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WO2003074752A1 - Cementation de titane - Google Patents

Cementation de titane Download PDF

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Publication number
WO2003074752A1
WO2003074752A1 PCT/US2003/005994 US0305994W WO03074752A1 WO 2003074752 A1 WO2003074752 A1 WO 2003074752A1 US 0305994 W US0305994 W US 0305994W WO 03074752 A1 WO03074752 A1 WO 03074752A1
Authority
WO
WIPO (PCT)
Prior art keywords
workpiece
titanium
metal
case
hardened
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.)
Ceased
Application number
PCT/US2003/005994
Other languages
English (en)
Inventor
Steven V. Marx
Sunniva R. Collins
Peter C. Williams
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.)
Swagelok Co
Original Assignee
Swagelok Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Swagelok Co filed Critical Swagelok Co
Priority to AU2003213601A priority Critical patent/AU2003213601A1/en
Publication of WO2003074752A1 publication Critical patent/WO2003074752A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C23C8/02—Pretreatment of the material to be coated
    • 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

Definitions

  • the present invention relates to case hardening of titanium by nitrogen diffusion and solid solution.
  • Titanium and its alloys like stainless steel, form a coherent oxide coating immediately upon exposure to air. See J.R. Birch and T.D. Burleigh, Corrosion, Vol. 56, No. 12, ⁇ 2000, NACE International. As further taught in this reference, this oxide coating is passive (i.e. unreactive) at room temperature. However, when heated up to 600° C, some passivity is lost while at 700° C passivity is significantly less. At 800° C, the oxide coating cracks and spalls.
  • U.S. Patent No. 4,768,757 teaches that a hardened titanium nitride surface layer which is golden in color and up to 2.5 microns thick can be produced by contacting the titanium workpiece with nitrogen gas at about 700° C to 880° C. See, also, U.S. Patent No. 3,656,995 and U.S. Patent No. 5,525,165. Some of these disclosures even indicate that hardened surface coatings as much as 20 microns thick can be obtained. See, for example U.S. Patent No. 4,511,411.
  • the hardened titanium nitride surface layers made in this way tend to exhibit poorer corrosion resistance than the base metal from which the workpiece is made, as determined by contact with 0.5% aqueous hydrofluoric acid.
  • these hardened surface layers are brittle and rough.
  • the fatigue strength of workpieces hardened in this way is lowered because of the crack nucleation sites introduced by this surface roughness. See the Background section of U.S. Patent No. 5,326,362 to Shetty et. al. As a result, this technology is not widely used as a practical matter.
  • the above-noted Shetty Patent describes a modified process in which the workpiece is contacted with nitrogen at temperatures below about 704° C for extended periods of time. Under these conditions, formation of titanium nitride is restricted to an extremely thin surface layer no more than 0.2 microns thick. In addition, a hardened- case layer up to several microns thick and free of titanium nitride forms below the titanium nitride surface layer by a solid solution hardening mechanism from diffused nitrogen, oxygen and carbon.
  • a hardened, corrosion resistant case 5 or more microns thick and containing substantially no titanium nitride can be produced in a titanium workpiece by contacting the workpiece with nitrogen and methane at temperatures above about 704° C for a time sufficient for molecular nitrogen to diffuse into the workpiece surfaces and produce a hardened case of a desired thickness by a solution hardening mechanism.
  • the present invention provides a new article of manufacture comprising a titanium or a titanium alloy workpiece having a hardened case essentially free of titanium nitride and having a resistance to corrosion by 0.5% aqueous hydrofluoric acid greater than that of the metal from which the workpiece, the hardened case being at least about 5 microns thick.
  • the present invention provides a new process for case hardening a metal workpiece made from titanium or titanium alloy comprising contacting the workpiece with a nitriding gas containing nitrogen and methane or analog at a temperature of about 700 to 850° C for a time sufficient to form a hardened case at least about 5 microns thick, the hardened case being essentially free of titanium nitride.
  • a titanium workpiece is surface treated to provide both improved hardness and enhanced corrosion resistance by contact with a nitriding gas containing nitrogen and methane or analog at a temperature above about 704° C for a time sufficient to form a hardened case at least about 5 microns thick and being essentially free of titanium nitride.
