100-130 5-10 30-120 5-3 Ti alloy". 2 0 100-130 5-10 30-120 5-3 5 0 100-120 5-10 100-130 3-4 0 5 100-120 5-10 100-130 3-4 5 0 100-120 7 100-130 3-4 3 0 90130 7 100-120 3-4 0 0 -130 7 -120 3-4 0 1 90-130 7 100-120 3-1 0 0 90-130 7 100-120 3-4 0 10 90-130 7 100-120 3-4 5 0 00-120 7 100-120 34 0 0 30-120 7 100-120 3-5 In the above table, the alloy of Exp. 8 consisted of 0.025% C, 0.065% Fe, 0.05% Si, 1.06% Mo, 4.53% Al, 2% Cr and rest Ti, while the alloy of Exp. 9 consisted of 0.2% C, 0.075% Fe, 0.015% Si, 4.36% Al, 4.54% Mn and rest Ti.
After the welding operation, hardness of these metal bodies was as indicated below, when measured by Vickers hardness meter (load 30 kgs.).
Exp. No.: Hardness 1 300-350 2 350-460 3 400-550 4 320-350 5 300-400 6 350-480 7 470-550 8 370-450 9 390-510 10 400-550 11 450-550 1.. 400-550 13 350-400 14 350-450 15 250-300 16 300-420 17 350-500 18 350-400 19 200-250 What we claim is:
1. A method of surface-hardening a metal body selected from the group consisting of titanium and zirconium, which comprises the steps of: forming a layer on the surface of the body by reacting said body with a reactive gaseous element in an inert gas-shielded arc welding arrangement by heating the body surface to a temperate at which it is molten, and introducing in the inert gas the reactive gaseous element so that said surface of the body while being arc-welded and shielded by the inert gas, is reacted with said reactive gaseous element to form the layer.
2. A method of surface hardening a metal body selected from the group consisting of titanium, zirconium, and titanium base alloys, said method comprising the steps of: shielding the body with an inert gas having mixed therewith a measured amount of reactive gas for reacting with the body and simultaneously arc welding the body in the gas shield at a temperature which provides a molten surface on said body so that the molten portion of the body reacts with the reactive gas to form a hard layer on the surface of said body.
3. A method of surface hardening a metal body selected from the group consisting of titanium, Zirconium, an alloy of 0.025% C, 0.065% Fe, 0.05% Si, 1.06% Mo, 4.53% Al, 2% Cr and the remainder titanium, and an alloy of 0.2% C, 0.075% Fe, 0.015% Si, 4.36% A1, 4.5% Mn and the remainder titanium, said method comprising the steps of shielding the body with an inert gas selected from the group consisting of argon and helium, and having mixed therewith a measured amount of reactive gas selected from the group consisting of oxygen and nitrogen for reacting with the body to thereby form a hard oxide and/or nitride layer, said inert gas being supplied at a rate of 10-30 ft. per hour and simultaneously arc welding the body in the gas shield at a temperature which provides a molten surface on said body so that the molten portion of the body reacts with the reactive gas to form a hard layer on the surface of said body.
4. A method as defined in claim 3 comprising depositing metal from a filler metal rod onto the body during arc welding.
References Cited in the file of this patent UNITED STATES PATENTS 1,748,378 Armstrong Feb. 25, 1930 2,523,883 Strauchen et a1 Sept. 26, 1950 2,892,743 Griest et a1 June 30, 1959 FOREIGN PATENTS 555,952 Canada Apr. 15, 1958 OTHER REFERENCES Titanium, McQuillan & McQuillan, pages 398-400, Butterworth, Scientific iublications, 1956.
Morris: Welding Principles for Engineers, page 53.

Claims (1)

