CN112048641A - Manufacturing method of novel medical titanium alloy ingot - Google Patents
Manufacturing method of novel medical titanium alloy ingot Download PDFInfo
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- CN112048641A CN112048641A CN202010948802.0A CN202010948802A CN112048641A CN 112048641 A CN112048641 A CN 112048641A CN 202010948802 A CN202010948802 A CN 202010948802A CN 112048641 A CN112048641 A CN 112048641A
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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
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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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
Abstract
The invention relates to the technical field of biomedical metal material manufacturing, in particular to a method for manufacturing a novel medical titanium alloy ingot, which comprises the following steps: putting a titanium rod, a zirconium rod and an aluminum boron rare earth rod into a vacuum consumable skull furnace, then determining the diameter of a consumable electrode according to the size of a crucible of the vacuum consumable skull furnace, determining the length of the consumable electrode according to the melting capacity of the crucible, and welding an assembled electrode by using plasma argon protection; clamping the assembled and welded consumable electrode on an electrode rod, putting an ingot casting mold made of heat-resistant cast iron into a furnace, aligning the mold, closing a furnace door, vacuumizing, determining smelting current and voltage according to the size of the furnace and the size of the electrode to ensure that the whole consumable electrode is completely melted, turning over a crucible, casting an ingot, breaking vacuum, and discharging; in the invention, on the basis of the main components of the original scheme, trace refined crystal grain element B and rare earth elements are added, and a unique smelting ingot casting manufacturing process is applied to manufacture the high-quality ingot casting with uniform components and no various segregants.
Description
Technical Field
The invention relates to the technical field of biomedical metal material manufacturing, in particular to a manufacturing method of a novel medical titanium alloy ingot.
Background
Titanium and its alloy have been applied more and more widely in clinic with its elastic modulus similar to human bone, good biocompatibility and excellent corrosion resistance in biological environment, the titanium alloy which is applied in clinic is mainly represented by pure titanium and Ti-6Al-4V, pure titanium has good corrosion resistance in physiological environment, but its intensity is lower, the abrasion resistance is poorer, limit its application in the position with larger bearing capacity, at present mainly used for oral cavity repair and bone replacement of smaller bearing part, Ti-6Al-4V titanium alloy has higher intensity and better processing property, this alloy has been widely used as surgery repair material in the seventies, such as hip joint knee joint, etc., and also used as femur and tibia substitute material in clinic, but this kind of alloy contains two elements of Al and V, v is considered to be an element toxic to organisms, which accumulates in the organism in the bone, liver, kidney, spleen, etc., and toxic effects are associated with biochemical metabolism of phosphate. In order to avoid the potential toxicity of V element, two new alpha + beta type medical titanium alloys Ti-5Al-2.5Fe and Ti-6Al-7Nb were developed in Europe in the middle of the 80's. The mechanical property of the alloy is similar to that of Ti-6Al-4V, and toxic elements V are replaced by Fe and Nb in the alloy.
In recent years, the development of novel medical beta-type titanium alloy mainly replaces V with high Mo and high Nb elements, further reduces the elastic modulus E of the titanium alloy to be close to that of human bones, avoids the phenomenon of stress shielding, so that the bone absorption around the implant is avoided, and finally the implant is loosened or broken to cause the implant failure. However, molybdenum or niobium is a refractory metal, and segregation is easily generated in the smelting process, so that the mechanical property stability of the alloy is seriously influenced. Therefore, the preparation of titanium alloy ingots with high component uniformity is a key technology for producing beta-type medical titanium alloys, and the titanium alloy processing materials produced on the basis of the high-quality ingots can ensure reliable and stable mechanical properties of plates, rods and wires.
The near-beta type titanium alloy Ti-15Mo-5Zr-3Al is one of the medical titanium alloy grades used abroad, and the grade is more and more emphasized by the fact that the grade has no vanadium, lower cost, better mechanical property, lower elastic modulus, excellent cold and hot processing performance and welding performance, and the record of the grade is not used at present in the field of biological medical treatment.
