CN114682778A - Method for preparing titanium-based product based on fine spherical titanium-based powder and titanium-based product - Google Patents
Method for preparing titanium-based product based on fine spherical titanium-based powder and titanium-based product Download PDFInfo
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Abstract
The invention provides a method for preparing a titanium substrate product based on fine spherical titanium substrate powder and the titanium substrate product, wherein the method comprises the following steps: mixing the composite powder and a binder according to a certain proportion, and crushing into granular feed; sequentially carrying out injection molding, degreasing and sintering treatment on the granular feed to prepare a titanium-based part; therein, compoundingThe powder is prepared by uniformly mixing micro spherical titanium-based powder and oxygen adsorbent powder; the oxygen adsorbent powder is CaC2、CaB6、LaB6、CeSi2At least one of; the adhesive comprises the following components in percentage by mass: 75-85% of polyformaldehyde, 3-8% of high-density polyethylene, 3-8% of ethylene-vinyl acetate copolymer, 5-10% of stearic acid and 0.5-3% of thermoplastic acrylic resin. The invention provides a high-efficiency recycling method of fine spherical titanium-based powder, and realizes near-net-shape manufacturing of a titanium product with high added value.
Description
Technical Field
The invention relates to the technical field of powder metallurgy, in particular to a method for preparing a titanium base part based on micro spherical titanium base powder and the titanium base part.
Background
The titanium alloy has excellent comprehensive mechanical properties such as high specific strength, good corrosion resistance, small thermal expansion coefficient, good biocompatibility, no brittleness at low temperature and the like, and has extremely high application value in the fields of aerospace, military industry and national defense, ocean engineering, biomedicine and the like. Additive manufacturing has unique advantages in the aspects of design freedom, complex part forming, material utilization rate and the like, and becomes a titanium alloy manufacturing technology with great prospect. The high-quality spherical powder is the basis of the titanium alloy additive manufacturing technology and is also the key for determining the cost and the performance of the finished product. In the past years, high-quality spherical titanium powder in China always depends on foreign import, the price is up to more than 3000 yuan/Kg, and technical blockade is always implemented in foreign countries. In recent years, with the continuous enhancement of the independent research and development capability of China, the self-sufficiency of high-quality spherical titanium powder is basically realized. With the vigorous development of the domestic spherical titanium powder industry, the industrial chain becomes more mature, but the problem brought by the industrial chain is the recycling of the micro titanium powder which is a byproduct produced in the spherical titanium powder production.
The additive manufacturing technology has strict requirements on the granularity of titanium powder, wherein the granularity of the titanium powder for Selective Laser Melting (SLM) is 30-45 mu m, the granularity of the titanium powder for selective Electron Beam Melting (EBM) is 40-110 mu m, and the granularity of the titanium powder for plasma beam additive manufacturing (PDM) is 50-100 mu m. However, at present, titanium powder preparation technologies such as GAs Atomization (GA) and rotary electrode atomization (PREP) inevitably generate a considerable amount of fine powder (<20 μm), and the content of the fine powder accounts for 10% to 15% of the total amount of the powder. At present, the powder is generally sold at low cost and used for civil products such as fireworks and firecrackers, chemical additives and the like or is melted into ingots again in a melting furnace, so that the great waste of titanium resources is caused, and the green and healthy development of the powder titanium industry is influenced. At present, the annual capacity of spherical titanium powder in China reaches 2000 tons, so that a large amount of residual powder is generated and is difficult to effectively utilize.
Therefore, the development of the high-efficiency recycling technology of the micro spherical titanium-based powder byproduct can bring great economic benefits and promote the sustainable development of the powder titanium industry.
