WO1999005332A1 - Materiaux en titane contenant du tungstene - Google Patents

Materiaux en titane contenant du tungstene Download PDF

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Publication number
WO1999005332A1
WO1999005332A1 PCT/US1998/015425 US9815425W WO9905332A1 WO 1999005332 A1 WO1999005332 A1 WO 1999005332A1 US 9815425 W US9815425 W US 9815425W WO 9905332 A1 WO9905332 A1 WO 9905332A1
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WO
WIPO (PCT)
Prior art keywords
titanium
alloy
tungsten
alloys
density
Prior art date
Application number
PCT/US1998/015425
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English (en)
Inventor
Stanley Abkowitz
Susan M. Abkowitz
Paul F. Weihrauch
Harold Heussi
Walter Zimmer
Original Assignee
Dynamet Technology, Inc.
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 Dynamet Technology, Inc. filed Critical Dynamet Technology, Inc.
Publication of WO1999005332A1 publication Critical patent/WO1999005332A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • C22C1/0458—Alloys based on titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents

Definitions

  • the present invention relates to titanium and to titanium-based alloys where additions enable the density of the resulting materials to be controllably increased up to 11.48 kg/m 3 .
  • the major alloying additions employed in the titanium and titanium-based alloys are tungsten or tantalum.
  • the materials from which drivers are constructed have evolved from a hardwood club head with a metal striking face, to a hollow cast head of conventional stainless steel ("metal woods"), and recently to cast titanium drivers. Because titanium alloys, such as Ti-6AI-4V, possess some of the highest strength-to-weight ratios of all structural metals and they exhibit a useful modulus of elasticity, they are attractive alternatives to the traditional ferrous driver materials. By substituting lower density titanium for the higher density steel materials, the dimensions of the driver can be proportionately increased. Specifically, the surface area of the striking face including both width and height can be enlarged without exceeding the weight restrictions of a "regulation" club. As an example of the benefit of this material substitution, the enlarged striking face area, or “sweet spot", permits golfers to achieve greater consistency in play with a club of prescribed swing weight.
  • the iron which is basically a plate inclined to the axis of the shaft of the golf club
  • a dimensionally enlarged face can be produced by redistributing the thickness of the plate.
  • the remaining material is distributed around the perimeter of the golf club face as a thicker "picture frame.”
  • this perimeter-weighted iron design increase the size of the "sweet spot” (i.e., zone of most responsive and repeatable impact behavior) on the face of the iron and increase the rotational stability of the iron about the axis of the shaft, but it also provides a means to control the distance between the center of gravity of the club and the intended point of impact on the face of the club.
  • the center of gravity is controlled in three dimensions by the thickness of each element of the cast shell.
  • the mechanics of elastic energy transfer can be used to determine the optimum design thickness of the intended impact region.
  • Some club designs seek to shift the center of gravity of the club head towards the sole plate, the portion of the driver that lies at the greatest distance from the grip end of the club.
  • a higher density material such as copper-infiltrated tungsten or bronze, is mechanically-attached or joined, for example by welding or brazing, to the rest of the club. The result is no longer a monolithic material structure, but a combination of at least two components of two dissimilar materials with differing densities.
  • Other recreational goods which incorporate structurally efficient titanium alloys and a geometry optimized to control the center of gravity of a component in motion, include such things as lacrosse sticks, tennis rackets, and sail boat keel weights.
  • Aircraft subcomponents such as rudders and flaps, also require control of center of gravity and moments of inertia, and often involve mounting counterweights in specific locations. Missile wings and fins, satellite structures, and control surfaces for submarine and aerodynamic applications require the same combination of titanium structural alloy properties and control of center of gravity.
  • Figure 1A is a photomicrograph at 100X of Commercially Pure (CP) titanium with 30.5 weight per cent tungsten produced from a P/M preform after forging, air cooling, polishing and chemical etching to reveal uniform microstructure.
  • CP Commercially Pure
  • Figure 1 B is the same material shown in Figure 1A at 500X showing islands of undissolved tungsten surrounded by tungsten-rich (white) beta phase. Darker etching impurities mark the grain boundaries. The intermixed (grey) areas contain fine alpha titanium (white) and impurities.
