CN118773478B - A copper-containing medical titanium alloy and preparation method thereof - Google Patents
A copper-containing medical titanium alloy and preparation method thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 148
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 82
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000003723 Smelting Methods 0.000 claims description 43
- 239000010936 titanium Substances 0.000 claims description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000005098 hot rolling Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
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- 239000000463 material Substances 0.000 claims description 5
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- 229910004353 Ti-Cu Inorganic materials 0.000 description 2
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- 239000007943 implant Substances 0.000 description 2
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/20—Arc remelting
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- 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
- C22C1/02—Making non-ferrous alloys by melting
-
- 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
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- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Transplantation (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Oral & Maxillofacial Surgery (AREA)
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Abstract
本发明公开了一种含铜医用钛合金及其制备方法，该含铜医用钛合金的化学式为Ti‑5Cu‑xZr，其中，0<x≤45；所述含铜医用钛合金的组织包括初生α板条，以及均匀分布在钛合金中的Zr2Cu析出相。该含铜医用钛合金具有高强度和高韧性。
The invention discloses a copper-containing medical titanium alloy and a preparation method thereof. The chemical formula of the copper-containing medical titanium alloy is Ti-5Cu-xZr, wherein 0<x≤45; the structure of the copper-containing medical titanium alloy comprises primary α laths and Zr 2 Cu precipitated phases uniformly distributed in the titanium alloy. The copper-containing medical titanium alloy has high strength and high toughness.
Description
Technical Field
The invention belongs to the field of metal alloys, and particularly relates to a medical titanium alloy containing copper and a preparation method thereof.
Background
Titanium and titanium alloy have the characteristics of high specific strength, low elastic modulus, strong corrosion resistance, good biocompatibility and the like, are widely applied to the biomedical field, such as artificial hip joints and knee joints, heart valves, vascular stents, mandibles, skull, sternum, vertebrae, dental implants, orthodontic fixtures, titanium bone nails, titanium bone plates and the like, and become one of the most promising medical metal materials after stainless steel and cobalt chromium alloy.
The TC4 alloy is taken as a typical alpha+beta type dual-phase alloy and is the most widely used medical titanium alloy at present. TC4 alloys are distinguished by their excellent mechanical properties (such as high strength, high hardness and excellent low cycle fatigue resistance), as well as excellent corrosion resistance and good cost effectiveness compared to other types of titanium alloys. However, after being implanted into a human body, the body fluid is eroded for a long time, and toxic metal ions (such as Al and V) are continuously released and accumulated, so that serious human health diseases such as peripheral neuropathy, osteomalacia, alzheimer disease and the like can be caused. In order to reduce the harm of TC4 alloy to human health to a greater extent, toxic elements such as Al, V and the like must be removed.
The copper-containing titanium alloy has excellent antibacterial property, good biocompatibility and multifunctionality, plays an important role in the medical field, and has wide application prospect in the implant fields of orthopaedics, dentistry and the like. Copper (Cu) has long been considered a trace element essential to the human body and has many excellent biological properties such as anti-inflammatory, antibacterial, antiproliferative, good cell compatibility, and osteogenesis stimulation.
The invention patent application with the publication number of CN114457258A discloses an ion slow-release high-strength Ti-Cu alloy, a 3D printing method and application thereof, wherein the mass percentage of Cu in the alloy is not more than 6%, the yield strength of the alloy is not less than 820MPa, the ultimate tensile strength is not less than 900MPa, the elongation is not less than 10%, the alloy does not contain beta columnar crystals, no obvious anisotropy exists, the macroscopic texture index of the alloy is lower than 1.5×random, the release amount of Cu 2+ ions in 35 days of the alloy is lower than 0.25mg/L, the alloy is prepared by a laser additive manufacturing technology, and the energy density is 80-100J/mm 3 during laser additive manufacturing. The product designed and prepared by the invention can be used for human bone implant materials. The invention has reasonable component design, simple and controllable preparation process and controllable shape of the formed product, and is suitable for large-scale application of bone grafts with special structures.
