EP3117016A2 - Alliage de titane nanostructuré et procédé de traitement thermomécanique de ce dernier - Google Patents

Alliage de titane nanostructuré et procédé de traitement thermomécanique de ce dernier

Info

Publication number
EP3117016A2
EP3117016A2 EP15811866.1A EP15811866A EP3117016A2 EP 3117016 A2 EP3117016 A2 EP 3117016A2 EP 15811866 A EP15811866 A EP 15811866A EP 3117016 A2 EP3117016 A2 EP 3117016A2
Authority
EP
European Patent Office
Prior art keywords
titanium alloy
nanostructured
article according
alloy article
developed
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.)
Withdrawn
Application number
EP15811866.1A
Other languages
German (de)
English (en)
Other versions
EP3117016A4 (fr
Inventor
Gian COLOMBO
Venkata ANUMALESETTY
Graham MCINTOSH
Yuliya MARDAKHAYEVA
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.)
Manhattan Scientifics Inc
Original Assignee
Manhattan Scientifics 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 Manhattan Scientifics Inc filed Critical Manhattan Scientifics Inc
Publication of EP3117016A2 publication Critical patent/EP3117016A2/fr
Publication of EP3117016A4 publication Critical patent/EP3117016A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

Definitions

  • the invention relates to a nanostructured material and, more particularly, a
  • nanostructured titanium alloy having a developed a-titanium structure with enhanced material properties.
  • microstructure plays a key role in the establishment of mechanical properties.
  • a material's structure can be developed to enhance material properties. For instance, it is possible to modify the grain or crystalline structure of the material using mechanical, or thermo-mechanical processing techniques.
  • United States Patent Application 2011/0179848 discloses a commercially pure titanium product having enhanced properties for biomedical applications.
  • the titanium product has a nanostructure, which provides enhanced properties in relation to the original mechanical properties, including mechanical strength, resistance to fatigue failure, and biomedical properties.
  • the known titaniu m product is first subject to severe plastic deformation (SPD) using an equal channel angular pressing (ECAP) technique at a temperature no more than 450° C with the total true accumulated strain e ⁇ 4, and then subsequently developed using thermomechanical treatment with a strain degree from 40 to 80%.
  • an object of the invention is to increase the level of strength and fatigue resistance of a titaniu m alloy.
  • the nanostructu red alloy includes a developed titanium structure having at least 80% of grains of a size ⁇ 1.0 microns.
  • Figure 1 is a micrograph of a known commercially pure titanium alloy taken using electron back scatter diffraction
  • Figure 2 is a micrograph of a nanostructured commercially pure titanium alloy accord ing to the invention taken using electron back scatter diffraction;
  • Figure 3 is a graphical representation, obtained using electron back scatter diffraction, showing the grain size distribution of the known commercially pure titanium alloy
  • Figure 4 is a graphical representation, obtained using electron back scatter diffraction, showing the grain size distribution of the nanostructured commercially pure titanium alloy according to the invention.
  • Figure 5 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of the known commercially pure titanium alloy
  • Figure 6 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of the nanostructured commercially pure titanium alloy according to the invention.
  • Figure 7 is a graphical representation, obtained using electron back scatter diffraction, showing the grain shape aspect ratio distribution in the longitudinal plane of the nanostructu red commercially pure titanium alloy accord ing to the invention.
  • Figure 8 is a graphical representation, obtained using electron back scatter diffraction, showing the grain shape aspect ratio distribution in the transverse plane of the nanostructured commercially pure titanium alloy accord ing to the invention.
  • Figure 9 is a micrograph of the commercially pure nanostructured titanium alloy according to the invention having a plurality of equiaxed grains, obtained using transmission electron microscopy;
  • Figure 10 is a micrograph of the commercially pure nanostructured titanium alloy according to the invention having a plurality of grains with high dislocation density, obtained using transmission electron microscopy;
  • Figure 11 is a micrograph of the commercially pure nanostructured titanium alloy according to the invention showing a plurality of sub-grains, obtained using transmission electron microscopy;
  • Figure 12 is a micrograph of a known titanium alloy Ti6AI4V taken using electron back scatter diffraction
  • Figure 13 is a micrograph of a nanostructured titanium alloy Ti6AI4V according to the invention taken using electron back scatter diffraction;
  • Figure 14 is a graphical representation, obtained using electron back scatter diffraction, showing the grain size distribution of the nanostructured titanium alloy Ti6AI4V according to the invention.