  • Figure 2A is a photomicrograph at 100X of Commercially Pure (CP) titanium with 10.2 weight per cent tungsten produced from a P/M preform after forging, air cooling, polishing and chemical etching to reveal uniform microstructure. Islands of tungsten surrounded by tungsten-rich beta phase (white). Darker etched regions are impurities intermixed with alpha phase titanium.
  • CP Commercially Pure
  • Figure 2B is the same material shown in Figure 2A at 500X showing a typical (white) tungsten-rich island of beta titanium. Thin white regions in the surrounding area are alpha phase titanium.
  • Figure 3 is a photomicrograph at 50X of "micro-macro" composite, composed of a layer of CP Ti with 10.2 weight per cent tungsten (white layer), integrally bonded to a Ti-6AI-4V layer (grey) by forging a double-layered P/M perform at 1750F.
  • an alloy comprising titanium and tungsten having a density in the range of from approximately 4.8 to 11.5 kg/m 3 .
  • the alloy comprises titanium and partially dissolved tungsten particles.
  • the alloy can further include, as optional ingredients, metals selected from the group consisting of tantalum, molybdenum, niobium, ferrotungsten, and mixtures thereof. These additional metals are preferably particulates which are partially dissolved in the titanium.
  • the above heavy or high density titanium materials can be produced in a form near to the net shape of the final article based upon powder metallurgy ("P/M”) technology.
  • P/M powder metallurgy
  • Such an embodiment consists of blending commercially pure titanium powder with powders of pure tungsten, and then consolidating the blended powders into a structural solid ("green compact") through a controlled sequence of processes.
  • This sequence of processes includes blending the powders, either die pressing or cold isostatic pressing the powders into a free-standing solid or green compact, vacuum sintering the free-standing solid or green compact at an elevated temperature, and if necessary, hot isostatic pressing or hot forging the sintered solid.
  • the material may be further processed through traditional thermomechanical operations including hot isostatic pressing, extrusion, forging, rolling and diffusion bonding.
  • the objective of these operations is near-net shape making and microstructural control.
  • the powder metal solid may be alternatively melted and cast into final shape.
  • the alloy can be reduced to a powder form by a number of processes, including a rotating electrode process, pulverizing by hydriding/dehydriding, and atomization.
  • the P/M sequence results in a near-net shape P/M preform composed of a titanium alloy matrix, wherein the high density tungsten powder constituent is partially or totally dissolved.
  • the desirable compositions of this "heavy" titanium alloy which has been designated as "DensiTi”TM, covers alloys with theoretical densities of 4.80 to 11.48 kg/m 3 or 0.173 to 0.415 lb/in 3 achieved by the addition of 10.0 to 79.33 weight percent tungsten to titanium. This corresponds to a 2.82 to 49.99 atomic percent addition of tungsten.
  • Figures 1 , 2 and 3 Illustrated in Figures 1 , 2 and 3 are microstructures of alloys or composites illustrating embodiments of the invention produced by the preferred process of cold isostatic pressing, then vacuum sintering, followed by hot forging at 1750F.
  • Figure 1 is a 200X photomicrograph of Commercially Pure (CP) titanium with 30.5 weight per cent tungsten after forging, air cooling, polishing and chemical etching to reveal its microstructure.
  • Figure 2 is a 200X photomicrograph of Ti-6AI-4V with 10 weight per cent tungsten, forged at 1750F and air cooled.
  • Figure 3 is a 200X photomicrograph of "micro-macro composite", composed of a layer of CPTi with 10.2 weight per cent tungsten, integrally bonded to a Ti-6AI-4V layer. This two-layered puck was produced by forging a double-layered preform at 1750F.
  • the mechanical response of a given DensiTiTM alloy, its mechanical properties and structural integrity, are determined by the degree to which the tungsten alloying constituent is homogeneously dissolved within the titanium matrix.
  • Mechanical properties of typical heavy titanium alloys in the hot isostatically pressed condition, without forging, are presented in Table II.
  • the materials of the present invention exhibit increased values of density, hardness, strength and specific strength and can also be expected to show increased wear resistance and modulus of elasticity.
  • tungsten is completely soluble in titanium upon melting into the liquid phase, such as by consumable arc melting a P/M titanium-tungsten electrode.
  • concentration of tungsten within the titanium alloy matrix is not perfectly uniform throughout the solid, the resultant concentration gradients are generally lower than those achievable through sintering a P/M solid in the solid phase.