  • a nitriding gas containing nitrogen and methane or analog at a temperature above about 704° C for a time sufficient to form a hardened case at least about 5 microns thick and being essentially free of titanium nitride.
  • Titanium and its alloys are known to exist in a number of different crystallographic phases.
  • the most common phase known as the ⁇ -phase, is characterized by a hexagonal closely packed structure.
  • metal atoms arranged in this structure define octahedral interstitial sites between atoms.
  • Another phase exhibited by titanium and its alloys is the ⁇ -phase. In this phase, the atoms are not hexagonally closely packed. Nor do they define octahedral interstitial sites between atoms.
  • the - and /S-phases exist together. This is known as a duplex phase structure.
  • the present invention applies to all titanium and titanium alloys exhibiting the ⁇ -phase structure at least to some significant degree, typically 30% or more.
  • the present invention applies to titanium metal (i.e. essentially pure titanium) as well as to titanium alloys composed substantially completely of the ⁇ -phase.
  • the present invention also applies to duplex and other titanium alloys containing somewhat less than 100%) ⁇ -phase such as 90%, 80%, 70%, 60%, 50%, 40% and even 30% ⁇ -phase.
  • such alloys will contain at least about 90 wt.% titanium, although alloys containing as little as 65 wt.%>, 50 wt.% or even 35 wt.% titanium can also be used.
  • the workpiece to be treated in accordance with the present invention should contain enough metal in this phase to achieve a noticeable improvement in surface hardening as a result of this diffusion effect.
  • compatible metal means any other metal which will allow the alloy to exist at least partially in the ⁇ -phase and which will not otherwise prevent diffusion of nitrogen atoms into the octahedral interstitial sites in these alloys from occurring.
  • additional metals are aluminum, vanadium and molybdenum.
  • Ti-6A1-4N (6 wt.% Al, 4 wt.%> V, balance Ti), which is known as "Titanium 64" (also known as “Grade 5 Titanium”) and Ti-8Al-lN-lMo (8 wt.% Al, 1 wt.% N, 1 wt.% Mo, balance Ti), known as "Titanium 811.”
  • Titanium 811 exists almost entirely in the ⁇ -phase, while Titanium 64 has a duplex phase structure in which the - and -phases are present roughly equally. Nonetheless, both alloys show marked enhancements in both surface hardness and corrosion resistance when case hardened by this technology. Any other commercial titanium alloy, whether available today or sometime in the future, is also amenable to processing by the inventive technology, so long as at least some significant amount of the alloy is present in the - phase, as indicated above.
  • Nitriding Gas 6 wt.% Al, 4 wt.%> V, balance Ti
  • Ti-8Al-lN-lMo 8
  • the nitriding gas used in accordance with the present invention includes at least two components, a nitrogen-containing gas and a carbon-containing gas.
  • the nitrogen-containing gas supplies nitrogen atoms for producing a hardened case through diffusion of nitrogen atoms into the titanium metal matrix.
  • the preferred nitrogen- containing gas is molecular nitrogen, i.e. N 2 .
  • Commercially-available nitrogen gas, i.e. N 2 is the cheapest and easiest gas to use for this purpose.
  • Other nitrogen containing gases can also be used provided that, in the amounts and under the conditions used, they do not supply ingredients which would adversely affect the hardened case being formed. Examples of such other gases are ammonia and gaseous HCN, for example.
  • the second component of the nitriding gas of the present invention is a carbon-containing gas.
  • the carbon-containing gas supplies carbon atoms to the system which, as indicated above, impede the formation of titanium nitride precipitates.
  • nitriding can be accomplished by the inventive technology much faster than in the Shetty et al. Patent, thereby allowing a much deeper case to be formed than contemplated there.
  • hardened cases having thicknesses of 40 microns or more can be readily formed by the inventive technology, which is much thicker than the "several" microns in thickness contemplated by the Shelby Patent.
  • Carbon atoms also diffuse into the titanium metal matrix, at least to some degree, where they appear to act in a manner similar to the diffused nitrogen atoms in the sense of enhancing surface hardness without formation of undesirable precipitates, i.e. titanium carbide precipitates.
  • the amount of diffused carbon in the case hardened layer produced by the present invention will be less than that of diffused nitrogen.
  • the preferred carbon-containing gas is methane, i.e. CH .
  • Other carbon-containing gases can also be used provided that, in the amounts and under the conditions used, they do not supply ingredients which would adversely affect the hardened case being formed. Examples of such other carbon-containing gases are ethane, propane and HCN, for example.
