CN115125415B - Zn-Cu-Ti-Mo alloy, and preparation method and application thereof - Google Patents
Zn-Cu-Ti-Mo alloy, and preparation method and application thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C18/00—Alloys based on zinc
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- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
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- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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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
- C22F1/165—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 of zinc or cadmium or alloys based thereon
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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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
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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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
Abstract
The invention belongs to the technical field of metal material preparation, and particularly relates to a Zn-Cu-Ti-Mo alloy, and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing a casting blank: preparing raw materials according to Zn-Cu-Ti-Mo alloy components, smelting the raw materials, and then casting the smelted alloy melt into a casting blank; hot rolling: carrying out hot rolling on the casting blank, and obtaining a first blank after the hot rolling is finished; warm rolling: carrying out warm rolling on the first blank to obtain a Zn-Cu-Ti-Mo alloy plate after the warm rolling is finished; the Zn-Cu-Ti-Mo alloy comprises the following components in percentage by mass: 1.0 to 3.0 percent of Cu and not 1.0 percent. The preparation method remarkably improves the strength and plasticity of the Zn-Cu-Ti alloy with high copper content, and the prepared Zn-Cu-Ti-Mo alloy meets the performance requirements of biomedical degradable implant materials.
Description
Technical Field
The invention belongs to the technical field of metal material preparation, and particularly relates to a Zn-Cu-Ti-Mo alloy, and a preparation method and application thereof.
Background
The traditional medical implantation metal material mainly comprises 316L stainless steel and Ti 6 Al 4 The V-titanium alloy, the cobalt-based alloy and the like have excellent corrosion resistance, but once being implanted into a human body, the metal materials are difficult to degrade by the human body, and after the metal materials complete medical functions, the metal materials need to be taken out through a secondary operation, so that secondary pain and additional economic and mental stress are brought to a patient. Therefore, in recent years, research on degradable metal materials has become a hot spot for medical materials.
At present, the research on medical degradable metal materials mainly focuses on magnesium alloy, iron alloy and zinc alloy. Overall, the magnesium alloy has a faster degradation rate, andrelease of H during degradation 2 Causing subcutaneous emphysema and other adverse reactions. Although the ferroalloy can be degraded by human body, the degradation rate is extremely slow, and the requirement of degradable material implantation is difficult to meet. The standard electrode potential of metal Zn is 0.76V, higher than pure magnesium (-2.37V) and lower than pure iron (-0.44V), so that the corrosion rate of metal Zn is between that of metal Mg and metal Fe, and the metal Zn is expected to become a biodegradable metal material capable of being clinically applied.
As a biomedical degradable implant material, the mechanical property of the material needs to meet the indexes of tensile strength of more than 300MPa, yield strength of more than 200MPa and elongation of more than 18 percent; the Zn-Cu-Ti alloy with high Cu content (Cu mass fraction is more than 1%) has excellent antibacterial property and biocompatibility, and the elements are necessary elements which are nontoxic to human bodies, so that the Zn-Cu-Ti alloy has the potential of being suitable for being used as a biomedical degradable implant material. Although the conventional hot rolling process or hot rolling and cold rolling process can improve the mechanical property of the Zn-Cu-Ti alloy with high copper content, the strength and plasticity (the tensile strength is generally lower than 250MPa, the yield strength is generally lower than 180MPa, and the elongation is generally lower than 17%) of the Zn-Cu-Ti alloy can not meet the implantation requirement of biomedical metal materials.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a Zn-Cu-Ti-Mo alloy and a preparation method and application thereof, the invention adds Mo element into the Zn-Cu-Ti alloy, and combines the processes of hot rolling and warm rolling, so that the strength and plasticity of the Zn-Cu-Ti alloy with high copper content are obviously improved, the tensile strength of the prepared Zn-Cu-Ti-Mo alloy is more than 300MPa, the yield strength is more than 200MPa, and the elongation is more than 18%, thereby meeting the performance requirements of biomedical degradable implant materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a Zn-Cu-Ti-Mo alloy, which comprises the following steps:
preparing a casting blank: preparing raw materials according to Zn-Cu-Ti-Mo alloy components, smelting the raw materials, and then casting the smelted alloy melt into a casting blank;
hot rolling: carrying out hot rolling on the casting blank, and obtaining a first blank after the hot rolling is finished;
warm rolling: carrying out warm rolling on the first blank to obtain a Zn-Cu-Ti-Mo alloy plate after the warm rolling is finished;
the Zn-Cu-Ti-Mo alloy comprises the following components in percentage by mass:
1.0 to 3.0% and not 1.0% of Cu (for example, the mass percentage of Cu in the Zn-Cu-Ti-Mo alloy may be 1.1%, 1.8%, 3%, or the like).
According to the invention, by adding Mo element into Zn-Cu-Ti alloy and combining the processes of hot rolling and warm rolling, the strength and plasticity of the Zn-Cu-Ti alloy with high copper content are obviously improved, and the prepared Zn-Cu-Ti-Mo alloy has the tensile strength of more than 300MPa, the yield strength of more than 200MPa and the elongation of more than 18%, and meets the performance requirements of biomedical degradable implant materials.
In some embodiments, the Zn-Cu-Ti-Mo alloy consists of, in mass percent:
1.0 to 3.0 percent of Cu and not more than 1.0 percent (for example, the mass percent of Cu in the Zn-Cu-Ti-Mo alloy can be 1.1 percent, 1.8 percent or 3 percent, etc.), 0.1 to 0.2 percent of Ti, 0.05 to 0.2 percent of Mo, and the balance of Zn and inevitable impurities.
In some embodiments, in the hot rolling step, the cast slab is hot rolled to obtain a hot rolled slab, and the hot rolled slab is water quenched after the hot rolling is completed to obtain the first slab.
In some embodiments, in the warm rolling step, the first blank is warm rolled to obtain a warm rolled blank, and after the warm rolling is finished, the warm rolled blank is quenched with water to obtain the Zn-Cu-Ti-Mo alloy plate.
According to the invention, the tensile strength, yield strength and elongation of the Zn-Cu-Ti-Mo alloy are remarkably improved by performing water quenching on the hot rolled blank after hot rolling and performing water quenching on the warm rolled blank after warm rolling.
