EP0812924A1 - Matière à base de titane et procédé pour sa fabrication et utilisation - Google Patents

Matière à base de titane et procédé pour sa fabrication et utilisation

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Publication number
EP0812924A1
EP0812924A1 EP96810621A EP96810621A EP0812924A1 EP 0812924 A1 EP0812924 A1 EP 0812924A1 EP 96810621 A EP96810621 A EP 96810621A EP 96810621 A EP96810621 A EP 96810621A EP 0812924 A1 EP0812924 A1 EP 0812924A1
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Prior art keywords
titanium
weight
titanium material
grade
oxygen
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EP96810621A
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German (de)
English (en)
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Karl-Heinz Kramer
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Institut Straumann AG
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Institut Straumann AG
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    • 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
    • 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

Definitions

  • the present invention relates to a biocompatible titanium material with improved fatigue strength, a method for producing the titanium material and its preferred use.
  • Titanium and titanium alloys have become indispensable materials in medical technology for more than 20 years.
  • the main applications concern joint replacement (eg hip joint endoprostheses, knee and arm prostheses), osteosynthesis products (eg bone plates and screws, intramedullary nails) and dental implants.
  • joint replacement eg hip joint endoprostheses, knee and arm prostheses
  • osteosynthesis products eg bone plates and screws, intramedullary nails
  • dental implants eg bone plates and screws, intramedullary nails
  • the particular suitability of titanium as an implant material results from its excellent biocompatibility, which has not been achieved by any other metallic material.
  • highly resilient implants are obtained, such as Hip joint endoprostheses that have to withstand enormous, changing loads. In principle, this also applies to osteosynthesis products and dental implants. Titanium alloys with forged design and high fatigue strength are always used for the production of hip joint endoprostheses.
  • unalloyed titanium is advantageously used for the production of osteosynthesis products and dental implants (cf. SCHROEDER / SUTTER / BUSER / KREKELER: Orale Implantologie. Georg Thieme Verlag Stuttgart, 2nd ed. 1994, p. 37ff.).
  • the fatigue strengths previously achieved with unalloyed titanium - mostly measured as alternating bending fatigue strength - are ⁇ bw ⁇ 380 MPa, while values of ⁇ bw ⁇ 540 MPa were achieved with titanium alloys.
  • the present invention is thus aimed at achieving fatigue strengths in unalloyed titanium which at least come close to the known implant titanium alloys.
  • the oxygen content, the work hardening and, in some cases, a subsequent relaxation annealing have been used; However, it is important to perfect hardening mechanisms known per se to the metal scientist and to use them in a combination, as a result of which the mechanical material parameters can be further optimized.
  • Titanium has good corrosion resistance; its high resistance in oxidizing media is characteristic.
  • the strong affinity for oxygen with the immediate formation of an oxide layer - this inhibits further corrosion - is characteristic.
  • the special suitability of titanium and titanium alloys as implant materials has been demonstrated using current density potential curves. Both unalloyed titanium and titanium alloys show no significant differences in corrosion removal in physiological saline at 37 ° C in the relevant application range between -200mV and + 300mV.
  • the corrosion resistance of titanium, titanium alloys, zircon, niobium, tantalum and platinum is at a high level, whereby these materials are inert in the fabric.
  • the implant steel 316L (FeCrNiMo) and the cobalt-based alloy CoCrNiMo also have a high corrosion resistance, but these materials cause an undesirable tissue reaction in the body due to sequestration.
  • the ratios of silver, gold, aluminum, molybdenum and iron are even more unfavorable, the latter having the lowest corrosion resistance.
  • the elements cobalt, copper, nickel and vanadium are increasingly toxic as a result. This illustrates that a material with high corrosion resistance does not guarantee biocompatibility at the same time.
  • ideal implant materials are titanium, zircon, niobium, tantalum and their alloys.
  • titanium is essentially due to the strong affinity for oxygen, which means that the titanium surface immediately covers itself with an oxide film of atomic thickness, which behaves neutrally in the electrolyte - ie in the blood.