  • Complementary reactant gases that is gases which may react with the nitrogen-containing gas, carbon-containing gas and/or the workpiece during nitriding, may also be present provided that they too, in the amounts and under the conditions used, do not supply ingredients which would adversely affect the hardened case being formed. Normally, however, it is desirable to avoid such gases.
  • diluents such as helium, argon, the other inert gases, and any other gas which does not react under the conditions encountered during nitriding, can also be present.
  • the amounts of carbon-containing gas and nitrogen-containing gas (i.e. the "active gases") in the nitriding gas of the present invention can vary widely, and essentially any amounts can be used.
  • the nitriding gas can be composed solely of the active gases, if desired.
  • the active gases can form only a small part of the nitriding gas, with the vast majority of the nitriding gas being composed of an inert gas and/or a complementary reactant gas.
  • the active gases can be as little as 1%> of the nitriding gas, with concentrations on the order of 1 to 10%, or 2 to 5%, being typical. Larger concentrations of the active gases, e.g. at least 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%,
  • nitriding gases in which the amount of nitrogen-containing gas, and especially nitrogen, is at least about 50 mol.%, more typically at least about 65 mol.% or even 75 mol.% or more, while the amount of carbon-containing gas is about 5 to 40 mol.%, more typically about 10 to 15 mol.%.
  • nitriding gases containing as little as 1% nitrogen and 2% carbon-containing gas can also be used.
  • the relative amounts of the carbon-containing and nitrogen-containing gases used in the present invention can also vary widely. Generally, these gases can be used in amounts such that the atomic ratio of nitrogen atoms to carbon atoms in nitriding gas (the "N/C ratio") will be about 20:1 to 1:20, more typically about 5:1 to 1:5, more typically about 2:1 to 1:2. Nitriding Conditions
  • nitriding of titanium can be accomplished at temperatures as low as 200° C and as high as 1200° C.
  • nitriding is normally carried out below about 880° C so as to avoid the heat distortion temperature of titanium (882° C) and above about 700° C so that the protective titanium oxide layer depassivates significantly so that nitridization can occur at a practical, commercially-feasible rate.
  • nitridization is also carried out at temperatures ⁇ above about 700° C. This enables nitridization to proceed with the protective titanium oxide layer on the workpiece surfaces being significantly depassivated which, in turn, enables nitridization to occur at a significant rate for forming a deeper case than possible at slower rates. With respect to the maximum nitridization temperature, however, temperatures exceeding about 850° C should be avoided. This is because formation of titanium nitride cannot be avoided, as a practical matter, above these temperatures, even when methane or other carbon-containing gas is included in the system. Accordingly, nitridization will normally be accomplished in accordance with the present invention at temperatures of about 700° C to 850° C, more typically about 750 to 850° C, or even 800 to 840° C.
  • a titanium workpiece which is nitrided with a nitriding gas composed of 85% nitrogen and 15% methane at 800° C (for 90 hours) exhibits essentially no titanium nitride precipitates as reflected by the fact that the corrosion resistance of its surface in 0.5% aqueous hydrofluoric acid is greater than the corrosion resistance of the titanium metal from which the workpiece is made.
  • nitriding at 1 atmosphere pressure using 85% N 2 and 15% CH , as the nitriding gas at 700 to 800° C for 90 hours is effective.
  • nitriding pure titanium metal as well as titanium alloys such as Titanium 64 under these conditions produces case hardened surfaces 40 or more microns thick having outer hardnesses of 800 Nickers or more and corrosion resistances better than the base metal being nitrided, i.e. better than the corrosion resistance of the untreated metal from which the workpiece is made.
  • These cases are as good as or even better than the cases produced by prior art nitriding processes in terms of thickness, hardness and corrosion resistance.
  • nitriding can be carried out to provide case hardened layers of less thickness (e.g. >35 microns, >30 microns, >25 microns, >20 microns, >15 microns, >10 microns or even >5 microns) and/or less hardness (e.g. >750 Nickers, >700 Vickers, >650 Nickers, >600 Nickers, >550 Nickers), as desired. Regardless of the particular target thickness and hardness desired, and regardless of the particular titanium alloy used, hardened cases of superior corrosion resistance will be achieved so long as the particular nitriding conditions used are selected in the manner described above. Titanium Nitride Surface Layer