  • Figure 15 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of a known titanium alloy Ti6AI4V;
  • Figure 16 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of the nanostructured titanium alloy Ti6AI4V according to the invention.
  • Figure 17 is a micrograph of a known titanium alloy Ti6AI4V ELI taken using electron back scatter diffraction
  • Figure 18 is a micrograph of a nanostructured titanium alloy Ti6AI4V ELI according to the invention taken using electron back scatter diffraction;
  • Figure 19 is a graphical representation, obtained using electron back scatter diffraction, showing the grain size distribution of the nanostructured titanium alloy Ti6AI4V ELI according to the invention.
  • Figure 20 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of a known titanium alloy Ti6AI4V ELI.
  • Figure 21 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of the nanostructured titanium alloy Ti6AI4V ELI according to the invention.
  • the invention is a nanostructu red titanium alloy that can be used in different industries for production of various useful articles, such as orthopedic implants, medical and aerospace fasteners, aerospace structural components, and high performance sporting goods.
  • a composition of commercially pure titanium having an a-titaniu m matrix that may contain retained ⁇ -titanium particles, is processed to develop the structure to achieve a nanostructure with at least 80% of the grains being ⁇ 1 micron.
  • the nanostructured titanium alloy exhibits various material property changes such as an increase in tensile strength and/or shear strength and/or fatigue endurance limit.
  • the nanostructured titanium alloy structure is developed using a combination of thermomechanical processing steps according to the invention. This process provides a developed microstructure having a preponderance of ultrafine grain and/or nanocrystalline structures.
  • Figures 1, 12, and 17 show the starting commercially pure titanium alloy, Ti6AI4V, and Ti6AI4V ELI microstructure, respectively.
  • Figures 2, 13, and 18 show the resulting structure of the nanostructured commercially pure titanium alloy, Ti6AI4V, and Ti6AI4V ELI according to the invention, respectively. Examination of the figures clearly shows the d ifference between the starting and nanostructured titanium alloys.
  • the workpiece can be comprised of various commercially available titanium alloys known in the art, such as commercially pure titanium alloys (Gradesl-4), Ti-6AI-4V, Ti-6A1-4V ELI, ⁇ -6 ⁇ - 7N b, Ti-Zr, or other known alpha, near alpha, and alpha-beta phase titanium alloys.
  • an alpha-beta phase titanium alloy is processed from a combination of a severe plastic deformation process type and non-severe plastic deformation type thermomechanical processing steps to develop a nanostructure with at least 80% of the grains being ⁇ 1 micron.
  • a coarse grain commercially pu re titaniu m alloy is used for the workpiece, which has the following composition by weight percent: nitrogen (N ) 0.07% maximum, carbon (C) 0.1% maximu m, hydrogen (H) 0.015% maximum, iron (Fe) 0.50% maximu m, oxygen (O) 0.40% maximum, total of other trace impurities is 0.4% maximu m, and titanium (Ti) as the balance.
  • titanium alloys may be used, including but not limited to other commercially pure titanium alloys, Ti-6AI-4V, Ti-6A1-4V ELI, Ti-6AI-7Nb, and Ti-Zr. Standard chemical compositions of these titanium alloys can be fou nd in Tables 1-3, which identify the standard chemical compositions by wt% max.
  • the workpiece for instance a rod or bar, is subjected to severe plastic deformation ("SPD") and thermomechanical processing.
  • SPD severe plastic deformation
  • the combined processing steps induce a large amount of shear deformation that significantly refines the initial structure by creating a large number of high angle grain boundaries (misorientation angle > 15°) and high dislocation density.
  • the workpiece is processed using an equal channel angular pressing - conform (ECAP-C) machine, which consists of a revolving wheel having a circumferential groove and two stationary dies that form a channel that intersect at a defined angle.
  • ECAP-C equal channel angular pressing - conform
  • the workpiece is pressed into the wheel groove and is driven through the channel by frictional forces generated between the workpiece and the wheel.
  • a commercially pure titanium alloy workpiece is processed through the ECAP-C machine at temperatures below 500°C, preferably 100-300°C.
  • Other titanium alloys: Ti6AI4V, Ti6AI4V ELI, and Ti6Al7N b are processed through the ECAP-C machine at a temperature below 650°C, preferably 400- 600°C.
  • the workpiece passes through the ECAP-C machine between 1 and 12 times, preferably 4 to 8 times.
  • ECAP route B c This method of rotation is known as ECAP route B c .
  • the ECAP route may be changed, including but not limited to known routes A, C, B A , E, or some combination thereof.
  • thermomechanical processing further evolves the structu re of the workpiece, more than the ECAP-C alone.
  • one or more thermomechanical processing steps may be carried out, including but not limited to drawing, rolling, extrusion, forging, swaging, or some combination thereof.