In some embodiments, the water quenching after hot rolling is quenching the hot rolled blank to 10-40 ℃ (e.g., can be 10 ℃, 20 ℃, 21 ℃, 23 ℃, 24 ℃, 25 ℃, 28 ℃, 32 ℃, 35 ℃, or 40 ℃, etc.) out of the water.
In some embodiments, the water quenching after warm rolling is to cool the warm rolled billet to 10-40 ℃ (e.g., can be 10 ℃, 20 ℃, 21 ℃, 23 ℃, 24 ℃, 25 ℃, 28 ℃, 32 ℃, 35 ℃, or 40 ℃, etc.) out of the water.
The invention can avoid the coarsening of the second phase in the cooling process and the coarsening of crystal grains by limiting the finishing temperature of water quenching to be 10-40 ℃, and simultaneously enhance the strengthening effect of solid solution strengthening on the alloy.
In some embodiments, the feedstock includes pure Zn, pure Cu and/or a Cu-containing elemental master alloy, a Ti-containing elemental master alloy, a Mo-containing elemental master alloy.
In some embodiments, the Cu-containing master alloy is Zn-x 1 Cu、Zn-x 2 Cu-y 1 Ti、Mo-x 3 Cu-y 2 Ti、Cu-y 3 Ti、Cu-y 5 Ti-z 2 Mo、Cu-z 3 One or more of Mo, wherein x 1 、x 2 、x 3 、y 1 、y 2 、y 3 、y 5 、z 2 And z 3 Respectively represents the corresponding mass percentage content of each alloy element, and the unit is wt percent, x 1 Represents 5 to 20 (for example, may represent 5, 10, 15 or 20), x 2 Represents 5 to 20 (for example, may represent 5, 10, 15 or 20), y 1 Represents 1 to 5 (for example, may represent 1, 3 or 5), x 3 Represents 1 to 20 (for example, may represent 1, 5, 10, 15 or 20), y 2 Represents 1 to 20 (for example, may represent 1, 5, 10, 15 or 20, etc.), y 3 Represents 1 to 20 (for example, may represent 1, 5, 10, 15 or 20), y 5 Represents 1 to 20 (for example, may represent 1, 5, 10, 15 or 20), z 2 Represents 1 to 20 (for example, may represent 1, 5, 10, 15 or 20), z 3 Represents 1 to 50 (for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50 can be represented).
In some embodiments, the Ti-containing master alloy is Zn-y 4 Ti、Cu-y 3 Ti、Ti-z 1 Mo、Zn-x 2 Cu-y 1 Ti、Cu-y 5 Ti-z 2 In MoWherein, y 4 And z 1 Respectively represents the corresponding mass percentage content of each alloy element, and the unit is wt percent and y 4 Represents 1 to 20 (for example, may represent 1, 5, 10, 15 or 20, etc.), z 1 Represents 1 to 50 (for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50 may be represented).
In some embodiments, the Mo-containing master alloy is Cu-z 3 Mo、Cu-y 5 Ti-z 2 Mo、Ti-z 1 One or more of Mo.
In some embodiments, the raw material is preheated and dried before smelting, preferably, the temperature of the preheated and dried is 50 ℃ to 300 ℃ (for example, the temperature can be 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃, etc.), and the holding time of the preheated and dried is 1min to 15min (for example, the holding time can be 1min, 3min, 5min, 7min, 11min, 13min or 15min, etc.).
In some embodiments, the smelting comprises raw material melting and refining, wherein the raw material melting comprises putting pure Zn into a melting furnace for melting, and after the pure Zn is completely melted, adding pure Cu and/or a Cu-containing intermediate alloy, a Ti-containing intermediate alloy and a Mo-containing intermediate alloy in sequence;
preferably, the melting temperature is 500 to 800 ℃ (e.g., the temperature may be 500 ℃, 600 ℃, 700 ℃, or 800 ℃, etc.), and the refining temperature is the same as the melting temperature.
In some embodiments, the refining is performed for a time period of 2min to 30min (e.g., the time period can be 2min, 5min, 10min, 15min, 20min, 25min, or 30min, etc.), and the refining is performed by rotating a blower of argon, passing N through the blower 2 And Cl 2 The mixed gas method of (3) and the method of adding chloride.
In some embodiments, the refining method is by passing in N 2 And Cl 2 The mixed gas method of (1), said N 2 And Cl 2 The volume ratio of (1) to (60) is (10 to 20).
In some embodiments, a degassing and slagging step is further included after the refining and before the pouring.
In some embodiments, in the step of preparing the casting blank, the melt after degassing and slagging-off is cooled to 450-600 ℃ (for example, to 450 ℃, 500 ℃, 550 ℃ or 600 ℃, etc.), and then poured into a mold or a continuous casting machine, and an alloy casting blank is obtained after cooling and solidification.
In some embodiments, in the step of preparing the casting billet, the casting speed of the alloy casting billet obtained after the degassing and slagging-off is poured into a continuous casting machine for cooling and solidification is 0.5-15 m/min, for example, the casting speed can be 0.5m/min, 2m/min, 4m/min, 6m/min, 8m/min, 10m/min, 12m/min or 15m/min, and the like.
In some embodiments, the alloy billet has a width of 50 to 1000mm, for example the width may be 50mm, 100mm, 150mm, 250mm, 350mm, 450mm, 550mm, 650mm, 750mm, 850mm, 1000mm, or the like.
In some embodiments, the alloy billet has a thickness of 10 to 20mm, for example, the thickness may be 10mm, 12mm, 14mm, 16mm, 18mm, or 20mm, and the like.
In some embodiments, in the hot rolling step, the hot rolling temperature is 250 ℃ to 360 ℃ (e.g., the temperature may be 250 ℃, 270 ℃, 290 ℃, 310 ℃, 330 ℃, or 360 ℃, etc.), the hot rolling passes are 2 to 6 (e.g., the passes may be 2, 4, 5, or 6, etc.), and the reduction per pass is 15% to 40% (e.g., the reduction may be 15%, 20%, 25%, 30%, 35%, or 40%, etc.).