  • solid state diffusion can distribute the tungsten more uniformly throughout the titanium. If plastic flow conditions are imposed at elevated temperatures such as by forging or extrusion, a more homogeneous distribution of tungsten occurs even more quickly than by solid state diffusion at elevated temperature, as seen in Figure 1. Superimposing pressure but limiting flow at elevated temperatures such as by hot isostatic pressing, also accelerates solid state diffusion, reduces porosity in the P/M solid, and creates a more uniform distribution of tungsten in titanium.
  • This invention recognizes the difference in the degree of dissolution of the tungsten alloy attained, and encompasses titanium materials of this composition regardless of the end state of the alloying elements, i.e., either as a non-equilibrium metal composite, a homogeneous solid solution alloy, or a combination of both.
  • Substitution of tantalum, molybdenum, or niobium powder for part of the tungsten may be made.
  • the elements tantalum, molybdenum, or niobium are completely soluble in the beta phase of titanium, that is, they are beta isomorphous.
  • subsequent treatments such as hot isostatic pressing, forging, extrusion, or rolling, creates fully dense, heavy titanium alloys when these elements are substituted for tungsten.
  • tungsten may be accomplished by adding tungsten powder, or a precursor alloy powder such as ferrotungsten, a commercially available source of tungsten containing 78% W with the balance iron.
  • tungsten powder or a precursor alloy powder such as ferrotungsten, a commercially available source of tungsten containing 78% W with the balance iron.
  • chemical compatibility issues rather than economics, may dictate the substitution of tantalum, molybdenum, or niobium for tungsten as powder starting material, but the processing sequence, final near net shape forms, and intent to control center of gravity with density/location are essentially the same.
  • elemental powders a chemical element in powdered form, e.g. iron powder
  • master alloy powders an alloy of two or more elemental metals melted together then converted to powder
  • the objective of these alloy additions is to facilitate the densification of the material during sintering, to reduce the sintering temperature and/or time and to enhance specific material properties.
  • elemental titanium serves as the matrix continuum into which tungsten particulate along with Ta, Mo, and Nb can be added to increase density.
  • the same tungsten, tantalum, molybdenum, niobium particulates could be added to improve density and mechanical properties of titanium-based matrix alloys, including the following classes: alpha, including commercially pure titanium containing less than 1% deliberate alloy addition such as ASTM B 348-94 Grades 1 , 2, 3, 4, 7, and 14; near alpha, including alloys such as Ti-6AI-2Sn-4Zr-2Mo-0.08Si; alpha-beta alloys, including alloys such as Ti-6AI-4V (ASTM B 381-93 Grade F-5, ASTM B 348-94 Grade 5) as demonstrated in Table II and Figure 3, and Ti-6AI-6V- 2Sn; beta-rich alloys, including alloys such as Ti-13 Zr-13Nb; and metastable beta alloys, including alloys such as Ti-1AI-8V-5Fe, Ti-15
  • particulate-reinforced, titanium-alloy-matrix composites such as those designated CermeTi® and described in U.S. Patents #4,731 ,115, #4,968,348, and #5,102,451 , hereby incorporated by reference, may serve as a compositional basis for creating "heavy" titanium alloys with tungsten, tantalum and niobium additions.
  • the CermeTi® composites are created using powder metallurgical methods by adding particulate TiC, TiB, TiB 2 , and TiAI to titanium alloy matrix materials.
  • the above alloys with particulate additions of TiC, TiB, TiB 2 and TiAI, formulated by P/M methods, may be further thermomechanically processed or cast into shapes.
  • a composite of titanium carbide and tungsten particles within a matrix of Ti-6AI-4V serves to increase the elastic modulus, extend the service temperature capability, and improve the wear-resistance and enhance the corrosion resistance.
  • a macro-micro composite is produced from a multilayered P/M preform.
  • a layer(s) of P/M titanium-tungsten alloy can be alternated with layers of P/M Ti-6AI-4V, then cold isostatically pressed, vacuum sintered, then forged to form an integral, fully dense component with a microcomposite of P/M Ti-W interlayered with Ti-6AI-4V, as shown in Figure 3.
  • the same layering or patterning of materials can be accomplished in radial fashion through extrusion, or in a planar fashion through rolling.