  • the thermomechanical processing for commercially pure titanium alloy is carried out at temperatures T ⁇ 500°C, preferably room temperatu re to 250°C.
  • Thermomechanical processing of titanium alloys Ti6AI4V, Ti6AI4V ELI, and Ti6Al7N b is carried out at temperatures not greater than 550°C, preferably 400-500°C.
  • Thermomechanical processing provides a cross-sectional area reduction of > 35%, preferably > 65%.
  • the combination of severe plastic deformation and thermomechanical processing substantially refines the initial structure, which consists of an a-titaniu m matrix that may contain retained ⁇ -titanium particles, to a predominantly submicron grain size.
  • the ECAP-C process fragments the starting grain structure by introducing large numbers of twins and dislocations that organize to form dislocation cells with walls having a low misorientation angle ⁇ 15°.
  • the resulting nanostructured titanium alloy includes an a- titanium matrix that may contain retained ⁇ -titanium particles.
  • Figure 3 is a histogram showing the grain size distribution in the starting commercially pure titanium alloy.
  • Figures 4, 14, and 19 are histograms showing the grain size distribution in the nanostructured commercially pure titanium alloy, nanostructu red Ti6AI4V, and nanostructured Ti6AI4V ELI, respectively, according to the invention.
  • the average grain size of the nanostructured titanium alloys is red uced from the starting titanium alloys.
  • Figure 5 shows that the starting commercially pure titanium alloy has 90%-95% of the grain boundaries with misorientation angle > 15°
  • Figure 6 shows that the nanostructured commercially pure titanium alloy retains 20%- 40% of the grain boundaries with misorientation angle > 15°.
  • Figures 15 and 20 show that the starting titanium alloys: Ti6AI4V and Ti6AI4V ELI has 40-55% of the grain boundaries with misorientation angle > 15°
  • Figures 16 and 21 show that the nanostructured Ti6AI4V and Ti6AI4V ELI retains 20-40% of the grain boundaries with misorientation angle > 15°. These distributions contribute to the retention of useful ductility levels.
  • Figures 7 and 8 show the grain aspect ratio distribution in the longitudinal and transverse planes of the nanostructured commercially pure titanium alloy, which demonstrates an increased proportion of lower grain shape aspect ratio grains in the longitudinal plane compared to the transverse plane. The similar aspect ratio is observed in nanostructured Ti6AI4V and Ti6AI4V ELI alloys.
  • FIGS. 9-11 are TEM micrographs showing equiaxed grains, high dislocation density, and a high number of sub-grains in the nanostructured commercially pure titanium alloy, according to the invention.
  • the eq uiaxed grains are highlighted by continuous lines
  • Figure 10 the high dislocation density regions are highlighted with continuous lines.
  • the grains are highlighted with continuous lines and the sub-grains are highlighted with dotted lines.
  • Table 4 shows typical room temperature mechanical property levels of the starting titanium alloys and the nanostructured titanium alloys accord ing to the invention that can be achieved because of structure development.
  • Nanostructured 1200 1050 10 25 650 700 650 Commercially
  • the resulting nanostructured titanium alloys exhibit various material property changes, such as increased tensile strength and/or shear strength and/or fatigue endu rance limit.
  • the nanostructured titanium alloys according to the exemplary embodiment of the invention have a total tensile elongation greater than 10% and a reduction of area greater than 25%.
  • the nanostructured titanium alloys have at least 80% of the grains with a size ⁇ 1.0 microns, with approximately 20-40% of all grains having high angle grain boundaries, and > 80% of all grains have a grain shape aspect ratio in the range 0.3 to 0.7.
  • the nanostructured titanium alloy articles have grains with an average crystallite size below 100 nanometers and a dislocation density of > 10 15 m "2 .
  • the invention provides a nanocrystalline structure having enhanced properties from the starting workpiece, as a result of severe plastic deformation and thermomechanical processing.
  • Titaniu m alloys that may be used in accordance with the present invention include commercially pure titanium alloys (Grades 1-4), Ti-6AI-4V, Ti-6A1-4V ELI, Ti-Zr, or Ti-6AI-7Nb.
  • the nanostructured titanium alloy in accordance with the present invention can be used to produce useful articles with enhanced material properties, includ ing aerospace fasteners, aerospace structural components, high performance sporting goods, as well as articles for medical applications, such as spinal rods, screws, intramedullary nails, bone plates and other orthopedic implants.
  • the invention may provide aerospace fasteners comprised of nanostructured Ti alloy having increased ultimate tensile strength, such as above 1200 M Pa, and increased shear strength, such as above 650 M Pa.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Powder Metallurgy (AREA)
  • Forging (AREA)
  • Catalysts (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Extrusion Of Metal (AREA)