In some embodiments, in the warm rolling step, the warm rolling temperature is from 100 ℃ to 200 ℃ (e.g., the temperature may be 100 ℃, 120 ℃, 150 ℃, 160 ℃, 180 ℃, or 200 ℃, etc.), the warm rolling has 2 to 3 rolling passes, and the reduction per pass is from 30% to 50% (e.g., the reduction may be 30%, 35%, 40%, 45%, or 50%, etc.).
The invention can avoid alloy cracking and keep the plate shape good by limiting the reduction of each pass of warm rolling to 30-50%.
In a second aspect, the present invention provides a Zn-Cu-Ti-Mo alloy made by the method of making provided in the first aspect.
In some embodiments, the Zn-Cu-Ti-Mo alloy has a tensile strength of 300MPa to 400MPa (e.g., tensile strength can be 300MPa, 320MPa, 340MPa, 360MPa, 380MPa, or 400MPa, etc.), a yield strength of 200MPa to 300MPa (e.g., yield strength can be 200MPa, 220MPa, 240MPa, 260MPa, 280MPa, or 300MPa, etc.), and an elongation of 30% to 95% (e.g., elongation can be 30%, 40%, 50%, 60%, 70%, 80%, or 95%, etc.). The zinc alloy prepared by the method has excellent mechanical properties of both strength and plasticity.
In a third aspect, the invention provides a use of the Zn-Cu-Ti-Mo alloy according to the second aspect for medical degradable metallic materials.
Compared with the prior art, the beneficial effects of the invention at least comprise one of the following items:
1) Mo is one of the essential trace elements, and has high content in liver and kidney, and at least 50 kinds of biological enzymes contain Mo. By introducing trace Mo element required by human body into Zn-Cu-Ti alloy with high copper content, moZn with fine size and dispersion distribution is generated 7 Phase, moZn 7 The phase hardness is high, which not only plays a role in strengthening the second phase, but also provides more polymorphic nuclear energy and nucleation sites for the dynamic recrystallization process, and obviously refines the zinc alloy grains.
2) According to the invention, by adding Mo element into the Zn-Cu-Ti alloy and combining the hot rolling and warm rolling processes, the strength and plasticity of the Zn-Cu-Ti alloy with high copper content are obviously improved, the tensile strength of the prepared Zn-Cu-Ti-Mo alloy is more than 300MPa, the yield strength is more than 200MPa, the elongation is more than 18%, the performance requirements of biomedical degradable implant materials are met, the preparation process is simple, and the application prospect is wide.
3) Because the recrystallization temperature of metal Zn is lower, about 100 ℃, the zinc alloy can not only avoid alloy cracking and keep the plate shape good in the warm rolling process with the rolling reduction of 30-50% in 2-3 passes and each pass, but also can be dynamically recrystallized to a greater degree, thereby being beneficial to the grain refinement of the zinc alloy; a large number of refined second phases can be obtained in the warm rolling process, the refined second phases can block dislocation lines and grain boundary movement during alloy plastic deformation, and meanwhile, high-density nano-size Mo-rich phases are likely to be separated out in the hot rolling and warm rolling processes, so that the mechanical property of the alloy is improved.
4) According to the invention, by adding Mo element into the Zn-Cu-Ti alloy and combining the hot rolling and warm rolling processes, the grain refinement strengthening, the second phase strengthening and the precipitation strengthening are cooperated, so that the strength and plasticity of the Zn-Cu-Ti alloy are greatly improved, and the alloy keeps good antibacterial property, biocompatibility and corrosion resistance.
Drawings
Fig. 1 is a microstructure view of an alloy plate prepared in example 1 of the present application.
FIG. 2 is a microstructure view of an alloy plate prepared in comparative example 1 of the present application.
FIG. 3 is a microstructure view of an alloy plate prepared in comparative example 2 of the present application.
FIG. 4 is a microstructure view of an alloy plate prepared in comparative example 3 of the present application.
FIG. 5 is a macro-topography of an alloy sheet prepared in comparative example 5 of the present application.
Fig. 6 is a Scanning Electron Microscope (SEM) image of an alloy plate prepared in example 1 of the present application.
Detailed Description
The following examples further illustrate the content of the present application in detail, and the scope of the present application includes but is not limited to the following examples. The following examples are only for illustrating the advantages and effects of the technical solutions of the present application, and do not limit the scope of protection of the present application. Equivalents may be substituted for those skilled in the art based on the teachings herein without departing from the scope of the present application.
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. The experimental reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the dosage of the experimental reagent is the dosage of the reagent in the conventional experimental operation if no special instruction is provided; the experimental methods are conventional methods unless otherwise specified.
The Zn-Cu-Ti-Mo alloy provided by the embodiment of the invention comprises the following components in percentage by mass:
1.0 to 3.0% and not 1.0% of Cu (for example, the mass percentage of Cu in the Zn-Cu-Ti-Mo alloy may be 1.1%, 1.8%, 3%, or the like), 0.1 to 0.2% of Ti, 0.05 to 0.2% of Mo, and the balance of Zn and unavoidable impurities.
The preparation method of the Zn-Cu-Ti-Mo alloy provided by the embodiment of the invention comprises the following steps:
s1, preheating and drying: preheating and drying raw materials at the temperature of 50-300 ℃, wherein the heat preservation time of the preheating and drying is 1-15 min, wherein the raw materials comprise pure Zn, pure Cu and/or intermediate alloy containing Cu element, intermediate alloy containing Ti element and intermediate alloy containing Mo element; the intermediate alloy containing Cu is Zn-x 1 Cu、Zn-x 2 Cu-y 1 Ti、Mo-x 3 Cu-y 2 Ti、Cu-y 3 Ti、Cu-y 5 Ti-z 2 Mo、Cu-z 3 One or more of Mo, wherein x 1 、x 2 、x 3 、y 1 、y 2 、y 3 、y 5 、z 2 And z 3 Respectively represents the corresponding mass percentage content of each alloy element, and the unit is wt percent, x 1 Represents 5 to 20,x 2 Represents 5 to 20,y 1 Represents 1 to 5,x 3 Represents 1 to 20,y 2 Represents 1 to 20,y 3 Represents 1 to 20,y 5 Represents 1 to 20,z 2 Represents 1 to 20,z 3 Represents 1 to 50; the intermediate alloy containing Ti element is Zn-y 4 Ti、Cu-y 3 Ti、Ti-z 1 Mo、Zn-x 2 Cu-y 1 Ti、Cu-y 5 Ti-z 2 One or more of Mo, wherein y 4 And z 1 Respectively represents the corresponding mass percentage content of each alloy element, and the unit is wt percent and y 4 Represents 1 to 20,z 1 Represents 1 to 50; the Mo-containing intermediate alloy is Cu-z 3 Mo、Cu-y 5 Ti-z 2 Mo、Ti-z 1 One or more of Mo.