  • the electrically non-conductive oxide film acts as a strong barrier against further dissolution of the metal. Electrically neutral hydrolysis products do not develop an attempt to react with organic molecules.
  • implant steel on the other hand, there are twofold electrical-positive undesirable reaction products charged ions that can form toxic antigens with the proteins of the human body. Nickel is known for its allergic and toxic effects.
  • the static and dynamic, mechanical properties are also extremely important.
  • the static, mechanical properties normally determined in the tensile test are the tensile strength R m (maximum stress occurring in the stress-strain diagram) and the often more significant proof stress R p (limit stress at which a material no longer behaves exclusively elastically and changes into the plastic state ).
  • the technical proof stress is usually specified with 0.2% proof stress R p0.2 .
  • a high-strength material should have both a high R m value and a high R p0.2 value so that no plastic deformation occurs under real loads.
  • Table 1 below shows the characteristic strength values according to DIN standard 17 869 from Titan Grade 1, Titan Grade 4 and the titanium alloy TiAl6V4: Table 1 Strength values (guide values) Titan Grade 1 Titan Grade 4 Titanium alloy TiAl6V4 Tensile strength R m [MPa] 350 640 930 0.2% proof stress R p0.2 [MPa] 240 480 865 Elongation A 5 [%] 45 25th 13
  • the specification values for the strength of titanium materials for implants are in the ASTM standards F 67-89, F 136-92, F 1295-92 and F 1341-92 as well as in ISO standards 5832 / II, 5832-3 and 5832 -11 fixed.
  • Table 2 shows the characteristic strength values according to ASTM standard F 67-89 for bars made of annealed, unalloyed titanium of various degrees: Table 2 Titan grades Tensile strength R m min. [MPa] 0.2% proof stress Rp 0.2 min. [MPa] Elongation A 4 min. [%] Constriction Z min. [%] 1 240 170 24th 30th 2nd 345 275 20th 30th 3rd 450 380 18th 30th 4th 550 483 15 25th
  • Table 3 shows the characteristic strength values for wire according to ASTM standard F 1341-92 annealed, unalloyed titanium of various grades: Table 3 Titan grades Diameter D [mm] Tensile strength R m min. [MPa] 0.2% proof stress R p0.2 min. [MPa] Elongation A 4 min. [%] Constriction Z min.
  • An essential property of a heavily loaded material is the remaining ductility, which e.g. if a component is overloaded, its abrupt failure is excluded.
  • part of the ductility is lost through the work hardening process, i.e. With increasing degree of cold deformation, the elongation A or the ductility decreases.
  • the metallurgist can use various hardening methods in accordance with Table 4 below to influence the mechanical material parameters: Table 4 Hardening process Operation Mixed crystal hardening Substitution of titanium by other metallic elements soluble in it (e.g. zircon, niobium, tantalum) Hardening by adding interstitially dissolved elements Additive (e.g. oxygen, carbon, nitrogen) Cold forming Rolling, pulling, hammering Grain refinement Recrystallization annealing Precipitation hardening Additive (e.g. iron, copper, silicon) Cold forming and precipitation hardening Additive (e.g. iron, copper, silicon) and cold working
  • Additive e.g. iron, copper, silicon
  • the titanium alloy TiAl6V4 has been introduced as a standard alloy for decades.
  • a forgeable alloy for implants for bone and dental surgery is known from CH-A-539 118.
  • This alloy consists of 3-50% by weight X and otherwise essentially Z, where X is one of the elements niobium, tantalum, chromium, molybdenum, tungsten, iron or aluminum or any mixture of these elements, while Z is one the elements are titanium or zirconium or any mixture of these elements.
  • the vanadium present in the standard alloy was then either replaced by iron or in a further improvement by niobium, so that the alloys TiAl5Fe2.5 and TiAl6Nb7 were formed.
  • the titanium materials known in this respect cannot be regarded as optimal with regard to the totality of all requirements - ie biocompatibility, in particular "osseointegration", mechanical parameters, production expenditure and cold deformability.