The common manufacturing method of the titanium alloy ingots at home and abroad is a vacuum consumable electrode furnace smelting method. The specific method comprises the following steps:
the raw materials are sponge titanium, molybdenum-aluminum intermediate alloy containing molybdenum and sponge zirconium; and extruding the consumable electrode on an extruder, and performing vacuum consumable melting for more than 3 times to prepare an ingot. Because the method is limited by the characteristics of the vacuum consumable electrode furnace, the size and the height of a molten pool are limited, alloy components can only be uniform in a certain area, and the chemical component segregation degree of the whole titanium alloy ingot is greatly influenced by the uniformity of artificial distribution when the consumable electrode is extruded, the problem of component segregation of beta type titanium alloy smelting ingots with higher alloy content in China has no fundamental breakthrough all the time, and therefore, the method for manufacturing the novel medical titanium alloy ingot is provided for solving the problems.
Disclosure of Invention
The invention aims to provide a method for manufacturing a novel medical titanium alloy ingot, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a manufacturing method of a novel medical titanium alloy ingot comprises the following steps:
the method comprises the following steps: preparing raw materials: putting a titanium rod, a zirconium rod and an aluminum boron rare earth rod into a vacuum consumable skull furnace, then determining the diameter of a consumable electrode according to the size of a crucible of the vacuum consumable skull furnace, determining the length of the consumable electrode according to the melting capacity of the crucible, and welding an assembled electrode by using plasma argon protection;
step two: casting in a vacuum consumable skull furnace: clamping the assembled and welded consumable electrode on an electrode rod, putting an ingot casting mold made of heat-resistant cast iron into a furnace, aligning the mold, closing a furnace door, vacuumizing, determining smelting current and voltage according to the size of the furnace and the size of the electrode, controlling the pressure and flow of cooling water of a smelting crucible, controlling the smelting time and speed, ensuring that the complete consumable electrode is completely melted, turning over the crucible, casting an ingot, cooling the titanium alloy ingot casting furnace to below 200 ℃, breaking vacuum, and discharging the ingot casting furnace;
step three: checking a mother alloy ingot: cleaning the surface of a titanium alloy master alloy cast ingot cast by a vacuum consumable skull furnace, peeling, sampling and analyzing chemical components;
step four: and casting in a secondary vacuum consumable electrode furnace.
Preferably, in the first step, the purity of the titanium rod is 99.9%, the purity of the zirconium rod is 99.9%, the purity of the aluminum boron rare earth rod is 99%, and the ingredient composition of molybdenum is 14.5-15.5%, the ingredient composition of zirconium is 4.5-5.5%, the ingredient composition of aluminum is 2.8-3.3%, the ingredient composition of boron is less than 0.01%, and the ingredient composition of rhenium is less than 0.03%.
Preferably, the vacuum consumable skull furnace in the step one adopts a furnace type of casting more than 500 kg.
Preferably, the vacuum degree is controlled to be less than 3Pa when the vacuum is pumped in the second step.
Preferably, the outlet temperature of the cooling water in the second step is less than 30 ℃.
Preferably, the primary consumable smelting process and the secondary consumable smelting process in the fourth step are basically similar, the size of the second cast ingot is increased, the smelting current and voltage are adjusted according to the size of the cast ingot, the second cast ingot consumable smelting is finished by paying attention to cast ingot feeding, and the shrinkage cavity is controlled within the range of less than 50 mm.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, on the basis of the main components of the original scheme, trace refined crystal grain element B and rare earth elements are added, and a unique smelting ingot casting manufacturing process is applied to manufacture the high-quality ingot casting with uniform components and no various segregants.