S2, preparing a casting blank: according to the composition of Zn-Cu-Ti-Mo alloyPreparing raw materials, smelting the raw materials, degassing and slagging off, cooling the melt subjected to degassing and slagging off to 450-600 ℃, pouring the melt into a mold or a continuous casting machine, and cooling and solidifying to obtain an alloy casting blank with the width of 50-1000 mm and the thickness of 10-20 mm; the smelting comprises raw material melting and refining, wherein the raw material melting comprises the steps of putting pure Zn into a melting furnace for melting, and after the pure Zn is completely melted, sequentially adding pure Cu and/or intermediate alloy containing Cu element, intermediate alloy containing Ti element and intermediate alloy containing Mo element; the melting temperature is 500-800 ℃; the temperature of the refining is the same as the temperature of the melting; the refining time is 2min-30min; the refining method comprises a rotary argon blowing method and N introduction 2 And Cl 2 One of the mixed gas method and the chloride salt adding method; said N is 2 And Cl 2 The volume ratio of (10-60) to (1); and pouring the melt subjected to degassing and slagging-off into a continuous casting machine for cooling and solidifying to obtain the alloy casting blank, wherein the casting speed is 0.5-15 m/min.
S3, hot rolling: the casting blank is subjected to hot rolling to obtain a hot rolled blank, and after the hot rolling is finished, the hot rolled blank is subjected to water quenching to obtain a first blank, wherein the water quenching after the hot rolling is to quench the hot rolled blank to 10-40 ℃ and discharge water, the hot rolling temperature is 250-360 ℃, the hot rolling passes are 2-6 times, and the reduction of each pass is 15-40%.
S4, warm rolling: and carrying out warm rolling on the first blank to obtain a warm-rolled blank, and after the warm rolling is finished, carrying out water quenching on the warm-rolled blank to obtain the Zn-Cu-Ti-Mo alloy plate, wherein the water quenching after the warm rolling is to cool the warm-rolled blank to 10-40 ℃ for water outlet, the warm rolling temperature is 100-200 ℃, the number of rolling passes of the warm rolling is 2-3, and the reduction of each pass is 30-50%.
In the following examples and comparative examples:
the method for measuring the tensile strength, the yield strength and the elongation is national standard: GB/T228.1-2010.
Example 1
The Zn-Cu-Ti-Mo alloy provided in this embodiment comprises the following chemical components in percentage by mass: zn-1.8Cu-0.15Ti-0.15Mo, namely Cu 1.8 percent, ti 0.15 percent, mo 0.15 percent, and the balance of Zn and inevitable impurities.
The preparation method of Zn-1.8Cu-0.15Ti-0.15Mo provided in this embodiment specifically includes the following steps:
s1, calculating and weighing raw materials required for preparing the Zn-1.8Cu-0.15Ti-0.15Mo alloy according to the chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the embodiment and the mass of the prepared Zn-1.8Cu-0.15Ti-0.15Mo alloy, wherein the raw materials comprise a Ti-50Mo intermediate alloy containing Mo element, pure zinc and a Zn-20Cu intermediate alloy, and preserving heat of the raw materials in a drying furnace at the temperature of 200 ℃ for 5min for preheating and drying.
S2, putting pure Zn into a melting furnace, heating to 600 ℃, and after the pure Zn is completely melted, sequentially adding a Zn-20Cu master alloy and a Ti-50Mo master alloy into the pure Zn melt;
and after all elements are completely melted, refining the Zn-Cu-Ti-Mo alloy melt by adopting a rotary argon blowing method for 10min, degassing and slagging off, cooling the melt subjected to degassing and slagging off to 480 ℃, pouring the melt into a graphite mould, and cooling and solidifying to obtain an alloy casting blank with the thickness of 16mm, the length of 300mm and the width of 150 mm.
S3, heating the alloy casting blank to 350 ℃, carrying out 5-pass hot rolling with the reduction of 25% per pass to obtain a hot rolling blank, and carrying out water quenching on the hot rolling blank after the hot rolling is finished, wherein the water outlet temperature is 21 ℃, so as to obtain a first blank.
S4, heating the first blank to 150 ℃, carrying out 2-pass warm rolling with the reduction of each pass being 40% to obtain a warm rolled blank, putting the warm rolled blank into water for quenching after the warm rolling is finished, wherein the effluent temperature is 23 ℃, and preparing the Zn-Cu-Ti-Mo alloy plate with excellent mechanical properties. The microstructure of the alloy is shown in FIG. 1, and it can be seen that the microstructure is fine and uniform. As shown in FIG. 6, it can be seen from FIG. 6 that MoZn having a fine size and a dispersed distribution is produced by introducing a trace amount of Mo element required for a human body into a Zn-Cu-Ti alloy having a high copper content 7 And (4) phase.
Example 2
The Zn-Cu-Ti-Mo alloy provided in this embodiment comprises the following chemical components by mass percent: zn-3Cu-0.1Ti-0.05Mo, namely Cu 3 percent, ti0.1 percent, mo0.05 percent, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-3Cu-0.1Ti-0.05Mo alloy provided in this embodiment specifically includes the following steps:
s1, calculating and weighing raw materials required for preparing the Zn-3Cu-0.1Ti-0.05Mo alloy according to the chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the embodiment and the mass of the prepared Zn-3Cu-0.1Ti-0.05Mo alloy, wherein the raw materials comprise a Ti-32Mo intermediate alloy containing Mo element, pure zinc and pure copper, and preserving the heat of the raw materials in a drying furnace at the temperature of 300 ℃ for 3min for preheating and drying.