  • the compromises found so far are unsatisfactory, in particular it has so far not been possible to achieve the highest possible biocompatibility and "osseointegration”, as well as high tensile strength R m and fatigue strength.
  • the manufacturing outlay for the materials is relatively high, and improved cold formability, for example for the production of long products such as bars and profiles, is also particularly desirable.
  • Wire, rods, profiles, plates, sheet metal and strip of any desired dimensions can be produced from the material.
  • the titanium material according to the invention is used primarily for use in medical technology for implants - e.g. Dental implants, root posts, posts, bone plates and screws, intramedullary nails, heart valves and prostheses -, for instruments and for devices. Another important area of application is the watch and jewelry industry, where the excellent material properties in contact with the skin are essential.
  • the starting point for the production of the titanium material is a melt with the chemical composition according to Table 5 , which corresponds to the requirements for titanium implant materials according to ASTM F 67-89: Table 5 element Mass content [%] O 0.30 Fe 0.15 C. 0.007 N 0.01 H 0.0031
  • Iron is an accompanying element or an impurity and can be contained in the titanium ore up to 20% by weight. It has to be extracted in a treatment process in order to achieve the desired low iron content in the titanium sponge.
  • the sponge quality used depends on the goal.
  • the iron content of commercially produced titanium can vary from 0.035 to 0.5% by weight, depending on the use of very clean to heavily contaminated titanium sponge.
  • a raw material with a relatively high iron content is used in a targeted manner.
  • a possibly too low oxygen content is compensated for by adding titanium oxide.
  • the oxygen content is increased up to 0.40% by weight, normally up to 0.35% by weight. It has proven to be advantageous here to limit the oxygen content to 0.35% by weight - oxygen contents up to this value improve the strength without reducing the ductility too much.
  • Figure 2 shows the influence of the proportions of oxygen, nitrogen and carbon on the mechanical properties - proof stress, tensile strength, elongation and hardness.
  • an oxygen content for example of 0.30% by weight
  • the yield strength of conventional titanium is R P0.2 ⁇ 500 MPa, a tensile strength R m ⁇ 650 MPa and an elongation A of just over 20%.
  • Comparable values for the yield strength R P0.2 and the elongation A can be seen in Figures 3 to 5 .
  • the carbon and nitrogen contents shown in Figures 4 and 5 are sometimes outside the maximum values permitted by ASTM standard F 67-89 (for carbon up to 0.10% by weight and for nitrogen between 0.03% by weight and 0.05% by weight depending on the titanium grade).
  • the carbon and nitrogen fractions that actually occur in unalloyed titanium are ⁇ 0.01% by weight. At higher proportions, there is a risk of the formation of titanium carbides and nitrides, which can lead to material breaks.
  • the carbon and nitrogen fractions are considered to be normal admixtures and not as alloying elements.
  • Table 6 gives an overview of the possible heat treatments for titanium and titanium alloys for setting specific material properties with the most important types of annealing - soft annealing, stress relieving, solution annealing and aging and the associated annealing temperatures ⁇ (see also DIN standards 17869 and 65084). Within the entire process sequence for the production of the titanium material according to the invention, heat treatments known per se are carried out in some cases.
  • the increase in strength achieved by the cold-forming process is more or less reversed.
  • Complete softening down to the initial state is achieved by annealing above the recrystallization threshold (soft state).
  • annealing temperatures below the recrystallization threshold only partial softening - called recovery - is brought about. The transition between recovery and recrystallization can be demonstrated most impressively by means of X-ray or electron microscopic examinations.
  • annealing in the heat treatment of titanium denotes the reversal of a hardening caused by forming or hardening. As a rule, the annealing is carried out above the recrystallization temperature.
  • a prerequisite for recrystallization - this means a complete recrystallization of the material - is a previous cold working.
  • the recrystallization starts at the most disturbed places of the crystal lattice.
  • No recrystallization occurs below a critical degree of deformation, which depends on the thermal and mechanical pretreatment, depending on the material.