  • the P/M preform or component described above may serve as a finished object such as an architectural fitting or golf club striking face insert, a semi-finished solid such as a machining preform requiring metal removal to produce a dimensioned surface, a consumable arc melting electrode such as feedstock for melting and investment casting, or as an intermediate solid preform, shaped specifically for further processing by forging, rolling or extrusion.
  • the following articles can be made from the invention: sporting and recreational goods, including golf club heads, lacrosse sticks, and tennis rackets; counter weight applications, including sail boat keel weights, aircraft and missile subcomponents, such as rudders, flaps and fins, and aerodynamic or submarine control surfaces; and wear resistant and cutting blade applications, including ski edges, knife blades, ice skate blades and the wearing surfaces of implanted hip and knee joint prosthetic devices.
  • sporting and recreational goods including golf club heads, lacrosse sticks, and tennis rackets
  • counter weight applications including sail boat keel weights, aircraft and missile subcomponents, such as rudders, flaps and fins, and aerodynamic or submarine control surfaces
  • wear resistant and cutting blade applications including ski edges, knife blades, ice skate blades and the wearing surfaces of implanted hip and knee joint prosthetic devices.
  • the inventors have further determined that the center of gravity of a titanium or titanium alloy component such as golf club head or wing flap assembly may be controlled by adding predetermined amounts of tungsten and/or tantalum powder to specific regions of the component by any of the following processing methods.
  • the first processing methods include forging, extruding, or rolling a monolithic P/M preform.
  • Each of the processes begins with a P/M preform, produced by consolidation and sintering of one powder blend.
  • the P/M preform would have a three-dimensional geometry dictated by the forging tooling cavity, hot flow behavior of the Ti-W matrix alloy, and desired final shape of the finished article.
  • elevated temperatures can be used to consolidate the preform, creating a fully dense solid with an extended linear dimension.
  • By rolling the P/M preform a fully dense sheet or plate can be created.
  • the hot isostatic pressing process can be employed after sintering to consolidate the powder preform into a more fully dense solid using high temperatures and pressures.
  • the second processing methods include forging, extruding, rolling, or hot isostatically pressing a macro-micro composite P/M preform.
  • the process begins with a cold-isostatically pressed preform composed of several powder metallurgy precursor materials. As shown by Figure 3, it is metallurgically possible to build up a P/M preform, by placing material of prescribed density in specific locations within the preform.
  • the three-dimensional geometry of a macro-micro composite forging preform is dictated by the forging tooling cavity, hot flow behavior of the various materials, and desired final shape of the finished article.
  • the dense material flows to specific, predetermined regions of the forging, creating a structural solid with specific solid density in specific regions.
  • Hot extrusion of a macro-micro composite preform can create a linear solid product, yet with higher density material distributed in specific regions within the cross-sectional area.
  • An example of this could be an extruded bar for flywheel applications with a Ti-6AI-4V core and a higher density Ti-W periphery.
  • Rolling of a macro-micro composite P/M preform can create a sheet or plate with an internal layered structure or lattice-patterned distribution, of increased density regions.
  • Hot isostatic pressing can be employed after sintering to consolidate a macro-micro composite into a free- form solid using high temperatures and pressures.
  • the third processing method includes diffusion bonding titanium alloy subcomponents.
  • a structural component of a titanium alloy such as a wing flap with an integral weight can be produced by diffusion bonding a structural member, such as wing skin/spar assembly to a "heavy" titanium counterweight. Because both components are titanium based alloys, conventional titanium diffusion-bonding at elevated temperatures will permit joining of the two components with a structurally sound interface.
  • the "heavy" titanium component could be produced by P/M processing or could be investment cast preferably from a P/M electrode starting stock.
  • alloy as used herein is not limited to single phase or multiple phase microstructures and includes mixtures of pure materials such as commercially pure titanium and tungsten particles, whether or not the particles have diffused into the surrounding material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne un matériau à base de titane qui contient du tungstène et d'autres métaux, y compris le tantale, le molybdène et le niobium. Le matériau contenant du titane possède une densité comprise entre 4,8 et 11,5 kg/m3 et des propriétés mécaniques améliorées, y compris le module d'élasticité, la résistance, la dureté et la résistance à l'usure.
