CN111945032A - 3D printing fine-grain titanium alloy and preparation method thereof - Google Patents
3D printing fine-grain titanium alloy and preparation method 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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- C22C14/00—Alloys based on titanium
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- 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
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Abstract
The invention provides a 3D printing fine-grain titanium alloy and a preparation method thereof, wherein the titanium alloy comprises the following elements in parts by mass: 3-5% of Al, 0.05-0.15% of B, 0.3-0.6% of C and the balance of Ti and other impurity elements. The fine-grained titanium alloy can effectively refine the crystal grains of the alloy by doping boron and carbon elements, improve the alloy strength without reducing the plasticity performance, so as to replace the Ti6Al4V material which is widely applied at present; the fine-grained titanium alloy does not contain expensive and harmful vanadium elements, can effectively reduce the cost of the alloy, and is green and environment-friendly; the fine-grained titanium alloy is prepared by adopting a 3D printing method, so that the fine-grained titanium alloy is more suitable for preparing parts which are complex in shape and difficult to process, the preparation difficulty is reduced, and the time and the labor cost are saved.
Description
Technical Field
The invention belongs to the technical field of metal materials, and relates to a 3D printing fine-grain titanium alloy and a preparation method thereof.
Background
The metal 3D printing technology has the advantages of high dimensional precision, good surface quality, excellent performance of formed parts and the like, the forming process is formed by stacking powder or wire materials layer by layer, the material utilization rate is high, the product production and development period is short, meanwhile, the shape of the product is almost not limited, and complex structures such as grids, cavities and the like can be directly formed, so the metal 3D printing technology is often used for manufacturing parts with complex shapes and difficult processing, is preferentially popularized by various countries, and is widely applied in various fields.
Titanium alloy is a new structural metal, and is widely applied to the fields of aerospace, medical treatment and the like due to the advantages of high specific strength, excellent heat resistance, super-strong corrosion resistance and the like, but the melting point of titanium is extremely high, the titanium belongs to refractory metals and is very easy to react with oxygen, so that the melting cost is very high, and the titanium alloy has high processing difficulty and high processing cost due to the low thermal expansion coefficient of the titanium. Pure metal titanium has low density, good corrosion resistance and wide application, but the strength performance of the titanium material is limited due to the limit of the strength of the titanium material, so that titanium alloy is often used, wherein the most widely used titanium alloy is Ti6Al4V alloy, but the cost of the alloy is high due to V belonging to a scarce resource.
CN 101501228A discloses a method for preparing a high-strength, high-hardness and high-toughness titanium alloy, which comprises: combining boron with the titanium alloy such that the boron concentration in the boron-modified titanium alloy does not exceed a eutectic limit, maintaining the carbon concentration in the boron-modified titanium alloy below a predetermined limit to avoid embrittlement, heating the boron-modified alloy above a beta transus temperature to remove supersaturated excess boron, and deforming the boron-modified titanium alloy at a rate slow enough to prevent destruction of the microstructure and reduction of toughness; the titanium alloy used in the method is titanium-aluminum-vanadium alloy and the like, and boron is doped to improve the mechanical property of the titanium alloy, but the boron doping process in the method is complex and difficult to control, the strength of the initial titanium alloy is high, and the boron is difficult to uniformly dope.
CN 101392338A discloses a composite reinforced high-strength high-elasticity modulus titanium alloy, which comprises the following components and the mass percent of the components are Ai 5.1-6.5%, V3.3-4.3%, B0.06-0.91%, C0.07-1.27%, and the balance is titanium, wherein vanadium is added in the form of aluminum-vanadium intermediate alloy, the raw material components are mixed and pressed into electrodes, the electrodes are placed into an electric arc furnace, a titanium alloy cast ingot containing reinforcing phases TiB and TiC is obtained by smelting, the titanium alloy cast ingot is subjected to cogging forging in a beta phase region, then conventional forging is performed in an alpha phase region and a beta phase region, and after the forging is completed, oxide skin, shrinkage cavity segregation and inclusion defects on the surface are removed, so that the titanium alloy is obtained; the titanium alloy still contains titanium with higher cost in composition, so that the cost is difficult to be obviously reduced, and the crystal grain and the plasticity of the alloy are not determined.