  • the lower recrystallization temperature (recrystallization threshold) decreases with increasing degree of deformation.
  • the number of bacteria increases so that a more fine-grained structure is created.
  • the process serves to reduce residual stresses, e.g. after welding, machining or straightening.
  • the process is carried out at low temperatures without changing the structure.
  • This annealing is carried out in order to enrich the mixed crystal on the alloy components which are to be precipitated during the subsequent aging.
  • the alloy components are dissolved in the supersaturated state during solution annealing.
  • a prerequisite for the hardening of an alloy is a decrease in the solubility of alloy components as the temperature drops.
  • a prerequisite for solution annealing is rapid cooling or quenching at the end of the annealing in order to keep the alloy components in the supersaturated solution.
  • Table 6 does not contain temperature information for solution annealing and aging for titanium grades 1 and 4, since unalloyed titanium of this type cannot be hardened due to the normally low proportion of admixtures. No hardening alloy components are specifically added.
  • the elements oxygen, nitrogen, carbon and hydrogen are fully soluble in titanium up to the specified maximum values.
  • the iron originating from the titanium ore as an impurity is tolerated, for example, in titanium grade 4 up to 0.5% by weight (cf. ASTM standard F 67-89) and normally occurs in the form of coarse, spherical precipitations, preferably at grain boundaries.
  • the hardening exponent n as the degree for the hardening tendency of a material, is shown in Figure 8 (Titan Grade 1 - material 3.7025 and Titan Grade 2 - material 3.7035) depending on the position of the rolling direction. It becomes clear that with hexagonal titanium there is a strong directional dependency of the hardening exponent n with respect to the rolling direction. In the longitudinal direction, the highest values are measured for the mean hardening exponent n with 0.17 or 0.15 and for the transverse direction (90 ° to the rolling direction) the lowest values for the hardening exponent n ⁇ 0.12.
  • EP-B-0 436 910 provides a method for cold-forming unalloyed titanium with an intermediate annealing, this taking place below the recrystallization temperature and without the formation of cell structures.
  • the tensile strength R m is obtained through cold working steps increased from 30% each with intermediate annealing at temperatures ⁇ ⁇ 500 ° C to values between 900 MPa and 1000 MPa.
  • the elongation A drops only moderately between the individual hardening steps, as a result of which the required 10% limit can be maintained.
  • Titan Grade 4 behaves differently with an oxygen content of 0.30% by weight, an iron content of 0.15% by weight and a basic strength of ⁇ 700 MPa in the annealed condition. With a degree of deformation of 15%, the tensile strength R m already exceeds the limit of 860 MPa and the elongation A is still ⁇ 13%. It is a very fine-grained material with a grain size of ⁇ 10 ⁇ m (measured according to ASTM standard E 112-88). The grain boundaries provide an additional consolidation contribution because they represent an obstacle to dislocations that build up in front of the grain boundaries and make further deformation more difficult (cf. B ⁇ HM, H .: Introduction in the metallurgy.
  • the extremely fine-grained The structure results on the one hand from the relatively high iron content of 0.15% by weight - compared to the qualities usually used in medical technology with ⁇ 0.05% above the highest solubility of iron in titanium lattice at ⁇ 700 ° C - and on the other hand the intensive work hardening.
  • a fine grain size of 10 results in optimal consolidation and an increase in the 0.2 proof stress R p0.2 according to the Hall-Petch relationship.
  • the fine-grain structure also increases the fatigue strength ⁇ bw . Only with the increased iron content of> 0.08% by weight, preferably from 0.10% by weight to 0.20% by weight, does the full inhibitory effect on grain growth come about Carry. The extreme fine granularity is assumed in the method according to the invention to achieve the desired mechanical properties and is used consistently.
  • the separation of supersaturated mixed crystals is known to have a strong influence on the physical and mechanical properties of a material. Since segregation processes are generally associated with a significant increase in the proof stress R p0.2 , the tensile strength R m and the hardness of an alloy, this is referred to as hardening.