PCT/US1998/015425 1997-07-25 1998-07-24 Materiaux en titane contenant du tungstene WO1999005332A1 (fr)

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US60/053,806 1997-07-25

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006053044A1 (fr) * 2004-11-10 2006-05-18 Dynamet Technology, Inc. Article en alliage de titane a grain fin et articles dotes de surfaces de titane poreuses enrobees
WO2006073428A2 (fr) * 2004-04-19 2006-07-13 Dynamet Technology, Inc. Alliages de titane et de tungstene produits par addition de nanopoudre de tungstene
WO2006091489A1 (fr) * 2005-02-22 2006-08-31 Dynamet Technology, Inc. Composites a matrice de metal de titane a rapport de filage eleve
WO2008048343A2 (fr) * 2006-02-14 2008-04-24 Dynamet Technology, Inc. Alliages titane-tungstène homogènes obtenus par technologie de poudre métallique
US9573192B2 (en) 2013-09-25 2017-02-21 Honeywell International Inc. Powder mixtures containing uniform dispersions of ceramic particles in superalloy particles and related methods
JP2021525152A (ja) * 2018-05-28 2021-09-24 ライフ バスキュラー デバイシズ バイオテック，エス．エル． ベータ相チタンとタングステンの合金
CN114101680A (zh) * 2021-11-17 2022-03-01 北京理工大学 一种钛合金表面硬质层的制备方法
US20220388090A1 (en) * 2021-06-04 2022-12-08 The Boeing Company Fabrication of thick stock via diffusion bonding of titanium alloys
CN116987920A (zh) * 2023-09-26 2023-11-03 海朴精密材料(苏州)有限责任公司 一种Ti基全金属含能结构材料、制备方法及其应用
CN117123779A (zh) * 2023-07-28 2023-11-28 西安欧中材料科技有限公司 一种战斗部壳体及其粉末热等静压成形方法

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006073428A2 (fr) * 2004-04-19 2006-07-13 Dynamet Technology, Inc. Alliages de titane et de tungstene produits par addition de nanopoudre de tungstene
WO2006073428A3 (fr) * 2004-04-19 2006-10-05 Dynamet Technology Inc Alliages de titane et de tungstene produits par addition de nanopoudre de tungstene
WO2006053044A1 (fr) * 2004-11-10 2006-05-18 Dynamet Technology, Inc. Article en alliage de titane a grain fin et articles dotes de surfaces de titane poreuses enrobees
WO2006091489A1 (fr) * 2005-02-22 2006-08-31 Dynamet Technology, Inc. Composites a matrice de metal de titane a rapport de filage eleve
US8043404B2 (en) 2005-02-22 2011-10-25 Dynamet Technology, Inc. High extrusion ratio titanium metal matrix composites
WO2008048343A2 (fr) * 2006-02-14 2008-04-24 Dynamet Technology, Inc. Alliages titane-tungstène homogènes obtenus par technologie de poudre métallique
WO2008048343A3 (fr) * 2006-02-14 2008-08-28 Dynamet Technology Inc Alliages titane-tungstène homogènes obtenus par technologie de poudre métallique
US10391554B2 (en) 2013-09-25 2019-08-27 Honeywell International Inc. Powder mixtures containing uniform dispersions of ceramic particles in superalloy particles and related methods
US9573192B2 (en) 2013-09-25 2017-02-21 Honeywell International Inc. Powder mixtures containing uniform dispersions of ceramic particles in superalloy particles and related methods
JP2021525152A (ja) * 2018-05-28 2021-09-24 ライフ バスキュラー デバイシズ バイオテック，エス．エル． ベータ相チタンとタングステンの合金
US20220388090A1 (en) * 2021-06-04 2022-12-08 The Boeing Company Fabrication of thick stock via diffusion bonding of titanium alloys
CN114101680A (zh) * 2021-11-17 2022-03-01 北京理工大学 一种钛合金表面硬质层的制备方法
CN114101680B (zh) * 2021-11-17 2022-08-19 北京理工大学 一种钛合金表面硬质层的制备方法
CN117123779A (zh) * 2023-07-28 2023-11-28 西安欧中材料科技有限公司 一种战斗部壳体及其粉末热等静压成形方法
CN116987920A (zh) * 2023-09-26 2023-11-03 海朴精密材料(苏州)有限责任公司 一种Ti基全金属含能结构材料、制备方法及其应用
CN116987920B (zh) * 2023-09-26 2023-12-08 海朴精密材料(苏州)有限责任公司 一种Ti基全金属含能结构材料、制备方法及其应用

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