The invention patent application with publication number of CN108103353A discloses a medical TiMoCu alloy and a preparation method thereof, which belong to the field of medical titanium alloy and the preparation method thereof, wherein the medical TiMoCu alloy consists of Ti, mo and Cu elements, the mass ratio of Ti to Mo to Cu= (100-x-y) to x to y, x=10-20 and y=5-20, the density of the medical TiMoCu alloy is 98.5-99.9, the preparation method comprises the steps of 1) uniformly mixing commercial Ti powder, commercial Mo powder and commercial Cu powder according to the proportion to obtain a mixture, 2) pressing the mixture of the Ti powder, the Mo powder and the Cu powder into a blank with a set shape, 3) placing the blank in a die, heating the blank to 1150-1200 ℃ at a speed of less than or equal to 10 ℃ under vacuum, preserving heat for 4-6 hours, continuously pressurizing for 5-30 MPa, and cooling the alloy to room temperature along with a furnace after 2-4 hours, and obtaining the medical TiMoCu alloy prepared by the patent is used for tooth root or bone replacement and has a continuous inhibition effect on army bacteria and staphylococcus aureus.
However, the addition of Cu as an antibacterial agent disclosed in the above patent has a great adverse effect on the mechanical properties of titanium alloys, which may lead to deterioration of workability of the alloys and deterioration of application properties.
Disclosure of Invention
The invention provides a high-strength high-toughness medical copper-containing titanium alloy.
The invention provides a copper-containing medical titanium alloy, which has a chemical formula of Ti-5Cu-xZr, wherein x is more than 0 and less than or equal to 45;
The structure of the medical copper-containing titanium alloy comprises a primary alpha lath and a Zr 2 Cu precipitated phase which is uniformly distributed in the titanium alloy.
By adding Zr element and Cu element, the invention forms Zr 2 Cu precipitated phase, and obviously reduces the beta transition temperature of the alloy, so that Zr 2 Cu is uniformly distributed in the alloy, and meanwhile, the alloy alpha lath is obviously thinned. The Zr 2 Cu precipitated phase and the thinned structure can effectively block dislocation movement and improve the deformation resistance of the alloy.
In the titanium alloy, cu is used as eutectoid element, and can generate eutectoid reaction with Ti element to generate Ti 2 Cu precipitated phase, and the main function of Ti 2 Cu precipitated phase in the titanium alloy is to improve the mechanical property of the alloy through mechanisms such as dispersion strengthening, grain refinement and the like. However, the maximum solubility of Cu in the titanium alloy α phase is 1.6 at%, and the maximum solubility in the β phase is 13.5. 13.5 at%, in the ti—cu alloy, since about 5% of Cu element does not lower the titanium alloy β transformation temperature to a lower value, during the alloy cooling process, the β phase precipitates first α phase, and Cu element is concentrated in the remaining β phase, so that the Ti 2 Cu precipitated phase appears only in the second α phase, which limits the dispersion distribution of the Ti 2 Cu precipitated phase, often in the form of aggregation in the alloy structure.
The addition of Zr element makes up for this defect. Zr is considered as a neutral element and also shows transition from a low temperature hcp alpha phase to a high temperature bcc beta phase in a solid state, ti and Zr are completely mutually soluble in all phases, and a large addition of Zr element can significantly lower the titanium alloy beta transition temperature. Meanwhile, the Cu element and the Zr element can also generate eutectoid reaction to form a Zr 2 Cu precipitated phase, in the respective binary alloy systems, the eutectoid transition temperature of Ti and Cu is 790 ℃, the eutectoid transition temperature of Zr and Cu is 810 ℃, and the Zr 2 Cu is formed before the Ti 2 Cu, so that the Cu element is consumed in advance, and the precipitated phase is changed into Zr 2 Cu after the Zr element is doped in the copper-containing titanium alloy.