  • a precondition for a hardenable alloy is a dependency of the dissolving power for an added element on the temperature in the alloy system.
  • the maximum solubility for iron in titanium in the temperature range of approx. 700 ° C is 0.05% by weight. As the temperature drops, the solubility decreases sharply and is only 0.006% by weight at 400 ° C. At even lower temperatures, the solubility of titanium for iron should be less than 0.001% by weight. With the solubility limit of ⁇ 0.05% by weight at ⁇ 700 ° C, there is always in unalloyed titanium with higher iron contents TiFe excretions. Their shape is determined by the mass fraction in% by weight, the manufacturing process and the size range of the end product.
  • unalloyed titanium is used in the annealed condition. Due to the needs of the chemical industry, Titan Grade 2 is clearly the most frequently used material. For higher demands on the mechanical properties, titanium grade 4 annealed is used. In order to achieve even higher tensile strengths R m > 680 MPa (according to ISO standard 58321 / II), cold forming is necessary. The relevant standards do not refer to precipitation hardening of unalloyed titanium. This is certainly because the titanium grades Grade 1 to Grade 4 apart from oxygen - this is up to 0.4% interstitially dissolved - no metallic alloy element is added. The iron contained in the titanium ore rutile up to 20% by weight as an impurity is elaborately removed.
  • the prerequisite In order to be able to use precipitation hardening in the titanium-iron two-component system at all by separating the intermetallic TiFe phase, the prerequisite must be created in the form of thermal treatment as annealing or also as hot deformation in the temperature range of maximum solubility. This is followed by aging at temperatures far below 700 ° C in order to remove as much of the TiFe phase as possible.
  • phase which has separated out has the same lattice structure as that Matrix, but differs in composition.
  • Coherent particles require a lower formation energy and, depending on the alloy, separate out flat, plate, spherical or needle-shaped.
  • the second type of segregation is the partially coherent separation, in which there is coherence at least with an interface with the matrix.
  • Partially coherent excretions are usually not the equilibrium phase, but rather metastable intermediate phases. According to the higher interfacial energy, the nucleation work in partially coherent phases is greater than in coherent phases.
  • the last stage of the decay of a supersaturated mixed crystal is the elimination of an incoherent phase as a continuous or discontinuous elimination.
  • the reason for the occurrence of coherent, partially coherent or incoherent phases lies in the different energy that has to be applied to form the interfaces.
  • incoherent phases In contrast to incoherent excretions, the easier nucleation in the intermediate phases leads to a higher nucleation frequency and consequently to a finer distribution of the excretions, which is associated with a greater hardening. Due to their higher nucleation work, incoherent phases are preferably eliminated at lattice defects such as dislocations and grain boundaries. The strong acceleration of segregation processes due to a previous cold working is therefore due to the increase in the number of foreign germs as a result of the increased dislocation density.
  • the production of grade 4 titanium rods with a diameter of 5 mm and the chemical composition according to Table 5 proceeds as follows.
  • the melt is melted, forged, hot rolled and drawn into wire using conventional techniques.
  • the thermal or thermomechanical treatment necessary for optimal curing takes place in the temperature range from 650 ° C to 750 ° C. This is followed by rapid cooling in order to keep as much iron as possible in solution. Annealing between 200 ° C and 500 ° C with steps of 25 ° are carried out.
  • the diffraction images within the images 16 to 18 of all three heat treatment states show strikingly pronounced superstructure reflections that occur as a result of finely separated coherent titanium-iron particles.
  • the particles were detected by dark field imaging in the light of a superstructure reflex (see Figure 17 ). At the low tempering temperature of 250 ° C, the particles have a rounded shape (see Fig . 19 ) and change to an oval shape at 450 ° C (see Fig . 20 ).
  • TiCu2 An examination of the titanium alloy TiCu2 also showed the appearance of a very fine phase as the result of a precipitation annealing.
  • the Ti-Si state diagram shows another alloy system with eutectoid segregation. Silicon additives of 0.2% by weight are already used in the high-strength ⁇ -titanium alloys to improve creep resistance and are generally suitable for a biocompatible, hardenable material - also for implants.