Detailed Description
Example 1: the invention provides a technical scheme that:
a manufacturing method of a novel medical titanium alloy ingot comprises the following steps:
the method comprises the following steps: preparing raw materials: putting a titanium rod, a zirconium rod and an aluminum boron rare earth rod into a vacuum consumable skull furnace, then determining the diameter of a consumable electrode according to the size of a crucible of the vacuum consumable skull furnace, determining the length of the consumable electrode according to the melting capacity of the crucible, and welding an assembled electrode by using plasma argon protection;
step two: casting in a vacuum consumable skull furnace: clamping the assembled and welded consumable electrode on an electrode rod, putting an ingot casting mold made of heat-resistant cast iron into a furnace, aligning the mold, closing a furnace door, vacuumizing, determining smelting current and voltage according to the size of the furnace and the size of the electrode, controlling the pressure and flow of cooling water of a smelting crucible, controlling the smelting time and speed, ensuring that the complete consumable electrode is completely melted, turning over the crucible, casting an ingot, cooling the titanium alloy ingot casting furnace to below 200 ℃, breaking vacuum, and discharging the ingot casting furnace;
step three: checking a mother alloy ingot: cleaning the surface of a titanium alloy master alloy cast ingot cast by a vacuum consumable skull furnace, peeling, sampling and analyzing chemical components;
step four: and casting in a secondary vacuum consumable electrode furnace.
The melting of the vacuum consumable furnace is carried out by melting the consumable electrode and cooling the titanium alloy molten metal in a water-cooled copper crucible simultaneously, and the melting and the solidification are carried out simultaneously, so the melting pool is shallow, the height of the melting pool is about 200-300mm generally, the chemical components of the titanium alloy can only be uniform within the range, and the whole consumable electrode cannot be uniform under the molten metal, so the components of the consumable electrode are required to be very uniform.
The vacuum consumable skull furnace is the most main equipment for casting titanium alloy castings, and is characterized in that a consumable electrode is molten into a titanium alloy metal liquid by a complete consumable electrode, the titanium alloy metal liquid is stored in a water-cooled copper crucible titanium alloy skull in a molten state, all components of the titanium alloy metal liquid in a molten pool can be homogenized under the action of electromagnetic stirring, and then the crucible is turned over, and cast ingots are cast; ingot casting was performed similarly to vacuum induction furnace.
In the invention, on the basis of the main components of the original scheme, trace refined crystal grain element B and rare earth elements are added, and a unique smelting ingot casting manufacturing process is applied to manufacture the high-quality ingot casting with uniform components and no various segregants.
The purity of the titanium rod in the first step is 99.9 percent, the purity of the zirconium rod is 99.9 percent, the purity of the aluminum-boron rare earth rod is 99 percent, the ingredient composition of molybdenum is 14.5-15.5 percent, the ingredient composition of zirconium is 4.5-5.5 percent, the ingredient composition of aluminum is 2.8-3.3 percent, the ingredient composition of boron is less than 0.01 percent, and the ingredient composition of rhenium is less than 0.03 percent, so that the grade of the raw materials is effectively limited, and the quality of the cost can be effectively ensured, the vacuum consumable skull furnace in the first step adopts a furnace type of fusion casting more than 500 kilograms, so that the cost utilization rate can be reduced to the maximum extent, the material utilization rate is improved, the vacuum degree is controlled to be less than 3Pa when the vacuum is pumped in the second step, the outlet temperature of cooling water is less than 30 ℃, so that the production quality is effectively ensured, the first consumable smelting process in the fourth step is basically similar to the second consumable ingot casting process, and the size of the second ingot casting is, the smelting current and voltage are adjusted according to the size of the cast ingot, the second time of the consumable smelting of the cast ingot is finally carried out by paying attention to the feeding of the cast ingot, the shrinkage cavity is controlled within the range of less than 50mm, because the titanium alloy master alloy cast ingot is carried out in a vacuum consumable skull furnace, the uniformity of alloy components is good, but the cast ingot structure is thick when molten metal is directly cast, the shrinkage cavity and shrinkage porosity exist, the secondary vacuum consumable casting is used for adjusting the master alloy cast ingot structure, and the uniformity of the components of the titanium alloy cast ingot and the compactness and stability of the structure are ensured.