After Zr element is doped, in the cooling process of the titanium alloy, cu element exists in a beta phase in a solid solution state due to the sufficiently low beta transition temperature, because the solubility of the Cu element in the beta phase is about 8 times of that of the alpha phase, when the alpha phase starts to nucleate and grow, zr and Cu eutectoid reaction is carried out, the alpha phase and the Zr 2 Cu precipitated phase are almost formed at the same time, and finally the dispersed Zr 2 Cu phase is obtained. In addition, zr element can also obviously reduce the size of the titanium alloy alpha plate strip, thereby achieving the dual purposes of dispersion strengthening and fine crystal strengthening.
Preferably, the density of Zr 2 Cu in the medical titanium alloy containing copper is 10-130/(100 μm 2).Zr2) when the content of the Cu precipitated phase is low, the strengthening effect is not obvious, and when the content is too high, the precipitated phase tends to be aggregated, so that the alloy becomes brittle.
Preferably, the primary alpha slats have an average width of 0.4-3.2 μm.
Preferably, the copper-containing medical titanium alloy has a tensile strength of 740-1130 MPa and an elongation of 8-16%.
Preferably, when the mass percentage of Zr is 25-35%, the average width of the primary alpha lath is 0.5-0.9 mu m, and the density of Zr 2 Cu in the copper-containing medical titanium alloy is 47-109/(100 mu m 2).
The invention obtains a primary alpha lath with proper width and proper density of Zr 2 Cu phase by controlling the adding amount of Zr, and can maintain better elongation while obviously improving the tensile strength, thereby obtaining the copper-containing medical titanium alloy with the tensile strength of 1020-1030 MPa and the elongation of 13-14 percent. If the Zr content is too much, the average width of the primary alpha lath is too low, and the tensile strength is further improved, but the elongation is obviously reduced, so that the better comprehensive mechanical property is not obtained.
On the other hand, the invention also provides a preparation method of the medical copper-containing titanium alloy, which comprises the following steps:
(1) Batching according to the chemical formula of the copper-containing medical titanium alloy to obtain a mixed material;
(2) Carrying out secondary vacuum consumable smelting on the mixed material to obtain a titanium alloy secondary ingot;
(3) Uniformly annealing the titanium alloy secondary ingot at a temperature of 40-60 ℃ above the beta transformation point for 30-60 min%, and then carrying out hot rolling with a deformation of 75-85%;
(4) And carrying out solution treatment on the blank after hot rolling to obtain the copper-containing medical titanium alloy.
Homogenizing and hot-rolling at 40-60 deg.C above beta transition point can make the precipitated phase fully dissolved in high-temperature beta phase, ensure uniform diffusion of each element, and refine structure at the same time, so that alloy alpha strip width is more uniform and precipitated phase distribution is more uniform.
Preferably, the raw materials for the batching are titanium sponge, zirconium sponge and copper particles.
Preferably, the secondary vacuum consumable smelting comprises a first vacuum consumable smelting and a second vacuum consumable smelting;
The technological parameters of the first vacuum consumable smelting are that the current is 0.9-1.8 KA, the voltage is 30-33V, the pre-vacuum degree is 0-1 Pa, and the working vacuum degree is 0-8 Pa;
The technological parameters of the secondary vacuum consumable smelting are that the current is 0.9-3.6 KA, the voltage is 31.5-34V, the pre-vacuum degree is 0-0.8 Pa, and the working vacuum degree is 0-5 Pa.
In a vacuum consumable smelting process, smelting current and smelting voltage are critical parameters that need to be carefully controlled. The melting rate, the melting pool temperature and the arc length of the metal elements can be effectively controlled by selecting proper melting current and voltage, so that the uniform dissolution of the titanium, zirconium and copper elements is ensured, and excellent mechanical performance and chemical stability are obtained.
Preferably, the temperature of the solution treatment is 40-60 ℃ below the beta transus temperature for a period of 60-90 min.