In summary, for the selection of the element types in the titanium alloy, the cost can be significantly reduced, and the comprehensive mechanical property can be improved, and the method can be suitable for the preparation of the complex-structure formed part.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a 3D printing fine-grain titanium alloy and a preparation method thereof, the fine-grain titanium alloy can effectively refine the crystal grains of the alloy and improve the alloy strength by doping boron and carbon elements, and the alloy does not contain vanadium element which is commonly added in the existing titanium alloy, so that the alloy cost can be effectively reduced; the preparation method is adopted for preparation by a 3D printing method, so that the preparation method is more suitable for preparation of parts with complex shapes and difficult processing, the preparation difficulty is reduced, and the time and the labor cost are saved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a 3D printed fine-grained titanium alloy, the elemental composition of which comprises, in mass percent: 3-5% of Al, 0.05-0.15% of B, 0.3-0.6% of C and the balance of Ti and other impurity elements.
In the invention, except for the main element titanium, other doped elements mainly comprise aluminum, boron and carbon, wherein the aluminum element is a common element of the titanium alloy, has higher solubility in an alpha phase and plays a role in solid solution strengthening.
Wherein, the mass fraction of each doping element is 3-5% of Al, such as 3%, 3.5%, 4%, 4.5% or 5%, but not limited to the recited values, and other unrecited values within the numerical range are also applicable; b0.05 to 0.15%, for example 0.05%, 0.06%, 0.08%, 0.1%, 0.12%, 0.14%, or 0.15%, etc., but not limited to the recited values, and other values not recited within the range of the values are also applicable; c0.3 to 0.6%, for example, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, or 0.6%, etc., but is not limited to the recited values, and other values not recited within the range of the values are also applicable.
Based on the effects of boron and carbon elements in the alloy, if the mass fraction of B element is lower, the grain refining effect is weakened, and if the mass fraction of B element is higher, element segregation is caused and uniform distribution is difficult; if the mass fraction of the element C is too high, part of the element C is difficult to dissolve, reducing the plasticity of the material, and if the mass fraction of the element C is too low, there is no significant strengthening effect.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
In a preferred embodiment of the present invention, the other impurity elements include N, H and O.
Preferably, the other impurity elements include, in mass fraction: n.ltoreq.0.03%, for example 0.03%, 0.025%, 0.02%, 0.015% or 0.01%, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable; h.ltoreq.0.01%, for example 0.01%, 0.009%, 0.008%, 0.006%, or 0.005%, etc., but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable; o.ltoreq.0.15%, for example 0.15%, 0.14%, 0.12%, 0.1% or 0.08%, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In a preferred embodiment of the present invention, the titanium alloy has an as-cast grain size of 100 to 300. mu.m, for example, 100. mu.m, 150. mu.m, 180. mu.m, 200. mu.m, 240. mu.m, 270. mu.m, or 300. mu.m, but the invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
In the invention, the grain size of the obtained alloy will be different according to the addition amount of boron and carbon elements, the grain size will be different naturally, and the alloy can be divided into a plurality of grades, and all belong to the category of fine grains and below.
In another aspect, the present invention provides a method for preparing the above fine-grained titanium alloy, comprising the steps of:
(1) titanium sponge, an aluminum simple substance, an aluminum-titanium-boron intermediate alloy, a boron simple substance and carbon powder are proportioned according to the mass fraction of the elements and then subjected to vacuum melting to obtain a sample base material;
(2) preparing alloy powder from the sample base material obtained in the step (1) by adopting an air atomization method, and screening to obtain alloy powder for 3D printing;
(3) preparing an alloy sample from the 3D printing alloy powder obtained in the step (2) by adopting a selective laser melting method, and performing heat treatment to obtain the 3D printing fine-grain titanium alloy.
As a preferable technical scheme of the invention, the titanium sponge in the step (1) is 0-grade titanium sponge.
In the invention, the sponge titanium is sponge metal titanium produced by a metallothermic reduction method, and is divided into different grades according to different purities, wherein the purity of 0-grade sponge titanium can reach more than 99.7%.