After the production, the control range of the chemical components of the finished cast ingot is as follows: (weight percent) molybdenum 15.10-15.15, zirconium 5.00-5.05, aluminum 2.95-3.05, boron <0.005, rhenium <0.02, oxygen <0.08, nitrogen <0.005, hydrogen < 0.001.
The deviation of the chemical components of the finished cast ingot is far better than the Chinese and international standards of the medical titanium alloy, and the consistency and uniformity of the chemical components are far higher than those of products of other domestic enterprises.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. The foregoing is only a preferred embodiment of the present invention, and it should be noted that there are objectively infinite specific structures due to the limited character expressions, and it will be apparent to those skilled in the art that a plurality of modifications, decorations or changes may be made without departing from the principle of the present invention, and the technical features described above may be combined in a suitable manner; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.
Claims (6)
1. A manufacturing method of a novel medical titanium alloy ingot is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: preparing raw materials: putting a titanium rod, a zirconium rod and an aluminum boron rare earth rod into a vacuum consumable skull furnace, then determining the diameter of a consumable electrode according to the size of a crucible of the vacuum consumable skull furnace, determining the length of the consumable electrode according to the melting capacity of the crucible, and welding an assembled electrode by using plasma argon protection;
step two: casting in a vacuum consumable skull furnace: clamping the assembled and welded consumable electrode on an electrode rod, putting an ingot casting mold made of heat-resistant cast iron into a furnace, aligning the mold, closing a furnace door, vacuumizing, determining smelting current and voltage according to the size of the furnace and the size of the electrode, controlling the pressure and flow of cooling water of a smelting crucible, controlling the smelting time and speed, ensuring that the complete consumable electrode is completely melted, turning over the crucible, casting an ingot, cooling the titanium alloy ingot casting furnace to below 200 ℃, breaking vacuum, and discharging the ingot casting furnace;
step three: checking a mother alloy ingot: cleaning the surface of a titanium alloy master alloy cast ingot cast by a vacuum consumable skull furnace, peeling, sampling and analyzing chemical components;
step four: and casting in a secondary vacuum consumable electrode furnace.
2. The method for manufacturing a novel medical titanium alloy ingot according to claim 1, characterized in that: in the first step, the purity of the titanium rod is 99.9%, the purity of the zirconium rod is 99.9%, the purity of the aluminum-boron rare earth rod is 99%, the ingredient composition of molybdenum is 14.5-15.5%, the ingredient composition of zirconium is 4.5-5.5%, the ingredient composition of aluminum is 2.8-3.3%, the ingredient composition of boron is less than 0.01%, and the ingredient composition of rhenium is less than 0.03%.
3. The method for manufacturing a novel medical titanium alloy ingot according to claim 1, characterized in that: and the vacuum consumable skull furnace in the step one adopts a furnace type of casting more than 500 kg.
4. The method for manufacturing a novel medical titanium alloy ingot according to claim 1, characterized in that: and in the second step, the vacuum degree is controlled to be less than 3Pa during vacuum pumping.
5. The method for manufacturing a novel medical titanium alloy ingot according to claim 1, characterized in that: in the second step, the outlet temperature of the cooling water is less than 30 ℃.
6. The method for manufacturing a novel medical titanium alloy ingot according to claim 1, characterized in that: and in the fourth step, the primary consumable smelting process and the secondary consumable smelting process are basically similar, the size of the second cast ingot is increased, the smelting current and voltage are adjusted according to the size of the cast ingot, the second cast ingot consumable smelting process is finally carried out by paying attention to cast ingot feeding, and the shrinkage cavity is controlled within the range of less than 50 mm.
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| CN114000010A (en) * | 2021-11-05 | 2022-02-01 | 云南钛业股份有限公司 | High-quality titanium alloy ingot and production method thereof |
| CN114953633A (en) * | 2022-06-16 | 2022-08-30 | 王晓凤 | 2132AH aerospace material with high temperature resistance, high pressure resistance, corrosion resistance and high ductility and preparation method thereof |
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