Further preferably, the temperature of the solution treatment is 630-750 ℃.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, zr element is added into the Ti-Cu based alloy, so that a Zr 2 Cu precipitated phase is formed with Cu element, the beta transition temperature of the alloy is obviously reduced, the Zr 2 Cu precipitated phase is uniformly dispersed and distributed in the alloy, and meanwhile, the alloy alpha plate strip is obviously thinned. Under the condition of no toxic elements, the mechanical property of the medical titanium alloy material can be greatly improved, and the good plastic property is maintained.
Drawings
FIG. 1 is a DSC test of a high strength, high toughness copper-containing medical titanium alloy of examples 1-4 and comparative example 1 of the present invention;
FIG. 2 is an XRD pattern of the high strength, high toughness copper-containing medical titanium alloys obtained in examples 1-4 and comparative example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a high strength, high toughness copper-containing medical titanium alloy according to examples 1-4 and comparative example 1 of the present invention;
FIG. 4 is a graph showing the statistics of the dimensions of alpha-laths of the high strength, high toughness copper-containing medical titanium alloys obtained in examples 1-4 and comparative example 1 of the present invention;
FIG. 5 is a graph showing the comparison of mechanical properties of the high strength and high toughness copper-containing medical titanium alloys obtained in examples 1-4 and comparative example 1 of the present invention;
FIG. 6 is a graph showing the hardness comparison of the copper-containing medical titanium alloys of the present invention obtained in examples 1-4 and comparative example 1;
FIG. 7 is a statistical chart of Zr 2 Cu densities of the high-strength high-toughness copper-containing medical titanium alloys obtained in examples 1-4 and comparative example 1 according to the present invention;
FIG. 8 is a graph showing the scanning transmission electron image and the distribution of alloy elements of the high-strength and high-toughness copper-containing medical titanium alloy obtained in example 3 of the present invention;
FIG. 9 is a selected area electron diffraction image of the alpha phase and Zr 2 Cu phase of the high-strength high-toughness copper-containing medical titanium alloy obtained in example 3 of the present invention.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is evident that the embodiments described are only some embodiments of the present application, but not all embodiments.
Example 1 vacuum consumable arc melting Ti-15Zr-5Cu, comprising the following steps:
(1) Weighing titanium sponge, zirconium sponge and copper particles, and mixing the titanium sponge, the zirconium sponge and the copper particles according to the mass ratio of Ti 80%, zr 15% and Cu 5%;
(2) Pressing electrodes, namely pressing the raw materials mixed in proportion into electrode blocks, wherein each electrode block is controlled at 1 kg, and the raw materials are uniformly mixed and distributed;
(3) Welding electrodes, namely welding every two pressed electrodes into a smelting electrode;
(4) Vacuum consumable smelting primary ingot, namely putting the welded smelting electrode into a vacuum consumable arc smelting furnace to smelt, wherein the current is 1.8 KA, the voltage is 33V, the pre-vacuum degree is less than or equal to 1 Pa, the working vacuum degree is less than or equal to 8 Pa, and a copper crucible with the diameter of 100 mm is adopted to smelt primary titanium alloy ingot with the diameter of 100 mm;
(5) Removing the head and the tail of the obtained primary ingot, carrying out secondary smelting in a vacuum consumable arc smelting furnace, wherein the current is 3.6 KA, the voltage is 34V, the pre-vacuum degree is less than or equal to 0.8 Pa, the working vacuum degree is less than or equal to 5 Pa, and a copper crucible with the diameter of 140 mm is adopted to smelt an ingot with the diameter of 140 mm;
(6) Homogenizing the cast ingot at 850 ℃ for 30 min, and then carrying out hot rolling with 85% deformation;
(7) And (3) carrying out heat treatment on the hot rolled sample, wherein the treatment system is 750 ℃ for 1h of solution treatment, and finally obtaining the copper-containing titanium alloy with high strength and high toughness, namely TZC-15Zr.