Preferably, the purity of the aluminum in step (1) is above 99.99%, such as 99.99%, 99.992%, 99.995% or 99.996%, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the purity of the carbon powder in step (1) is 99.9% or more, such as 99.9%, 99.92%, 99.94%, 99.95%, 99.96%, or 99.98%, etc., but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferable technical scheme of the invention, the aluminum-titanium-boron intermediate alloy in the step (1) comprises the following elements in percentage by mass: b0.9 to 1.1%, for example, 0.9%, 0.92%, 0.95%, 0.98%, 1.0%, 1.03%, 1.05%, 1.08%, or 1.1%, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable; 2.5 to 3.5% of Ti, for example, 2.5%, 2.7%, 2.8%, 3.0%, 3.2%, 3.4% or 3.5%, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable; the balance being Al.
In the invention, one of the key points of the preparation of the fine-grained titanium alloy is the selection of the raw material, and part of boron element is added in the form of aluminum-titanium-boron intermediate alloy, so that the dissolution speed of boron can be improved.
Preferably, the boron element added in the form of the al-ti-b master alloy accounts for 35-45%, for example 35%, 36%, 38%, 40%, 42%, 44% or 45% of the boron element in the titanium alloy, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In a preferred embodiment of the present invention, the vacuum melting in step (1) is performed in a consumable vacuum melting furnace.
Preferably, the number of times of vacuum melting in step (1) is at least 2, for example, 2, 3, 4 or 5, and the like, and the specific times are selected according to factors such as parameters of vacuum melting, composition of mixed raw materials, and the like, and preferably 2 to 3 times.
Preferably, the vacuum degree of the vacuum melting in the step (1) is lower than 10-2Pa, e.g. 10-2Pa、8×10-3Pa、6×10-3Pa、5×10-2Pa、4×10-3Pa、2×10-3Pa or 10-3Pa, etc., but are not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the temperature of the vacuum melting in the step (1) is 1680 to 1720 ℃, such as 1680 ℃, 1685 ℃, 1690 ℃, 1695 ℃, 1700 ℃, 1710 ℃ or 1720 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable; the time is 5 to 10min, for example, 5min, 6min, 7min, 8min, 9min or 10min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In a preferred embodiment of the present invention, before the gas atomization method in step (2) is performed, the sample substrate is first subjected to surface scale removal.
Preferably, the gas atomization method in step (2) is: firstly, melting a sample substrate, then spraying gas into a mist shape, and then condensing to form alloy powder.
In the present invention, the gas used in the gas atomization method is a compressed gas, and specifically, an inert gas, for example, argon gas having a purity of 99.99% or more, may be selected.
Preferably, the vacuum degree of the sample substrate when melting and atomizing is independently not higher than 10-2Pa, e.g. 10-2Pa、8×10-3Pa、6×10-3Pa、5×10-2Pa、4×10-3Pa、2×10-3Pa or 10-3Pa, etc., but are not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the particle size range of the 3D printing alloy powder obtained after sieving in step (2) is 15 to 53 μm, for example, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 53 μm, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferable technical scheme of the invention, the selective laser melting method in the step (3) is a 3D printing forming method, alloy powder is melted by adopting laser, the powder is repeatedly spread after sintering and solidification, and the alloy sample is formed by stacking layer by layer.
In the invention, the selective laser melting method is one of 3D printing and forming methods, and a sample with a required structure is prepared by utilizing the high precision and high temperature characteristics of laser.
Preferably, the heat treatment mode in the step (3) is annealing heat treatment.
Preferably, the annealing temperature is 600 to 700 ℃, such as 600 ℃, 620 ℃, 640 ℃, 660 ℃, 680 ℃, or 700 ℃, but not limited to the recited values, and other values not recited within the range of values are equally applicable; the holding time is 1 to 2 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours or 2 hours, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the alloy sample after the annealing treatment is cooled along with the furnace.