  • a very thin surface layer of titanium nitrides may be formed on the nitride-free, case hardened layer produced by the present invention.
  • This nitride surface layer may be as much as 2 microns thick but is usually much thinner, i.e., ⁇ L.5 microns, --1.0 microns, and even --0.5 microns.
  • the thickness of this outer layer is less than about 10%), more typically less than about 5% and even less than about 3% of the thickness of the nitride-free, case hardened layer produced by the present invention.
  • This is much thinner than the titanium nitride-containing surface layers produced by conventional nitriding, which as indicated above are typically 5 to 20 microns thick or more.
  • the corrosion resistance of the nitride-containing surface layer produced by the present invention is unclear as of this writing. It is clear, however, that the corrosion resistance of the nitride-free hardened case produced by the present invention is superior to that of the base metal from which the workpiece is made. This is due at least in part, it is believed, to the essentially complete absence of titanium nitrides and carbides from this layer.
  • the corrosion resistance of workpieces produced by the present invention as a whole are vastly superior to the corrosion resistance of workpieces produced by conventional nitriding and as good as and often better than the corrosion resistance of untreated metal.
  • the fatigue strength of workpieces produced by the present invention compare quite favorably to the fatigue strength of similar workpieces which are either untreated or nitrided by conventional technology.
  • the fatigue strength of workpieces nitrided by conventional technology can decrease by as much as a factor of seven and, in general, are at least 40%) less than those of untreated workpieces. This is because the relatively thick, roughened surfaces produced by conventional nitriding introduce crack propagation sites into the workpiece surfaces. In the present invention, however, the nitride surface layer is so thin that effect of this roughened surface in terms of crack initiation is minimal.
  • workpieces produced by the present invention can have fatigue strengths, although less than otherwise identical workpieces which are untreated, are still better than the fatigue strengths of conventionally nitrided workpieces of the same hardness. Indeed, some workpieces produced by the present invention have fatigue strengths as good as or even better than that of otherwise identical but untreated workpieces.
  • Underlayment Layer
  • the titanium workpiece is provided with an iron coating prior to the nitriding process.
  • an iron coating prior to the nitriding process.
  • This can be most easily be done by electroplating the workpiece with iron in accordance with conventional electroplating techniques.
  • the iron coating can be applied by any other technique capable of providing a metal coating on a metal substrate. Examples are vapor deposition, sputtering and the like. Coating thickness of 0.3 to 1.5 microns, more particularly 0.9 to 1.2 microns, are appropriate.
  • the workpiece is coated with iron in accordance with this aspect of the invention, it can then be subjected to nitriding in accordance with the procedure described above.
  • the iron on the workpiece surfaces appears to diffuse substitutionally into the body of the workpiece ahead of the nitrogen from the nitriding process where it deposits in the form of a discrete underlayment layer.
  • the product formed in this aspect of the invention is composed of the body of the workpiece whose metal composition is unchanged, a hardened case layer of the same composition and thickness described above and an iron-containing intermediate layer which exhibits an a/ ⁇ duplex phases structure and in which some of the titanium atoms in the metal lattice have been replaced by iron atoms.
  • other "foundation metals" such as nickel which will substitutionally diffuse into ⁇ -phase titanium to form an ot/ ⁇ duplex phase structure may be used for this purpose.
  • Example 1 In order to more thoroughly define the present invention, the following working examples are provided.
  • Example 1 In order to more thoroughly define the present invention, the following working examples are provided.
  • a titanium disc made from Titanium 64 (Grade 5) and measuring 0.75 inch in diameter and 0.08 inch thick was subjected to nitriding by contact with a nitriding gas composed of 2.0% methane, 1.0% N 2 and 97% argon at 840° C for 45 hours.
  • the nitrided product was removed from the furnace and allowed to cool to room temperature.