Example 2 vacuum consumable arc melting Ti-25Zr-5Cu, comprising the following steps:
(1) Weighing titanium sponge, zirconium sponge and copper particles, and mixing the titanium sponge, the zirconium sponge and the copper particles according to the mass ratio of Ti 70%, zr 25% and Cu 5%;
(2) Pressing electrodes, namely pressing the raw materials mixed in proportion into electrode blocks, wherein each electrode block is controlled at 1 kg, and the raw materials are uniformly mixed and distributed;
(3) Welding electrodes, namely welding every two pressed electrodes into a smelting electrode;
(4) Vacuum consumable smelting primary ingot, namely putting the welded smelting electrode into a vacuum consumable arc smelting furnace to smelt, wherein the current is 1.8 KA, the voltage is 33V, the pre-vacuum degree is less than or equal to 1 Pa, the working vacuum degree is less than or equal to 8 Pa, and a copper crucible with the diameter of 100 mm is adopted to smelt primary titanium alloy ingot with the diameter of 100 mm;
(5) Removing the head and the tail of the obtained primary ingot, carrying out secondary smelting in a vacuum consumable arc smelting furnace, wherein the current is 3.6 KA, the voltage is 34V, the pre-vacuum degree is less than or equal to 0.8 Pa, the working vacuum degree is less than or equal to 5 Pa, and a copper crucible with the diameter of 140 mm is adopted to smelt an ingot with the diameter of 140 mm;
(6) Homogenizing the cast ingot at 810 ℃ for 30 min%, and then carrying out hot rolling with 85% deformation;
(7) And carrying out heat treatment on the hot rolled sample, wherein the treatment system is 710 ℃ for 1h of solution treatment, and finally obtaining the copper-containing titanium alloy with high strength and high toughness, namely TZC-25Zr.
Example 3 vacuum consumable arc melting Ti-35Zr-5Cu, comprising the following steps:
(1) Weighing titanium sponge, zirconium sponge and copper particles, and mixing the titanium sponge, the zirconium sponge and the copper particles according to the mass ratio of Ti 60%, zr 35% and Cu 5%;
(2) Pressing electrodes, namely pressing the raw materials mixed in proportion into electrode blocks, wherein each electrode block is controlled at 1 kg, and the raw materials are uniformly mixed and distributed;
(3) Welding electrodes, namely welding every two pressed electrodes into a smelting electrode;
(4) Vacuum consumable smelting primary ingot, namely putting the welded smelting electrode into a vacuum consumable arc smelting furnace to smelt, wherein the current is 1.8 KA, the voltage is 33V, the pre-vacuum degree is less than or equal to 1 Pa, the working vacuum degree is less than or equal to 8 Pa, and a copper crucible with the diameter of 100mm is adopted to smelt primary titanium alloy ingot with the diameter of 100 mm;
(5) Removing the head and the tail of the obtained primary ingot, carrying out secondary smelting in a vacuum consumable arc smelting furnace, wherein the current is 3.6 KA, the voltage is 34V, the pre-vacuum degree is less than or equal to 0.8 Pa, the working vacuum degree is less than or equal to 5 Pa, and a copper crucible with the diameter of 140 mm is adopted to smelt an ingot with the diameter of 140 mm;
(6) Homogenizing the cast ingot under 760 ℃ atmosphere for 30 min%, and then carrying out hot rolling with 85% deformation;
(7) And carrying out heat treatment on the hot rolled sample, wherein the treatment system is 660 ℃ for 1h of solution treatment, and finally obtaining the copper-containing titanium alloy with high strength and high toughness, namely TZC-35Zr.