S2, putting pure Zn into a melting furnace, heating to 660 ℃, and after the pure Zn is completely melted, sequentially adding pure Cu and Ti-32Mo intermediate alloy into the pure Zn melt;
after all elements are completely melted, introducing N into the melt 2 And Cl 2 Mixed gas method (N) 2 And Cl 2 Is 40: 1) Refining the melt for 8min, cooling the melt after degassing and slagging off to 500 ℃, pouring the melt into a graphite mould, cooling and solidifying to obtain an alloy casting blank with the thickness of 14mm, the length of 300mm and the width of 150 mm.
S3, heating the alloy casting blank to 320 ℃, carrying out 4-pass hot rolling with the reduction of 30% per pass to obtain a hot rolled blank, and carrying out water quenching on the hot rolled blank after the hot rolling is finished, wherein the water outlet temperature is 25 ℃, so as to obtain a first blank.
S4, heating the first blank to 100 ℃, carrying out 3-pass warm rolling with the reduction of 30% per pass to obtain a warm-rolled blank, and after the warm rolling is finished, putting the warm-rolled blank into water for quenching, wherein the water outlet temperature is 28 ℃, so that the Zn-Cu-Ti-Mo alloy plate with excellent mechanical properties is prepared.
Example 3
The Zn-Cu-Ti-Mo alloy provided in this embodiment comprises the following chemical components by mass percent: zn-1.1Cu-0.2Ti-0.2Mo, namely Cu 1.1 percent, ti 0.2 percent, mo 0.2 percent, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-1.1Cu-0.2Ti-0.2Mo alloy provided in this embodiment specifically includes the following steps:
s1, calculating and weighing raw materials required for preparing the Zn-1.1Cu-0.2Ti-0.2Mo alloy according to the chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the embodiment and the mass of the prepared Zn-1.1Cu-0.2Ti-0.2Mo alloy, wherein the raw materials comprise a Cu-15Mo intermediate alloy containing Mo element, pure zinc and a Zn-5Ti intermediate alloy, and preserving heat of the raw materials in a drying furnace at the temperature of 60 ℃ for 15min for preheating and drying.
S2, putting pure Zn into a melting furnace, heating to 630 ℃, and after the pure Zn is completely melted, sequentially adding a Zn-5Ti intermediate alloy and a Cu-15Mo intermediate alloy into the pure Zn melt;
after all elements are completely melted, introducing N into the melt 2 And Cl 2 Mixed gas method (N) 2 And Cl 2 Is 30: 1) Refining the melt for 6min, degassing and slagging off, cooling the melt to 500 ℃, pouring the melt into a graphite mold, cooling and solidifying to obtain an alloy casting blank with the thickness of 15mm, the length of 300mm and the width of 150 mm.
And S3, heating the alloy casting blank to 300 ℃, carrying out 6-pass hot rolling with the reduction of each pass being 20% to obtain a hot rolled blank, and carrying out water quenching on the hot rolled blank after the hot rolling is finished, wherein the water outlet temperature is 21 ℃, so as to obtain a first blank.
S4, heating the first blank to 200 ℃, carrying out 2-pass warm rolling with the reduction of 50% per pass to obtain a warm-rolled blank, putting the warm-rolled blank into water for quenching after the warm rolling is finished, wherein the effluent temperature is 24 ℃, and preparing the Zn-Cu-Ti-Mo alloy plate with excellent mechanical properties.
Comparative example 1
Compared with the Zn-Cu-Ti alloy in the embodiment 1, the Zn-Cu-Ti alloy in the comparative example has the difference that Mo is not introduced, and specifically comprises the following components in percentage by mass: zn-1.8Cu-0.15Ti, namely 1.8 percent of Cu, 0.15 percent of Ti and the balance of Zn and inevitable impurities in percentage by mass.
The preparation method of the Zn-1.8Cu-0.15Ti alloy provided by the present comparative example is substantially the same as that of example 1, except that the alloy raw materials are pure Zn, a Zn-20Cu master alloy and a Zn-5Cu-5Ti master alloy, an alloy containing Mo is not included, and the warm rolling process is replaced with a cold rolling process, specifically including the following steps:
s1 to S3: the same procedures as in steps S1 to S3 of example 1 were repeated except for the differences in the starting materials.
And S4, carrying out 2-pass cold rolling on the first blank, wherein the reduction of each pass is 40%, and preparing the Zn-Cu-Ti alloy plate. As shown in FIG. 2, the microstructure of the alloy was small in the proportion of recrystallization, coarse in the structure, and non-uniform in the grain size.
Comparative example 2
Compared with the chemical components and the mass percent of the Zn-Cu-Ti alloy provided by the comparative example 1, the difference is that Mo element is not introduced, and the specific steps are as follows: zn-1.8Cu-0.15Ti, namely 1.8 percent of Cu, 0.15 percent of Ti, and the balance of Zn and inevitable impurities by mass percent.
The comparative example provided a Zn-1.8Cu-0.15Ti alloy that was prepared in substantially the same manner as in example 1, except that the alloy raw materials were pure Zn, a Zn-20Cu master alloy, and a Zn-5Cu-5Ti master alloy, excluding alloys containing Mo element. The microstructure of the alloy thus produced is shown in FIG. 3, and it is found that the alloy is partially recrystallized, the microstructure is coarse, and the grain size is not uniform.
Comparative example 3
The chemical components and mass percentages of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the Zn-Cu-Ti-Mo alloy in the example 1, and the chemical components and mass percentages are as follows: zn-1.8Cu-0.15Ti-0.15Mo, namely 1.8 percent of Cu, 0.15 percent of Ti and 0.15 percent of Mo by mass, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-1.8Cu-0.15Ti-0.15Mo alloy provided by the comparative example is basically the same as that of the example 1, except that only the hot rolling process is adopted, the warm rolling process is not included, and the preparation method specifically comprises the following steps:
s1 to S2: the same procedure as in steps S1 to S2 of example 1 was repeated.
And S3, heating the alloy casting blank to 350 ℃, performing water quenching by adopting a hot rolling process with the reduction of 25% per pass, and obtaining the Zn-Cu-Ti-Mo alloy plate with the same thickness as that of the Zn-Cu-Ti-Mo alloy plate in the embodiment 1, wherein the water outlet temperature is 21 ℃. The microstructure of the alloy thus produced is shown in FIG. 4, and it is found that the alloy is partially recrystallized, the microstructure is coarse, and the grain size is not uniform.