  • Annealing also has a significant share in the mechanical properties of the titanium material created. Comparative experiments on temper annealing with conventional implant material (iron content 0.05% by weight) and the inventive titanium grade 4 material, cold-formed, rod material, with an iron content of 0.15% by weight yielded the following results, which are shown in Figures 21 to 23 are shown.
  • the annealing temperatures from 200 ° C to 500 ° C cover the entire curing range. It can be seen that for both materials the 0.2% proof stress R p0.2 initially increases from ⁇ 750 MPa to values of 800 MPa at annealing temperatures up to ⁇ 250 ° C. Above this temperature, the yield strength R p0.2 of the conventional material drops sharply compared to the material according to the invention (see Figure 21 ).
  • Figure 23 shows a comparison of the conditions with regard to the elongation A 50 , which is ⁇ 10% for both materials when not tempered. Tempering temperatures ⁇ 200 ° C can significantly increase the strain values A 50 , especially for the conventional material, to 20%.
  • the improvements in the material according to the invention are clearly visible.
  • the tensile strength R m in the non-tempered state is 950 MPa, so confidently above the required specification limit of 860 MPa. Tempering reduces the tensile strength R m by ⁇ 100 MPa even at temperatures up to 400 ° C, while the conventional material only has a strength of ⁇ 700 MPa at the same tempering temperature.
  • the problem with every grade of work hardened titanium is always the ratio of tensile strength R m to elongation A. If too much cold deformation is used, the desired tensile strength R m can be achieved, but the required one The minimum elongation is not reached. This disadvantage is eliminated by tempering treatment, provided that there is a sufficiently high level of strength, which is reduced by tempering.
  • Precipitation hardening has an enormous influence on the fatigue strength ⁇ bw .
  • Surgical implants for example, are mainly stressed by fatigue. This is why this parameter is particularly important. This applies equally to hip joint endoprostheses, to osteosynthesis products and to dental implants, which of course are also subject to bending, torsional and shear forces.
  • the flexural fatigue strength ⁇ bw is by definition the stress that a material withstands 10 7 load cycles without breaking. It is known to increase the fatigue strength of titanium by adding oxygen.
  • the fatigue fatigue strength ⁇ bw of titanium grade 4 work hardened in the range from 357 MPa to 430 MPa. These values concern alternating bending fatigue strengths, which were determined with electropolished sample surfaces. IMI Titanium Ltd. published values are shown in Figure 24 .
  • Figure 24 shows that both the tensile strength R m and the fatigue strength ⁇ bw of soft-annealed samples increase with increasing oxygen content, with the curve for the tensile strength R m increasing more.
  • the values for notched samples are ⁇ 25% lower than those of the smooth comparison samples.
  • Figure 25 shows the influence of the oxygen content and the cold deformation on the tensile strength R m and fatigue strength ⁇ bw .
  • the fatigue bending fatigue strength ⁇ bw of the most cold-formed material is 380 MPa and thus coincides with the other values known from the literature.
  • solid solution hardening can be used within the manufacturing process for special use of the material.
  • Mixed crystal hardening replaces titanium atoms with other metallic atoms that are soluble in titanium.
  • Zircon for example, is particularly suitable for this, since it can be completely dissolved in both the ⁇ phase and the ⁇ phase.
  • Niobium and tantalum dissolve completely in ⁇ -titanium, but only to a limited extent in the ⁇ -phase, so that in this case ⁇ + ⁇ -titanium alloys are obtained.
  • Mixed crystal hardening can advantageously be used to improve tensile strength Raise R m decisively without having to accept an excessive loss of ductility.
  • the inventive precipitation hardening can consequently also be applied to a two-, three- or multi-material system, where zirconium, niobium or tantalum or any mixture thereof are added to the base material titanium.