1. A METHOD OF SURFACE-HARDENING A METAL BODY SELECTED FROM THE GORUP CONSISTING OF TITANIUM AND ZIRCONIUM, WHICH COMPRISES THE STEPS OF: FORMING A LAYER ON THE SURFACE OF THE BODY BY REACTING SAID BODY WITH A REACTIVE GASEOUS ELEMENT IN AN INERT GAS-SHIELDED ARC WELDING ARRANGEMENT BY HEATING THE BODY SURFACE TO A TEMPERATE AT WHICH IT IS MOLTEN, AND INTRODUCING IN THE INERT GAS THE REACTIVE GASEOUS ELEMENT SO THAT SAID SURFACE OF THE BODY WHILE BEING ARC-WELDING AND SHIELDED BY THE INERTG GAS, IS REACTED WITH SAID REACTIVE GASEOUS ELEMENT TO FORM THE LAYER.
US4635160 1960-08-01 1960-08-01 Surface hardening of metal body consisting of or containing titanium or zirconium Expired - Lifetime US3111434A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA713159A CA713159A (en) 1960-08-01 Surface hardening of metal body consisting of or containing titanium or zirconium
US4635160 US3111434A (en) 1960-08-01 1960-08-01 Surface hardening of metal body consisting of or containing titanium or zirconium
FR840300A FR1271837A (en) 1960-08-01 1960-10-04 Surface hardening of metal bodies made of titanium or zirconium
DEK41851A DE1182016B (en) 1960-08-01 1960-10-08 Surface hardening of a metal body, which consists of titanium or zirconium or contains such metals
GB3655660A GB906895A (en) 1960-08-01 1960-10-25 Surface hardening of metal articles consisting of or containing titanium or zirconium
CH134961A CH414302A (en) 1960-08-01 1961-02-06 Method for surface hardening of metal bodies made of titanium, a titanium alloy, zirconium or a zirconium alloy

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US4635160 US3111434A (en) 1960-08-01 1960-08-01 Surface hardening of metal body consisting of or containing titanium or zirconium
FR840300A FR1271837A (en) 1960-08-01 1960-10-04 Surface hardening of metal bodies made of titanium or zirconium
DEK41851A DE1182016B (en) 1960-08-01 1960-10-08 Surface hardening of a metal body, which consists of titanium or zirconium or contains such metals
GB3655660A GB906895A (en) 1960-08-01 1960-10-25 Surface hardening of metal articles consisting of or containing titanium or zirconium
CH134961A CH414302A (en) 1960-08-01 1961-02-06 Method for surface hardening of metal bodies made of titanium, a titanium alloy, zirconium or a zirconium alloy

Publications (1)

Publication Number Publication Date
US3111434A true US3111434A (en) 1963-11-19

Family

ID=41581174

Family Applications (1)

Application Number Title Priority Date Filing Date
US4635160 Expired - Lifetime US3111434A (en) 1960-08-01 1960-08-01 Surface hardening of metal body consisting of or containing titanium or zirconium

Country Status (6)

Country Link
US (1) US3111434A (en)
CA (1) CA713159A (en)
CH (1) CH414302A (en)
DE (1) DE1182016B (en)
FR (1) FR1271837A (en)
GB (1) GB906895A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3314827A (en) * 1963-12-24 1967-04-18 Shell Oil Co Process for the hardening of metals
US5330587A (en) * 1992-02-28 1994-07-19 Ingersoll-Rand Company Shaft of laser nitride-hardened surface on titanium
US5366563A (en) * 1992-12-28 1994-11-22 General Electric Company Hot argon cleaning and protective coating of components made of metal or alloy
EP0721997A1 (en) * 1993-10-27 1996-07-17 Fuji Oozx Inc. Method of treating the surface of TI or TI alloy valve element
US5551671A (en) * 1994-07-27 1996-09-03 General Electric Company Hot argon cleaning and protective coating of components made of metal or alloy
FR2962671A1 (en) * 2010-07-13 2012-01-20 Air Liquide METHOD FOR ARC WELDING AND INERT GASES OF ALUMINUM METALLIC PARTS
WO2012113019A1 (en) * 2011-02-24 2012-08-30 Mario Ciccotosto Method of forming durable working surfaces
US9321132B2 (en) 2010-07-13 2016-04-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Hybrid arc/laser-welding method for aluminized steel parts using gammagenic elements and a gas containing less than 10% of nitrogen or oxygen

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2831791C2 (en) * 1978-07-19 1982-09-09 Gkss - Forschungszentrum Geesthacht Gmbh, 2000 Hamburg Component made of metallic material with a surface at risk of being charged and use therefor
GB2211211B (en) * 1987-10-17 1991-08-21 Rolls Royce Plc Method of providing titanium and alloys thereof with a protective coating
GB2328221A (en) * 1997-08-15 1999-02-17 Univ Brunel Surface treatment of titanium alloys