Comparative example 4
The chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the example 1, and the specific steps are as follows: zn-1.8Cu-0.15Ti-0.15Mo, namely 1.8 percent of Cu, 0.15 percent of Ti and 0.15 percent of Mo by mass, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-1.8Cu-0.15Ti-0.15Mo alloy provided by the comparative example is basically the same as that of the example 1, except that the warm rolling process is replaced by a cold rolling process, and the preparation method specifically comprises the following steps:
s1 to S3: the same as in steps S1 to S3 of example 1.
And S4, carrying out 2-pass cold rolling on the first blank, wherein the reduction of each pass is 40%, and preparing the Zn-Cu-Ti-Mo alloy plate.
Comparative example 5
The chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the example 1, and the specific steps are as follows: zn-1.8Cu-0.15Ti-0.15Mo, namely Cu 1.8 percent, ti 0.15 percent, mo 0.15 percent, and the balance of Zn and inevitable impurities.
The comparative example provides a Zn-1.8Cu-0.15Ti-0.15Mo alloy whose preparation method is substantially the same as in example 1, except that the reduction per pass at the warm rolling is 70%. The macro-morphology of the alloy sheet prepared in this comparative example is shown in fig. 5, and edge cracking of the rolled sheet is severe.
Comparative example 6
Compared with the Zn-Cu-Ti alloy in the embodiment 2, the Zn-Cu-Ti alloy in the comparative example has the difference that Mo is not introduced, and specifically comprises the following components in percentage by mass: zn-3Cu-0.1Ti, namely Cu 3 percent, ti0.1 percent, and the balance of Zn and inevitable impurities in percentage by mass.
The preparation method of the Zn-3Cu-0.1Ti alloy provided by the present comparative example is substantially the same as that of example 2, except that the alloy raw materials are pure Zn, pure copper, and a Zn-5Cu-5Ti intermediate alloy, an alloy containing Mo element is not included, and the warm rolling process is replaced with a cold rolling process, specifically including the following steps:
s1 to S3: the procedure was as in steps S1 to S3 of example 2 except that the starting materials were different.
And S4, carrying out 3 times of cold rolling on the first blank, wherein the reduction of each time is 30%, and preparing the Zn-Cu-Ti alloy plate.
Comparative example 7
Compared with the chemical components and the mass percent of the Zn-Cu-Ti alloy in the embodiment 2, the Zn-Cu-Ti alloy in the comparative example has the difference that Mo is not introduced, and specifically comprises the following steps: zn-3Cu-0.1Ti, namely Cu 3 percent, ti0.1 percent, and the balance of Zn and inevitable impurities by mass percent.
The preparation method of the Zn-3Cu-0.1Ti alloy provided by the comparative example is basically the same as that of the example 2, except that the alloy raw materials are pure Zn, pure Cu and a Zn-5Cu-5Ti intermediate alloy, and the alloy containing Mo element is not included.
Comparative example 8
The chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the example 2, and the specific steps are as follows: zn-3Cu-0.1Ti-0.05Mo, namely Cu 3 percent, ti0.1 percent, mo0.05 percent, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-3Cu-0.1Ti-0.05Mo alloy provided by the present comparative example is substantially the same as that of example 2, except that only the hot rolling process is employed, and the warm rolling process is not included, and specifically includes the following steps:
s1 to S2: the same procedure as in steps S1 to S2 of example 1 was repeated.
And S3, heating the alloy casting blank to 320 ℃, performing water quenching by adopting a hot rolling process with the reduction of 30% per pass, wherein the effluent temperature is 25 ℃, and obtaining the Zn-Cu-Ti-Mo alloy plate with the thickness same as that of the Zn-Cu-Ti-Mo alloy plate in the example 2.
Comparative example 9
The chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the example 2, and the specific steps are as follows: zn-3Cu-0.1Ti-0.05Mo, namely Cu 3 percent, ti0.1 percent, mo0.05 percent, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-3Cu-0.1Ti-0.05Mo alloy provided by the present comparative example is substantially the same as that of example 2, except that the warm rolling process is replaced by a cold rolling process, specifically including the steps of:
s1 to S3: the same as in steps S1 to S3 of example 2.
And S4, carrying out 3 times of cold rolling on the first blank, wherein the reduction of each time is 30%, and preparing the Zn-Cu-Ti-Mo alloy plate.
Comparative example 10
The chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the example 2, and the specific steps are as follows: zn-3Cu-0.1Ti-0.05Mo, namely Cu 3 percent, ti0.1 percent, mo0.05 percent, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-3Cu-0.1Ti-0.15Mo alloy provided by the comparative example is basically the same as that of the example 2, except that the reduction per pass in warm rolling is 60%.
Comparative example 11
Compared with the Zn-Cu-Ti alloy in the embodiment 3, the Zn-Cu-Ti alloy provided by the comparative example has the difference that Mo is not introduced, and specifically comprises the following components in percentage by mass: zn-1.1Cu-0.2Ti, namely 1.1 percent of Cu, 0.2 percent of Ti, and the balance of Zn and inevitable impurities by mass percent.
The preparation method of the Zn-1.1Cu-0.2Ti alloy provided by the present comparative example is substantially the same as that of example 3, except that the alloy raw materials are pure Zn, a Zn-20Cu master alloy and a Zn-5Ti master alloy, a master alloy containing Mo is not included, and the warm rolling process is replaced with a cold rolling process, specifically including the following steps:
s1 to S3: the procedure was as in steps S1 to S3 of example 3 except that the starting materials were different.
And S4, carrying out 2-pass cold rolling on the first blank, wherein the reduction of each pass is 50%, and preparing the Zn-Cu-Ti-Mo alloy plate.
Comparative example 12
Compared with the Zn-Cu-Ti alloy in the embodiment 3, the Zn-Cu-Ti alloy provided by the comparative example has the difference that Mo is not introduced, and specifically comprises the following components in percentage by mass: zn-1.1Cu-0.2Ti, namely 1.1 percent of Cu, 0.2 percent of Ti, and the balance of Zn and inevitable impurities by mass percent.
The comparative example provides a Zn-1.1Cu-0.2Ti alloy having substantially the same preparation method as that of example 3, except that the alloy raw materials were pure Zn, a Zn-20Cu master alloy and a Zn-5Ti master alloy, excluding the alloy containing Mo element.