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EP96810621A 1996-06-11 1996-09-19 Matière à base de titane et procédé pour sa fabrication et utilisation Withdrawn EP0812924A1 (fr)

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CH146796 1996-06-11
CH1467/96 1996-06-11

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DE102009034566A1 (de) * 2009-07-23 2011-02-03 Eads Deutschland Gmbh Verfahren zum Herstellen eines Tanks für Treibstoff
EP2333130A1 (fr) * 2004-03-19 2011-06-15 Nippon Steel Corporation Feuille d'alliage en titane thermorésistante excellente en maleabilité à froid et son procédé de production
CN115976440A (zh) * 2023-01-05 2023-04-18 宝鸡鑫诺新金属材料有限公司 一种抗感染医用含铜钛合金棒丝材的加工方法

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JP3753380B2 (ja) * 2003-07-18 2006-03-08 株式会社古河テクノマテリアル 生体用超弾性チタン合金の製造方法及び生体用超弾性チタン合金
JP6737686B2 (ja) * 2016-10-24 2020-08-12 国立大学法人豊橋技術科学大学 純チタン金属ワイヤおよびその加工方法
PT3489375T (pt) * 2017-11-22 2020-07-14 Biotech Dental Ligas ternárias de ti-zr-o, métodos para a produção das mesmas e utilizações associadas das mesmas

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DE2044692A1 (de) * 1969-09-12 1971-04-22 Kobe Steel Ltd Titanlegierungen mit ausgezeich neten Alterungs Hartungseigenschaften
FR2465520A1 (fr) * 1979-09-19 1981-03-27 Hermsdorf Keramik Veb Elements a resistance elevee a l'usure, en particulier pour melangeurs et broyeurs
DE3424030A1 (de) * 1983-07-01 1985-02-07 Nippon Gakki Seizo K.K., Hamamatsu, Shizuoka Titanlegierung zur dekorativen anwendung
JPS62127442A (ja) * 1985-11-27 1987-06-09 Sumitomo Metal Ind Ltd チタン合金およびその製造方法
EP0322087A2 (fr) * 1987-12-23 1989-06-28 Nippon Steel Corporation Matériau à résistance à base de titane, présentant une ductilité améliorée et procédé pour sa fabrication
EP0436910A1 (fr) * 1990-01-08 1991-07-17 STAHLWERK ERGSTE GMBH & CO. KG Procédé pour le profilage à froid de titane non allié
JPH04184711A (ja) * 1990-11-20 1992-07-01 Kobe Steel Ltd 磁気ディスク用チタン基盤とその製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2777768A (en) * 1953-08-03 1957-01-15 Mallory Sharon Titanium Corp Alpha titanium alloys
DE2044692A1 (de) * 1969-09-12 1971-04-22 Kobe Steel Ltd Titanlegierungen mit ausgezeich neten Alterungs Hartungseigenschaften
FR2465520A1 (fr) * 1979-09-19 1981-03-27 Hermsdorf Keramik Veb Elements a resistance elevee a l'usure, en particulier pour melangeurs et broyeurs
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Cited By (6)

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EP2333130A1 (fr) * 2004-03-19 2011-06-15 Nippon Steel Corporation Feuille d'alliage en titane thermorésistante excellente en maleabilité à froid et son procédé de production
US9797029B2 (en) 2004-03-19 2017-10-24 Nippon Steel & Sumitomo Metal Corporation Heat resistant titanium alloy sheet excellent in cold workability and a method of production of the same
DE102009034566A1 (de) * 2009-07-23 2011-02-03 Eads Deutschland Gmbh Verfahren zum Herstellen eines Tanks für Treibstoff
DE102009034566B4 (de) 2009-07-23 2017-03-30 Airbus Defence and Space GmbH Verfahren zum Herstellen eines Tanks für Treibstoff
CN115976440A (zh) * 2023-01-05 2023-04-18 宝鸡鑫诺新金属材料有限公司 一种抗感染医用含铜钛合金棒丝材的加工方法
CN115976440B (zh) * 2023-01-05 2024-05-28 宝鸡鑫诺新金属材料有限公司 一种抗感染医用含铜钛合金棒丝材的加工方法

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