Example 4 vacuum consumable arc melting Ti-45Zr-5Cu, comprising the following steps:
(1) Weighing titanium sponge, zirconium sponge and copper particles, and mixing the titanium sponge, the zirconium sponge and the copper particles according to the mass ratio of Ti 50%, zr 45% and Cu 5%;
(2) Pressing electrodes, namely pressing the raw materials mixed in proportion into electrode blocks, wherein each electrode block is controlled at 1 kg, and the raw materials are uniformly mixed and distributed;
(3) Welding electrodes, namely welding every two pressed electrodes into a smelting electrode;
(4) Vacuum consumable smelting primary ingot, namely putting the welded smelting electrode into a vacuum consumable arc smelting furnace to smelt, wherein the current is 1.8 KA, the voltage is 33V, the pre-vacuum degree is less than or equal to 1 Pa, the working vacuum degree is less than or equal to 8 Pa, and a copper crucible with the diameter of 100 mm is adopted to smelt primary titanium alloy ingot with the diameter of 100 mm;
(5) Removing the head and the tail of the obtained primary ingot, carrying out secondary smelting in a vacuum consumable arc smelting furnace, wherein the current is 3.6 KA, the voltage is 34V, the pre-vacuum degree is less than or equal to 0.8 Pa, the working vacuum degree is less than or equal to 5 Pa, and a copper crucible with the diameter of 140 mm is adopted to smelt an ingot with the diameter of 140 mm;
(6) Homogenizing the cast ingot under 730 ℃ atmosphere for 30 min%, and then carrying out hot rolling with 85% deformation;
(7) And (3) carrying out heat treatment on the hot rolled sample, wherein the treatment system is 630 ℃ and the solution treatment is carried out for 1h, and finally obtaining the copper-containing titanium alloy with high strength and high toughness, namely TZC-45Zr.
Comparative example 1. Vacuum consumable arc melting Ti-5Cu was used, the specific steps were as follows:
(1) Weighing titanium sponge, zirconium sponge and copper particles, and mixing the titanium sponge, the zirconium sponge and the copper particles according to the mass ratio of Ti 95% and Cu 5%;
(2) Pressing electrodes, namely pressing the raw materials mixed in proportion into electrode blocks, wherein each electrode block is controlled at 1 kg, and the raw materials are uniformly mixed and distributed;
(3) Welding electrodes, namely welding every two pressed electrodes into a smelting electrode;
(4) Vacuum consumable smelting primary ingot, namely putting the welded smelting electrode into a vacuum consumable arc smelting furnace to smelt, wherein the current is 1.8 KA, the voltage is 33V, the pre-vacuum degree is less than or equal to 1 Pa, the working vacuum degree is less than or equal to 8 Pa, and a copper crucible with the diameter of 100 mm is adopted to smelt primary titanium alloy ingot with the diameter of 100 mm;
(5) Removing the head and the tail of the obtained primary ingot, carrying out secondary smelting in a vacuum consumable arc smelting furnace, wherein the current is 3.6 KA, the voltage is 34V, the pre-vacuum degree is less than or equal to 0.8 Pa, the working vacuum degree is less than or equal to 5 Pa, and a copper crucible with the diameter of 140mm is adopted to smelt an ingot with the diameter of 140 mm;
(6) Homogenizing the cast ingot at 920 ℃ for 30 min ℃ and then carrying out hot rolling with 85% deformation;
(7) And (3) carrying out heat treatment on the hot rolled sample, wherein the treatment system is 820 ℃ for 1h of solution treatment, and finally obtaining the copper-containing titanium alloy with high strength and high toughness, namely TZC-0Zr.
As shown in fig. 1, it is understood from the graph that the beta transus temperature of TZC alloy is continuously decreased with the increase of Zr element content, and is 870 ℃, 800 ℃, 760 ℃, 710 ℃ and 680 ℃, respectively. Meanwhile, as the content of Zr element increases, the absorption peak of Ti 2Cu/Zr2 Cu converted into beta phase gradually coincides with the alpha transition peak, which shows that after Zr element is doped, cu element exists in beta phase in solid solution state during the cooling process of the titanium alloy because the beta transition temperature is low enough, the solubility of Cu element in beta phase is about 8 times of that in alpha phase, when alpha phase starts nucleation and grows up, zr and Cu eutectoid reaction occurs, alpha phase and Zr 2 Cu precipitated phase are formed almost simultaneously, and finally dispersed Zr 2 Cu phase is obtained.
As shown in FIG. 2, the alpha phase and Ti 2 Cu phase exist in comparative example 1, as the content of Zr element increases, zr 2 Cu phase gradually appears in the alloy, the peak intensity is enhanced, and the Ti 2 Cu phase completely disappears in examples 2-4, which shows that the main Zr 2 Cu phase plays a role in strengthening in the TZC alloy.