Comparative example 13
The chemical components and mass percentages of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the Zn-Cu-Ti-Mo alloy in the example 3, and the chemical components and mass percentages are as follows: zn-1.1Cu-0.2Ti-0.2Mo, namely 1.1 percent of Cu, 0.2 percent of Ti and 0.2 percent of Mo by mass, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-1.1Cu-0.2Ti-0.2Mo alloy provided by the comparative example is basically the same as that of the example 3, except that only the hot rolling process is adopted, the warm rolling process is not included, and the method specifically comprises the following steps:
s1 to S2: the same procedure as in steps S1 to S2 of example 1 was repeated.
And S3, heating the alloy casting blank to 300 ℃, performing water quenching by adopting a hot rolling process with the reduction of 20% per pass, and obtaining the Zn-Cu-Ti-Mo alloy plate with the same thickness as that of the Zn-Cu-Ti-Mo alloy plate in the embodiment 3, wherein the effluent temperature is 21 ℃.
Comparative example 14
The chemical components and mass percentages of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the Zn-Cu-Ti-Mo alloy in the example 3, and the chemical components and mass percentages are as follows: zn-1.1Cu-0.2Ti-0.2Mo, namely Cu 1.1 percent, ti 0.2 percent, mo 0.2 percent, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-1.1Cu-0.2Ti-0.2Mo alloy provided by the present comparative example is substantially the same as that of example 3, except that the warm rolling process is replaced by a cold rolling process, specifically including the steps of:
s1 to S3: the same as in steps S1 to S3 of example 1.
And S4, carrying out 2-pass cold rolling on the first blank, wherein the reduction of each pass is 50%, and preparing the Zn-Cu-Ti-Mo alloy plate.
Comparative example 15
The chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the example 3, and the specific steps are as follows: zn-1.1Cu-0.2Ti-0.2Mo, namely Cu 1.1 percent, ti 0.2 percent, mo 0.2 percent, and the balance of Zn and inevitable impurities.
The comparative example provides a Zn-1.1Cu-0.2Ti-0.2Mo alloy whose preparation method is substantially the same as in example 3, except that the reduction per pass at warm rolling is 80%.
Comparative example 16
The chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the example 1, and the specific steps are as follows: zn-1.8Cu-0.15Ti-0.15Mo, namely Cu 1.8 percent, ti 0.15 percent, mo 0.15 percent, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-1.8Cu-0.15Ti-0.15Mo alloy provided by the present comparative example is substantially the same as that of example 1, except that the cooling mode after rolling specifically includes the following steps:
s1 to S2: the same as in steps S1 to S2 of example 1.
And S3, heating the alloy casting blank to 350 ℃, carrying out 5-pass hot rolling with the reduction of 25% per pass to obtain a hot rolled blank, and carrying out air cooling on the hot rolled blank to room temperature after the hot rolling is finished to obtain a first blank.
S4, heating the first blank to 150 ℃, carrying out 2-pass warm rolling with the reduction of each pass being 40% to obtain a warm rolled blank, and after the warm rolling is finished, carrying out air cooling on the warm rolled blank to room temperature to prepare the Zn-Cu-Ti-Mo alloy plate.
Comparative example 17
The chemical components and the mass percentage of the Zn-Cu-Ti-Mo alloy provided by the comparative example are the same as those of the example 1, and the specific steps are as follows: zn-1.8Cu-0.15Ti-0.15Mo, namely 1.8 percent of Cu, 0.15 percent of Ti and 0.15 percent of Mo by mass, and the balance of Zn and inevitable impurities.
The preparation method of the Zn-1.8Cu-0.15Ti-0.15Mo alloy provided by the present comparative example is substantially the same as that of example 1, except that the hot rolling and warm rolling is replaced with the hot rolling and warm rolling, and the cold rolling is performed after the hot rolling, specifically including the following steps:
s1 to S2: the same procedure as in steps S1 to S2 of example 1 was repeated.
S3, heating the alloy casting blank to 350 ℃, carrying out 3-pass hot rolling with the reduction of 25% per pass to obtain a hot rolling blank, and carrying out water quenching on the hot rolling blank after the hot rolling is finished, wherein the water outlet temperature is 21 ℃, so as to obtain a first blank.
S4, heating the first blank to 150 ℃, carrying out 2-pass warm rolling with the reduction of 40% per pass to obtain a warm-rolled blank, and after the warm rolling is finished, putting the warm-rolled blank into water for quenching, wherein the effluent temperature is 23 ℃, so as to obtain a second blank.
And S5, cold rolling the second blank, wherein the reduction per pass is 25%, and finally preparing the Zn-Cu-Ti-Mo alloy plate with the thickness same as that of the Zn-Cu-Ti-Mo alloy plate in the embodiment 1.
The microstructure diagrams of the alloy plate materials prepared in example 1 and comparative examples 1 to 3 are shown in fig. 1 to 4, and it is understood from fig. 1 to 4 that the microstructure of the alloy plate material prepared in example 1 is fine and uniform, and the microstructure of the alloy plate materials prepared in comparative examples 1 to 3 is coarse and the crystal grain size is not uniform. The invention obviously refines the crystal grains of the prepared zinc alloy by adding Mo element into the Zn-Cu-Ti alloy and combining the hot rolling and warm rolling processes.
The Zn-Cu-Ti-Mo alloys prepared in examples 1 to 3 and comparative examples 1 to 17 were tested for mechanical properties (tensile strength, yield strength, and elongation), and the alloy morphology after rolling was observed, and the specific results are detailed in table 1.
TABLE 1
From the mechanical properties of the Zn-Cu-Ti-Mo alloy prepared in the examples 1-3 and the Zn-Cu-Ti-Mo alloy prepared in the comparative examples 1-4, 6-9, 11-14 and 17, the invention obviously improves the strength and plasticity of the Zn-Cu-Ti alloy with high copper content by adding Mo element into the Zn-Cu-Ti alloy and combining the hot rolling and warm rolling processes, and the prepared Zn-Cu-Ti-Mo alloy has the tensile strength of more than 300MPa, the yield strength of more than 200MPa and the elongation of more than 18 percent, thereby meeting the performance requirements of biomedical degradable implant materials.