Abstract

L'invention concerne un article en alliage de titane nanostructuré. Cet alliage nanostructuré comporte une structure en titane développée comprenant au moins 80% de grains présentant une granulométrie strictement inférieure à 1,0 micromètre.
EP15811866.1A 2014-03-14 2015-03-13 Alliage de titane nanostructuré et procédé de traitement thermomécanique de ce dernier Withdrawn EP3117016A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14/212,344 US20160108499A1 (en) 2013-03-15 2014-03-14 Nanostructured Titanium Alloy and Method For Thermomechanically Processing The Same
PCT/US2015/020389 WO2015199769A2 (fr) 2014-03-14 2015-03-13 Alliage de titane nanostructuré et procédé de traitement thermomécanique de ce dernier

Publications (2)

Publication Number Publication Date
EP3117016A2 true EP3117016A2 (fr) 2017-01-18
EP3117016A4 EP3117016A4 (fr) 2017-11-08

Family

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Application Number Title Priority Date Filing Date
EP15811866.1A Withdrawn EP3117016A4 (fr) 2014-03-14 2015-03-13 Alliage de titane nanostructuré et procédé de traitement thermomécanique de ce dernier

Country Status (5)

Country Link
US (1) US20160108499A1 (fr)
EP (1) EP3117016A4 (fr)
JP (1) JP2017512901A (fr)
CN (1) CN106460101A (fr)
WO (1) WO2015199769A2 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105618775A (zh) * 2016-04-11 2016-06-01 西安欧中材料科技有限公司 一种制备Ti-6Al-7Nb医用钛合金球形粉末的方法
DE102016122575B4 (de) * 2016-11-23 2018-09-06 Meotec GmbH & Co. KG Verfahren zur Bearbeitung eines Werkstücks aus einem metallischen Werkstoff
KR102364142B1 (ko) * 2017-08-28 2022-02-18 닛폰세이테츠 가부시키가이샤 티타늄 합금 부재
MX2020008068A (es) * 2018-01-31 2020-12-11 Titanium Textiles Ag Implante de malla de autofijación a base de hilo de titanio y polímeros biorreabsorbibles.
CA3091619C (fr) * 2018-01-31 2023-02-28 Limited Liability Company "Elastic Titanium Implants" Materiau chirurgical composite pour sutures a base d'un fil de titane a filaments multiples et de polymeres bioresorbables
CN108893654A (zh) * 2018-08-03 2018-11-27 燕山大学 一种全α相细晶高强韧耐蚀钛合金及其制备方法
US11396690B2 (en) * 2020-01-14 2022-07-26 Prince Mohammad Bin Fahd University Method of producing medically applicable titanium
KR102589875B1 (ko) * 2021-04-22 2023-10-13 한국재료연구원 미세결정립 순수 타이타늄 및 그 제조 방법
CN114369779B (zh) * 2021-12-15 2022-10-11 中国科学院金属研究所 一种高强度抗氢脆纯钛及其制备方法

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US20060213592A1 (en) * 2004-06-29 2006-09-28 Postech Foundation Nanocrystalline titanium alloy, and method and apparatus for manufacturing the same
US7829014B2 (en) * 2004-11-05 2010-11-09 The Boeing Company Method for preparing pre-coated, ultra-fine, submicron grain titanium and titanium-alloy components and components prepared thereby
RU2383654C1 (ru) * 2008-10-22 2010-03-10 Государственное образовательное учреждение высшего профессионального образования "Уфимский государственный авиационный технический университет" Наноструктурный технически чистый титан для биомедицины и способ получения прутка из него
KR101225122B1 (ko) * 2009-09-07 2013-01-22 포항공과대학교 산학협력단 저 변형량에서의 나노 결정립 티타늄 합금의 제조 방법
JP4766408B2 (ja) * 2009-09-25 2011-09-07 日本発條株式会社 ナノ結晶チタン合金およびその製造方法
JP5725457B2 (ja) * 2012-07-02 2015-05-27 日本発條株式会社 α＋β型Ｔｉ合金およびその製造方法
US20140271336A1 (en) * 2013-03-15 2014-09-18 Crs Holdings Inc. Nanostructured Titanium Alloy And Method For Thermomechanically Processing The Same

Also Published As

Publication number Publication date
EP3117016A4 (fr) 2017-11-08
WO2015199769A3 (fr) 2016-03-03
US20160108499A1 (en) 2016-04-21
JP2017512901A (ja) 2017-05-25
CN106460101A (zh) 2017-02-22
WO2015199769A2 (fr) 2015-12-30

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