In the invention, the main function of the annealing heat treatment is to eliminate the residual stress in the sample prepared by the selective laser melting method, thereby improving the mechanical property of the sample.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) the method comprises the following steps of proportioning 0-grade sponge titanium, an aluminum simple substance, an aluminum-titanium-boron intermediate alloy, a boron simple substance and carbon powder according to the mass fraction of elements, wherein the aluminum-titanium-boron intermediate alloy comprises the following elements in percentage by mass: 2.5 to 3.5 percent of Tis, 0.9 to 1.1 percent of B and the balance of Al, wherein the boron element added in the form of Al-Ti-B intermediate alloy accounts for 35 to 45 percent of the boron element in the titanium alloy, and then the vacuum melting is carried out, the number of the vacuum melting is at least 2, and the vacuum degree during the vacuum melting is lower than 10-2Pa, vacuum melting at 1680-1720 ℃ for 5-10 min to obtain a sample base material;
(2) removing surface oxide skin of the sample substrate obtained in the step (1), and preparing alloy powder by adopting an air atomization method, wherein the air atomization method comprises the following steps: melting a sample substrate, spraying gas into a mist shape, condensing to form alloy powder, and screening to obtain alloy powder for 3D printing with the particle size range of 15-53 mu m;
(3) preparing an alloy sample from the 3D printing alloy powder obtained in the step (2) by adopting a selective laser melting method, then carrying out annealing heat treatment, wherein the annealing temperature is 600-700 ℃, the heat preservation time is 1-2 h, and cooling the alloy sample with a furnace after the annealing treatment to obtain the 3D printing fine-grained titanium alloy.
Compared with the prior art, the invention has the following beneficial effects:
(1) the fine-grained titanium alloy can effectively refine the crystal grains of the alloy by doping boron and carbon elements, improve the alloy strength without reducing the plasticity performance, so as to replace the Ti6Al4V material which is widely applied at present;
(2) the fine-grained titanium alloy does not contain expensive and harmful vanadium, can effectively reduce the cost of the alloy, and is green and environment-friendly;
(3) the fine-grain titanium alloy is prepared by adopting a 3D printing method, so that the fine-grain titanium alloy is more suitable for preparing parts which are complex in shape and difficult to process, the preparation difficulty is reduced, and the time and the labor cost are saved.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The specific embodiment of the invention provides a 3D printing fine-grain titanium alloy and a preparation method thereof, wherein the titanium alloy comprises the following elements in percentage by mass: 3-5% of Al, 0.05-0.15% of B, 0.3-0.6% of C and the balance of Ti and other impurity elements.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a 3D printing fine-grained titanium alloy, the elemental composition of which comprises, in mass percent: 3% of Al, 0.1% of B, 0.6% of C, and the balance of Ti and other impurity elements.
The other impurity elements include, in mass fraction: 0.03 percent of N, 0.01 percent of H and 0.1 percent of O.
The average grain size of the titanium alloy was 185 μm.
Example 2:
the embodiment provides a 3D printing fine-grained titanium alloy, the elemental composition of which comprises, in mass percent: 5% of Al, 0.15% of B, 0.5% of C, and the balance of Ti and other impurity elements.
The other impurity elements include, in mass fraction: 0.02% of N, 0.005% of H and 0.15% of O.
The average grain size of the titanium alloy was 131 μm.
Example 3:
the embodiment provides a 3D printing fine-grained titanium alloy, the elemental composition of which comprises, in mass percent: 4% of Al, 0.05% of B, 0.3% of C, and the balance of Ti and other impurity elements.
The other impurity elements include, in mass fraction: 0.01% of N, 0.007% of H and 0.08% of O.
The average grain size of the titanium alloy was 245 μm.
Example 4:
this embodiment provides a method for preparing a 3D-printed fine-grained titanium alloy, where the 3D-printed fine-grained titanium alloy is the titanium alloy in embodiment 1, and the method includes the following steps:
(1) the method comprises the following steps of proportioning 0-grade sponge titanium, an aluminum simple substance, an aluminum-titanium-boron intermediate alloy, a boron simple substance and carbon powder according to the mass fractions of the elements in the embodiment 1, wherein the purity of the aluminum simple substance is 99.99%, the purity of the carbon powder is 99.9%, and the aluminum-titanium-boron intermediate alloy comprises the following elements in percentage by mass: 3.0 percent of Ti, 1.0 percent of B and the balance of Al, wherein the boron element added in the form of the Al-Ti-B intermediate alloy accounts for 41 percent of the boron element in the titanium alloy, and then the vacuum melting is carried out, the number of times of the vacuum melting is 3, and the vacuum degree during the vacuum melting is 10-2Pa, the temperature of vacuum melting is 1685 ℃, and the time is 7min, so as to obtain a sample substrate;
(2) removing surface oxide skin of the sample substrate obtained in the step (1), and preparing alloy powder by adopting an air atomization method, wherein the air atomization method comprises the following steps: melting a sample substrate, spraying gas into a mist shape, condensing to form alloy powder, and screening to obtain the alloy powder for 3D printing with the average particle size of 41.6 microns;
(3) preparing an alloy sample from the 3D printing alloy powder obtained in the step (2) by adopting a selective laser melting method, then carrying out annealing heat treatment, wherein the annealing temperature is 600 ℃, the heat preservation time is 1h, and cooling the alloy sample along with a furnace after the annealing treatment to obtain the 3D printing fine-grained titanium alloy.