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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)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Abstract

L'invention concerne une pièce à travailler en titane comprenant une couche superficielle durcie dont l'épaisseur vaut au moins 5 microns, et qui est sensiblement exempte de nitrure de titane. On obtient cette pièce à travailler par mise en contact avec un gaz de nitruration contenant de l'azote et une petite quantité de méthane à une température comprise entre environ 700°C et 850°C.
PCT/US2003/005994 2002-02-28 2003-02-28 Cementation de titane Ceased WO2003074752A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003213601A AU2003213601A1 (en) 2002-02-28 2003-02-28 Case hardening of titanium

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US36061502P 2002-02-28 2002-02-28
US60/360,615 2002-02-28
US39276802P 2002-07-01 2002-07-01
US60/392,768 2002-07-01

Publications (1)

Publication Number Publication Date
WO2003074752A1 true WO2003074752A1 (fr) 2003-09-12

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PCT/US2003/005994 Ceased WO2003074752A1 (fr) 2002-02-28 2003-02-28 Cementation de titane

Country Status (2)

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AU (1) AU2003213601A1 (fr)
WO (1) WO2003074752A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008124247A1 (fr) * 2007-04-06 2008-10-16 Swagelok Company Activation de l'aluminium
EP2390378A1 (fr) * 2010-05-24 2011-11-30 Air Products and Chemicals, Inc. Procédé et appareil de nitratation des articles métalliques
US11060175B2 (en) 2016-06-02 2021-07-13 Danmarks Tekniske Universitet Case hardened component of titanium

Citations (9)

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Publication number Priority date Publication date Assignee Title
CH585278A5 (en) * 1974-03-05 1977-07-15 Goehring Werner Activation of mass transfer in gas hardening of metals - by introducing an additional gas at higher temperature into the furnace chamber
JPS58174572A (ja) * 1982-04-02 1983-10-13 Oriental Eng Kk ガス軟窒化法
GB2190100A (en) * 1986-05-07 1987-11-11 Thyssen Edelstahlwerke Ag A titanium alloy and machine parts made therefrom
JPH0790541A (ja) * 1993-09-13 1995-04-04 Demutetsuku Kk ガス複合浸透改質方法及び装置
WO1995029270A1 (fr) * 1994-04-25 1995-11-02 Sturm, Ruger & Company, Inc. Procede de traitement de pieces de titane
EP0721997A1 (fr) * 1993-10-27 1996-07-17 Fuji Oozx Inc. Méthode de traitement de la surface d'un élément de soupape en titane ou alliage de titane
JPH10306365A (ja) * 1997-05-07 1998-11-17 Citizen Watch Co Ltd 表面硬化チタン材料およびチタン材料の表面硬化方法ならびにその製品
JPH1143760A (ja) * 1997-07-25 1999-02-16 Citizen Watch Co Ltd チタン硬化部材とその硬化処理方法
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Publication number Priority date Publication date Assignee Title
CH585278A5 (en) * 1974-03-05 1977-07-15 Goehring Werner Activation of mass transfer in gas hardening of metals - by introducing an additional gas at higher temperature into the furnace chamber
JPS58174572A (ja) * 1982-04-02 1983-10-13 Oriental Eng Kk ガス軟窒化法
GB2190100A (en) * 1986-05-07 1987-11-11 Thyssen Edelstahlwerke Ag A titanium alloy and machine parts made therefrom
JPH0790541A (ja) * 1993-09-13 1995-04-04 Demutetsuku Kk ガス複合浸透改質方法及び装置
EP0721997A1 (fr) * 1993-10-27 1996-07-17 Fuji Oozx Inc. Méthode de traitement de la surface d'un élément de soupape en titane ou alliage de titane
WO1995029270A1 (fr) * 1994-04-25 1995-11-02 Sturm, Ruger & Company, Inc. Procede de traitement de pieces de titane
JPH10306365A (ja) * 1997-05-07 1998-11-17 Citizen Watch Co Ltd 表面硬化チタン材料およびチタン材料の表面硬化方法ならびにその製品
JPH1143760A (ja) * 1997-07-25 1999-02-16 Citizen Watch Co Ltd チタン硬化部材とその硬化処理方法
JP2001081544A (ja) * 1999-09-13 2001-03-27 Citizen Watch Co Ltd チタン、あるいはチタン合金製食器およびその表面処理方法

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SPIES H-J ET AL: "GAS- UND PLASMANITRIEREN VON TITAN UND TITANLEGIERUNGEN", HAERTEREI TECHNISCHE MITTEILUNGEN, CARL HANSER VERLAG. MUNCHEN, DE, vol. 53, no. 5, 1 September 1998 (1998-09-01), pages 294 - 305, XP000779520, ISSN: 0341-101X *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008124247A1 (fr) * 2007-04-06 2008-10-16 Swagelok Company Activation de l'aluminium
EP2390378A1 (fr) * 2010-05-24 2011-11-30 Air Products and Chemicals, Inc. Procédé et appareil de nitratation des articles métalliques
US8961711B2 (en) 2010-05-24 2015-02-24 Air Products And Chemicals, Inc. Method and apparatus for nitriding metal articles
US11060175B2 (en) 2016-06-02 2021-07-13 Danmarks Tekniske Universitet Case hardened component of titanium
EP3878999A1 (fr) 2016-06-02 2021-09-15 Danmarks Tekniske Universitet Procédé d'oxydation de titane

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