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1748378A (en) * 1928-10-06 1930-02-25 Percy A E Armstrong Process of casehardening ferrous articles
US2523883A (en) * 1947-06-20 1950-09-26 Cincinnati Milling Machine Co Heat-treating machine
CA555952A (en) * 1958-04-15 R. Ogden Horace Method of bright-hardening titanium and zirconium
US2892743A (en) * 1953-01-29 1959-06-30 Andrew J Griest Surface hardening of titanium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA555952A (en) * 1958-04-15 R. Ogden Horace Method of bright-hardening titanium and zirconium
US1748378A (en) * 1928-10-06 1930-02-25 Percy A E Armstrong Process of casehardening ferrous articles
US2523883A (en) * 1947-06-20 1950-09-26 Cincinnati Milling Machine Co Heat-treating machine
US2892743A (en) * 1953-01-29 1959-06-30 Andrew J Griest Surface hardening of titanium

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3314827A (en) * 1963-12-24 1967-04-18 Shell Oil Co Process for the hardening of metals
US5330587A (en) * 1992-02-28 1994-07-19 Ingersoll-Rand Company Shaft of laser nitride-hardened surface on titanium
US5366563A (en) * 1992-12-28 1994-11-22 General Electric Company Hot argon cleaning and protective coating of components made of metal or alloy
ES2108599A1 (en) * 1992-12-28 1997-12-16 Gen Electric Hot argon cleaning and protective coating of components made of metal or alloy
EP0721997A1 (en) * 1993-10-27 1996-07-17 Fuji Oozx Inc. Method of treating the surface of TI or TI alloy valve element
US5551671A (en) * 1994-07-27 1996-09-03 General Electric Company Hot argon cleaning and protective coating of components made of metal or alloy
FR2962671A1 (en) * 2010-07-13 2012-01-20 Air Liquide METHOD FOR ARC WELDING AND INERT GASES OF ALUMINUM METALLIC PARTS
WO2012022862A1 (en) * 2010-07-13 2012-02-23 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for arc-welding aluminum-coated metal parts using an inert gas containing nitrogen
CN102971103A (en) * 2010-07-13 2013-03-13 乔治洛德方法研究和开发液化空气有限公司 Method for arc-welding aluminum-coated metal parts using an inert gas containing nitrogen
US20130105445A1 (en) * 2010-07-13 2013-05-02 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method For Arc-Welding Aluminum-Coated Metal Parts Using An Inert Gas Containing Nitrogen
CN102971103B (en) * 2010-07-13 2016-01-20 乔治洛德方法研究和开发液化空气有限公司 The inert gas arc welding comprising nitrogen is used to aluminize the method for metal parts
US9321132B2 (en) 2010-07-13 2016-04-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Hybrid arc/laser-welding method for aluminized steel parts using gammagenic elements and a gas containing less than 10% of nitrogen or oxygen
WO2012113019A1 (en) * 2011-02-24 2012-08-30 Mario Ciccotosto Method of forming durable working surfaces

Also Published As

Publication number Publication date
CH414302A (en) 1966-05-31
GB906895A (en) 1962-09-26
FR1271837A (en) 1961-09-15
CA713159A (en) 1965-07-06
DE1182016B (en) 1964-11-19

Similar Documents

Publication Publication Date Title
US3111434A (en) Surface hardening of metal body consisting of or containing titanium or zirconium
US4731253A (en) Wear resistant coating and process
US2665475A (en) Highly refractory body
US3059326A (en) Oxidation resistant and ductile iron base aluminum alloys
US2280223A (en) Coated electrode and welding rod
US1893160A (en) Electrode for electric arc welding or soldering
JPS62183994A (en) Wire for gas shielded arc welding of stainless steel
EP0570219B1 (en) Use of a molten zinc resistant alloy
US6007922A (en) Chromium boride coatings
US3055088A (en) Composite metal body for high temperature use
US3184330A (en) Diffusion process
US2011706A (en) Arc welding electrode
US3208885A (en) Apparatus for nitriding of metals
US1641752A (en) Oxidation-resisting material
US3404969A (en) Cold-drawn alloy steel wire which can be hot dip coated with aluminum
US3015579A (en) Metal coating process
US3875363A (en) Composite electrode wire for electro-slag welding
US1599056A (en) Electrode for welding and like purposes
US1905247A (en) Welding electrode
US4684400A (en) Method for controlling the oxygen content in agglomerated molybdenum powders
US4715902A (en) Process for applying thermal barrier coatings to metals and resulting product
US1508032A (en) Corrosion-resisting ferrous alloy
JPH03281089A (en) Welding alloy improved for material with high yield strength, and welding method therefor
US1144390A (en) Electric welding and fusion deposition of metals.
JPS5961592A (en) Steel wire for arc welding