In the embodiment, the mechanical property of the 3D printed fine-grained titanium alloy is detected by sampling, the yield strength Rp0.2 reaches 801MPa, the tensile strength Rm reaches 851MPa and the elongation reaches 11.2% during transverse sampling; rp0.2 reaches 811MPa, Rm reaches 868MPa, the elongation reaches 10.6 percent and the comprehensive mechanical property is excellent during longitudinal sampling.
Example 5:
this embodiment provides a method for preparing a 3D-printed fine-grained titanium alloy, where the 3D-printed fine-grained titanium alloy is the titanium alloy in embodiment 2, and the method includes the following steps:
(1) proportioning 0-grade sponge titanium, an aluminum simple substance, an aluminum-titanium-boron intermediate alloy, a boron simple substance and carbon powder according to the mass fraction of the elements in the embodiment 2, wherein the purity of the aluminum simple substance is 99.995%, the purity of the carbon powder is 99.95%, and the aluminum-titanium-boron intermediate alloy comprises the following elements in percentage by mass: 3.5 percent of Ti, 1.1 percent of B and the balance of Al, wherein the boron element added in the form of the Al-Ti-B intermediate alloy accounts for 36 percent of the boron element in the titanium alloy, and then the vacuum melting is carried out, the number of times of the vacuum melting is 2, and the vacuum degree during the vacuum melting is 6 multiplied by 10-3Pa, the temperature of vacuum melting is 1680 ℃, and the time is 10min, so as to obtain a sample substrate;
(2) removing surface oxide skin of the sample substrate obtained in the step (1), and preparing alloy powder by adopting an air atomization method, wherein the air atomization method comprises the following steps: melting a sample substrate, spraying gas into a mist shape, condensing to form alloy powder, and screening to obtain alloy powder with the average grain diameter of 42.8 mu m for 3D printing;
(3) preparing an alloy sample from the 3D printing alloy powder obtained in the step (2) by adopting a selective laser melting method, carrying out annealing heat treatment at 700 ℃ for 1.5h, and cooling the alloy sample with a furnace after the annealing treatment to obtain the 3D printing fine-grained titanium alloy.
In the embodiment, the mechanical property of the 3D printed fine-grained titanium alloy is detected by sampling, Rp0.2 reaches 837MPa, Rm reaches 893MPa, and the elongation reaches 9.3% during transverse sampling; rp0.2 reaches 842MPa, Rm reaches 897MPa, the elongation reaches 9 percent and the comprehensive mechanical property is excellent during longitudinal sampling.
Example 6:
this embodiment provides a method for preparing a 3D-printed fine-grained titanium alloy, where the 3D-printed fine-grained titanium alloy is the titanium alloy in embodiment 3, and the method includes the following steps:
(1) titanium sponge of 0 grade, simple substance of aluminum and aluminum-titaniumThe boron intermediate alloy, the elemental boron and the carbon powder are proportioned according to the mass fractions of the elements in the embodiment 3, the purity of the elemental aluminum is 99.993%, the purity of the carbon powder is 99.98%, and the aluminum-titanium-boron intermediate alloy comprises the following elements in mass fraction: 2.5 percent of Ti, 0.9 percent of B and the balance of Al, wherein the boron element added in the form of the Al-Ti-B intermediate alloy accounts for 45 percent of the boron element in the titanium alloy, and then the vacuum melting is carried out, the number of times of the vacuum melting is 4, and the vacuum degree during the vacuum melting is 3 multiplied by 10-3Pa, vacuum melting at 1720 ℃ for 5min to obtain a sample base material;
(2) removing surface oxide skin of the sample substrate obtained in the step (1), and preparing alloy powder by adopting an air atomization method, wherein the air atomization method comprises the following steps: firstly, melting a sample substrate, spraying gas into a mist shape, condensing to form alloy powder, and screening to obtain the alloy powder for 3D printing with the average particle size of 50.6 microns;
(3) preparing an alloy sample from the 3D printing alloy powder obtained in the step (2) by adopting a selective laser melting method, carrying out annealing heat treatment at the annealing temperature of 650 ℃ for 2 hours, and cooling the annealed alloy sample along with a furnace to obtain the 3D printing fine-grained titanium alloy.