From the rolling patterns of the Zn-Cu-Ti-Mo alloys prepared in examples 1 to 3 and the Zn-Cu-Ti-Mo alloys prepared in comparative examples 5, 10, and 15, it can be seen that the present invention can prevent the alloy from cracking and maintain the plate shape good by limiting the reduction per pass of warm rolling to 30% to 50%.
From the mechanical properties of the Zn-Cu-Ti-Mo alloy prepared in example 1 and the Zn-Cu-Ti-Mo alloy prepared in comparative example 16, it can be seen that the tensile strength, yield strength and elongation of the Zn-Cu-Ti-Mo alloy are significantly improved by water quenching the hot rolled blank after hot rolling and water quenching the warm rolled blank after warm rolling.
In conclusion, the Zn-Cu-Ti-Mo alloy prepared by the invention meets the performance requirements of biomedical degradable implant materials, and has the advantages of simple preparation process and wide application prospect.
The Zn-Cu-Ti-Mo alloy provided by the invention, the preparation method and the application thereof are described in detail. The above description of the embodiments is only intended to help understand the method of the present application and its core ideas.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.
Claims (12)
1. A preparation method of a Zn-Cu-Ti-Mo alloy is characterized by comprising the following steps:
preparing a casting blank: preparing raw materials according to Zn-Cu-Ti-Mo alloy components, smelting the raw materials, and then casting the smelted alloy melt into a casting blank;
hot rolling: carrying out hot rolling on the casting blank, and obtaining a first blank after the hot rolling is finished, wherein the hot rolling temperature is 250-360 ℃, the pass of the hot rolling is 2-6 times, and the reduction of each pass is 15-40%;
warm rolling: carrying out warm rolling on the first blank, and obtaining a Zn-Cu-Ti-Mo alloy plate after the warm rolling is finished, wherein the warm rolling temperature is 100-200 ℃, the rolling passes of the warm rolling are 2-3 times, and the reduction of each pass is 30-50%;
the Zn-Cu-Ti-Mo alloy comprises the following components in percentage by mass:
1.0-3.0% of Cu0 but not 1.0%, 0.1-0.2% of Ti0.05-0.2%, and the balance of Zn and inevitable impurities.
2. The method of manufacturing a Zn-Cu-Ti-Mo alloy according to claim 1, wherein, in the hot rolling step, the cast slab is hot-rolled to obtain a hot-rolled slab, and after the hot rolling is finished, the hot-rolled slab is water-quenched to obtain a first billet;
in the warm rolling step, the first blank is subjected to warm rolling to obtain a warm rolling blank, and after the warm rolling is finished, the warm rolling blank is subjected to water quenching to obtain the Zn-Cu-Ti-Mo alloy plate.
3. The production method of a Zn-Cu-Ti-Mo alloy according to claim 2, characterized in that water quenching after hot rolling is to quench the hot-rolled billet to 10 to 40 ℃ with water;
and water quenching after warm rolling is to cool the warm rolled blank to 10 to 40 ℃ and discharge water.
4. The method of claim 1, wherein the raw material comprises pure Zn, pure Cu and/or a master alloy containing Cu, a master alloy containing Ti, and a master alloy containing Mo.
5. The method of claim 4, wherein the Cu-containing master alloy is Zn-x 1 Cu、Zn-x 2 Cu-y 1 Ti、Mo-x 3 Cu-y 2 Ti、Cu-y 3 Ti、Cu-y 5 Ti-z 2 Mo、Cu-z 3 One or more of Mo, wherein x 1 、x 2 、x 3 、y 1 、y 2 、y 3 、y 5 、z 2 And z 3 Respectively represents the corresponding mass percentage content of each alloy element, and the unit is wt percent, x 1 Represents 5 to 20,x 2 Represent 5 to 20,y 1 Represents 1 to 5,x 3 Represent 1 to 20,y 2 Represent 1 to 20,y 3 Represents 1 to 20,y 5 Represents 1 to 20,z 2 Represents 1 to 20,z 3 Represents 1 to 50;
the intermediate alloy containing Ti element is Zn-y 4 Ti、Cu-y 3 Ti、Ti-z 1 Mo、Zn-x 2 Cu-y 1 Ti、Cu-y 5 Ti-z 2 One or more of Mo, wherein y 4 And z 1 Respectively represents the corresponding mass percentage content of each alloy element, and the unit is wt percent and y 4 Represents 1 to 20,z 1 Represents 1 to 50;
the master alloy containing Mo element is Cu-z 3 Mo、Cu-y 5 Ti-z 2 Mo、Ti-z 1 One or more of Mo.
6. The method for preparing the Zn-Cu-Ti-Mo alloy according to claim 1, wherein the raw material is preheated and dried before smelting, wherein the temperature of the preheated and dried is 50-300 ℃, and the holding time of the preheated and dried is 1-15 min.
7. The method of claim 1, wherein the melting comprises raw material melting and refining, wherein the raw material melting comprises putting pure Zn into a melting furnace to melt, and after the pure Zn is completely melted, adding pure Cu and/or a Cu-containing intermediate alloy, a Ti-containing intermediate alloy, and a Mo-containing intermediate alloy in sequence.
8. The method of manufacturing Zn-Cu-Ti-Mo alloy as recited in claim 7, characterized in thatThe melting temperature is 500-800 ℃, the refining time is 2-30 min, and the refining method is a rotary argon blowing method and N is introduced 2 And Cl 2 The mixed gas method and the chloride salt adding method.
9. The method of claim 8, wherein the N is selected from the group consisting of Cu, ti, mo, ti, mo, and mixtures thereof 2 And Cl 2 The volume ratio of (10 to 60) to (1).
10. A Zn-Cu-Ti-Mo alloy, characterized in that it is produced by the production method according to any one of claims 1 to 9.
11. The Zn-Cu-Ti-Mo alloy of claim 10, wherein the Zn-Cu-Ti-Mo alloy has tensile strength of 300MPa to 400MPa, yield strength of 200MPa to 300MPa, and elongation of 30% to 95%.
12. Use of the Zn-Cu-Ti-Mo alloy according to claim 10, for medical degradable metallic materials.
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| CN114086012A (en) * | 2021-11-12 | 2022-02-25 | 森特士兴集团股份有限公司 | Preparation method of low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate and product |
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