Referring to fig. 3 and 4, fig. 3 shows the tissue topography of examples 1-4 and comparative example 1, wherein (a), (b), (c), (d), (e) of fig. 3 represent the tissue topography of comparative example 1 and examples 1-4, respectively. Fig. 4 shows a statistical plot of the alpha lath size of comparative example 1 and examples 1-4, and (a), (b), (c), (d), (e) of fig. 4 represent statistical plots of the grain size of comparative example 1 and examples 1-4, respectively. The TZC-0Zr alloy mainly comprises an alpha phase and Ti 2 Cu, the beta phase is completely converted into the alpha phase and Ti 2 Cu in the system, and the Ti 2 Cu precipitation phases all show an aggregation state. By adding a proper amount of Zr element, the microstructure of the titanium alloy is changed into a lamellar or basket structure, and forms a Zr 2 Cu precipitated phase with Cu element, and the Zr 2 Cu precipitated phase is uniformly dispersed in the alloy, so that the strength of the alloy is obviously improved. In addition, the addition of Zr element makes alpha lath obviously refined, and forms a high-density phase interface with precipitated phase Zr 2 Cu. This high density phase interface can effectively block dislocation movement, thereby improving the deformation resistance of the alloy.
Referring to fig. 5, fig. 5 shows stress-strain curves for comparative example 1 and examples 1-4. When the mass ratio of Zr element is 0-15%, the average alpha lath width of the titanium alloy is about 1.3-3.2 mu m, the tensile strength is 740-860 MPa, and the elongation is 15-16%. With the increase of the mass ratio of Zr element, the microstructure and mechanical property of the alloy continue to change. When the mass ratio of Zr element is 15-25%, the average alpha lath width of the titanium alloy is reduced to 0.9-1.3 mu m, the tensile strength is improved to 860-1020 MPa, and the elongation is 13-15%. When the mass ratio of Zr element is 25-35%, the average alpha lath width is further reduced to 0.5-0.9 mu m, the tensile strength is improved to 1020-1030 MPa, and the elongation is 13-14%. When the mass ratio of Zr element reaches 35-45%, the average alpha lath width of the titanium alloy is further reduced to 0.4-0.5 mu m, and the elongation is obviously reduced to 8-14% although the tensile strength is maintained between 1030-1130 MPa. The change rule reveals that the balance between the strength and the plasticity of the titanium alloy can be realized by regulating and controlling the doping amount of Zr element, so as to meet the requirements of different application scenes.
Microhardness of comparative example 1 and examples 1-4 is shown in fig. 6. With the addition of Zr element, the microhardness of the alloy is improved. Specific values are 258.8 HV0.2/20, 321.0 HV0.2/20, 322.5 HV0.2/20, 338.8 HV0.2/20, 343.8 HV0.2/20.
FIG. 7 shows statistics of the number of Zr 2 Cu phases contained in each 100 μm 2 of the scanning electron microscope pictures in comparative example 1 and examples 1-4, which can intuitively reflect the content of Zr 2 Cu phases in each alloy, the content of Zr 2 Cu precipitated phases increases with the increase of the content of Zr elements, the strengthening effect is not obvious when the content of the precipitated phases is low, and the tendency of aggregation of the precipitated phases occurs when the content is too high, so that the alloy becomes brittle.
Referring to fig. 8 and 9, fig. 8 shows the scanning transmission electron image and the alloy element distribution result of example 3, and fig. 9 (a) and (b) show the selected area electron diffraction image of example 3. The alloy element distribution diagram further verifies the existence of Zr 2 Cu phase, the size of the Zr 2 Cu phase is 100-300 nm, and the Zr 2 Cu phase is uniformly distributed in the matrix. FIG. 9 (b) is a selective electron diffraction image corresponding to Zr 2 Cu, and the phase is proved to be a C11b structure by identification.
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