In the embodiment, the mechanical property of the 3D printed fine-grained titanium alloy is detected by sampling, Rp0.2 reaches 755MPa, Rm reaches 792MPa, the elongation reaches 12%, and the mechanical property is excellent.
Comparative example 1:
this comparative example provides a 3D printed fine grained titanium alloy and method of making the same, the elemental composition of which is as in example 2, except that: the mass fraction of the element B was 0.17%, and the portion different from that in example 2 was distributed to the element titanium.
The preparation method is as described in example 5, except for the mass ratio in step (1), the other steps are the same.
Comparative example 2:
this comparative example provides a 3D printed fine grained titanium alloy and method of making the same, the elemental composition of which is as for example 3 except that: the mass fraction of the element B was 0.04%, and the portion different from that in example 3 was distributed to the element titanium.
The preparation method is as described in example 6, except for the mass ratio in step (1), the other steps are the same.
In comparative example 1, because the content of the element B in the alloy is too high, the element B in the alloy is segregated, so that the elongation of the alloy is reduced to only 5%; in comparative example 2, the grain size of the alloy was large due to the low content of element B in the alloy, and the as-cast grain size was 400 μm or more.
Comparative example 3:
this comparative example provides a 3D printed fine grained titanium alloy and method of making the same, the elemental composition of which is as in example 1, except that: the mass fraction of the element C was 0.65%, and the portion different from that in example 1 was distributed to the element titanium.
The preparation method is as described in example 4, except for the mass ratio in step (1), the other steps are the same.
Comparative example 4:
this comparative example provides a 3D printed fine grained titanium alloy and method of making the same, the elemental composition of which is as for example 3 except that: the mass fraction of the element C was 0.27%, and the portion different from that in example 3 was distributed to the element titanium.
The preparation method is as described in example 6, except for the mass ratio in step (1), the other steps are the same.
In comparative example 3, part of C is difficult to dissolve due to the excessively high content of the element C in the alloy, the plasticity of the alloy is reduced, and the elongation is only 0.5%; in comparative example 4, the C content in the alloy was too low, so that the alloy strengthening effect was reduced, and Rm was about 750 MPa.
The embodiment is integrated, so that the fine-grained titanium alloy can effectively refine the crystal grains of the alloy through doping of boron and carbon elements, improve the alloy strength without reducing the plasticity performance, and replace the Ti6Al4V material which is widely applied at present; the fine-grained titanium alloy does not contain expensive and harmful vanadium elements, can effectively reduce the cost of the alloy, and is green and environment-friendly; the fine-grained titanium alloy is prepared by adopting a 3D printing method, so that the fine-grained titanium alloy is more suitable for preparing parts which are complex in shape and difficult to process, the preparation difficulty is reduced, and the time and the labor cost are saved.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It will be apparent to those skilled in the art that any modification, equivalent substitution of the process of the invention and addition of ancillary operations, selection of specific means, etc., of the present invention are within the scope and disclosure of the invention.
Claims (10)
1. A3D printing fine-grained titanium alloy is characterized in that the elemental composition of the titanium alloy comprises, in mass percent: 3-5% of Al, 0.05-0.15% of B, 0.3-0.6% of C and the balance of Ti and other impurity elements.
2. The fine crystalline titanium alloy of claim 1 wherein the other impurity elements include N, H and O;
preferably, the other impurity elements include, in mass fraction: n is less than or equal to 0.03 percent, H is less than or equal to 0.01 percent, and O is less than or equal to 0.15 percent.
3. A fine-grained titanium alloy according to claim 1 or 2, characterized in that the as-cast grain size of the titanium alloy is 100 to 300 μm.
4. A method of producing the fine crystalline titanium alloy defined in any one of claims 1 to 3 including the steps of:
(1) titanium sponge, an aluminum simple substance, an aluminum-titanium-boron intermediate alloy, a boron simple substance and carbon powder are proportioned according to the mass fraction of the elements and then subjected to vacuum melting to obtain a sample base material;
(2) preparing alloy powder from the sample base material obtained in the step (1) by adopting an air atomization method, and screening to obtain alloy powder for 3D printing;
(3) preparing an alloy sample from the 3D printing alloy powder obtained in the step (2) by adopting a selective laser melting method, and performing heat treatment to obtain the 3D printing fine-grain titanium alloy.
5. The method according to claim 4, wherein the titanium sponge of step (1) comprises grade 0 titanium sponge;
preferably, the purity of the elementary aluminum in the step (1) is more than 99.99%;
preferably, the purity of the carbon powder in the step (1) is more than 99.9%.
6. The preparation method according to claim 4 or 5, wherein the elemental composition in the aluminum-titanium-boron master alloy of step (1) comprises, in mass fraction: 2.5-3.5% of Ti, 0.9-1.1% of B and the balance of Al;
preferably, the proportion of the boron element added in the form of the aluminum-titanium-boron intermediate alloy in the boron element in the titanium alloy is 35-45%.
7. The production method according to any one of claims 4 to 6, wherein the vacuum melting of step (1) is performed in a vacuum consumable melting furnace;
preferably, the number of times of vacuum melting in the step (1) is at least 2, preferably 2-3;
preferably, the vacuum degree of the vacuum melting in the step (1) is lower than 10-2Pa；
Preferably, the temperature of the vacuum melting in the step (1) is 1680-1720 ℃, and the time is 5-10 min.
8. The method according to any one of claims 4 to 7, wherein the sample substrate is subjected to surface descaling before the gas atomization in step (2);
preferably, the gas atomization method in step (2) is: melting a sample base material, spraying gas into a mist shape, and condensing to form alloy powder;
preferably, the sample substrate is meltedAnd the degree of vacuum during atomization is independently not higher than 10-2Pa；
Preferably, the particle size range of the 3D printing alloy powder obtained after screening in the step (2) is 15-53 μm.
9. The preparation method according to any one of claims 4 to 8, wherein the selective laser melting method in the step (3) is a 3D printing forming method, alloy powder is melted by laser, and after sintering and solidification, powder spreading is repeated, and alloy samples are formed by stacking layer by layer;
preferably, the heat treatment mode in the step (3) is annealing heat treatment;
preferably, the annealing temperature is 600-700 ℃, and the heat preservation time is 1-2 h;
preferably, the alloy sample after the annealing treatment is cooled along with the furnace.
10. Heat treatment process according to any one of claims 4 to 9, characterized in that it comprises the following steps:
(1) the method comprises the following steps of proportioning 0-grade sponge titanium, an aluminum simple substance, an aluminum-titanium-boron intermediate alloy, a boron simple substance and carbon powder according to the mass fraction of elements, wherein the aluminum-titanium-boron intermediate alloy comprises the following elements in percentage by mass: 2.5-3.5% of Ti, 0.9-1.1% of B and the balance of Al, wherein the proportion of boron element added in the form of Al-Ti-B intermediate alloy in the titanium alloy is 35-45%, and then the vacuum melting is carried out, the number of times of the vacuum melting is at least 2, and the vacuum degree during the vacuum melting is lower than 10-2Pa, vacuum melting at 1680-1720 ℃ for 5-10 min to obtain a sample base material;
(2) removing surface oxide skin of the sample substrate obtained in the step (1), and preparing alloy powder by adopting an air atomization method, wherein the air atomization method comprises the following steps: melting a sample substrate, spraying gas into a mist shape, condensing to form alloy powder, and screening to obtain alloy powder for 3D printing with the particle size range of 15-53 mu m;
(3) preparing an alloy sample from the 3D printing alloy powder obtained in the step (2) by adopting a selective laser melting method, then carrying out annealing heat treatment, wherein the annealing temperature is 600-700 ℃, the heat preservation time is 1-2 h, and cooling the alloy sample with a furnace after the annealing treatment to obtain the 3D printing fine-grained titanium alloy.
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