Disclosure of Invention
In order to overcome the drawbacks of the prior art, the main object of the present invention is to provide a method for preparing titanium substrates based on finely divided spherical titanium-based powder, based on powder injection molding technology, by introducing, on the one hand, an oxygen adsorbent (CaC)2、CaB6And the like) to convert the interstitial oxygen element in the raw material powder into ceramic reinforced phase particles, and realize the strengthening and hardening of the matrix while purifying the matrix; on the other hand, in order to prevent the agglomeration of high surface energy fine powder in the mixing process, acrylic resin is introduced to reduce the surface energy of the powder, injection molding feed with uniform components is prepared, the quality of an injection green body is ensured, and an optimized densification sintering technology is combined to establish a high-efficiency recycling technology of the fine spherical titanium-based powder, so that the near-net-shape manufacturing of the high value-added titanium product is realized.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a method for producing a titanium substrate article based on a fine spherical titanium-based powder.
The method for preparing the titanium-based product based on the superfine spherical titanium-based powder comprises the following steps:
mixing the composite powder and a binder according to a certain proportion, and crushing into granular feed;
sequentially carrying out injection molding, degreasing and sintering treatment on the granular feed to prepare a titanium-based part;
wherein the composite powder is prepared by uniformly mixing micro spherical titanium-based powder and oxygen adsorbent powder; the oxygen adsorbent powder is CaC2、CaB6、LaB6、CeSi2At least one of;
the adhesive comprises the following components in percentage by mass: 75-85% of polyformaldehyde, 3-8% of high-density polyethylene, 3-8% of ethylene-vinyl acetate copolymer, 5-10% of stearic acid and 0.5-3% of thermoplastic acrylic resin.
Further, when the powder is mixed, the mass percentage of the oxygen adsorbent powder to the total mass of the oxygen adsorbent powder and the fine spherical titanium-based powder is 0.4-1.5 wt.%;
preferably, a roller mill is used for powder mixing, the rotating speed is 80-120 r/min, and the time is 6-12 h.
Further, the particle size of the fine spherical titanium-based powder is 0-20 μm, and the oxygen content is 0.08-0.15 wt.%;
preferably, the superfine spherical titanium-based powder is dried under the constant temperature of 70-100 ℃ for 6-12 hours.
Further, the fine spherical titanium-based powder comprises Ti-6Al-4V alloy powder and pure titanium powder.
Further, the oxygen adsorbent powder is obtained by wet high-energy vibration ball milling treatment and drying and grinding treatment;
preferably, the purity of the oxygen adsorbent powder is more than or equal to 99.8 percent, and the particle size is less than or equal to 10 mu m.
Further, the wet high-energy vibration ball milling treatment process parameters are as follows: the ball-material ratio of the grinding balls to the oxygen adsorbent particles is 2-8: 1, the ball milling speed is 800-1200 r/min, the ball milling time is 6-12 h, the ball mill runs for 2-4 min, and the machine is stopped for 2-6 min;
and (3) drying under protective gas after ball milling at the drying temperature of 40-80 ℃ for 1-4 h, and grinding and screening to obtain the oxygen adsorbent powder.
Further, the composite powder accounts for 60-68 vol% of the feed material;
preferably, the mixing temperature is 170-200 ℃, the rotating speed is 10-30 r/min, and the time is 1-2 h.
Further, the injection molding is specifically as follows: heating the feed to 170-200 ℃, wherein the injection pressure is 60-110 MPa, the pressure maintaining pressure is 60-100 MPa, the pressure maintaining time is 5-25 s, the mold temperature is 70-120 ℃, and the injection speed is 50-80% of the maximum injection speed of the injection machine.
Further, the degreasing treatment is nitric acid catalytic degreasing, the degreasing temperature is 80-130 ℃, the acid feeding rate is 0.8-1.5 g/min, and the degreasing time is 6-12 hours.
Further, the sintering treatment is carried out under the protection of inert gas or under the vacuum condition, wherein the vacuum degree is 10-2～10-4Pa; heating to 450-600 ℃ from room temperature at a speed of 1-5 ℃/min, preserving heat for 0.5-2 h, and sintering at the first stage; heating to 800-1000 ℃ at a speed of 5-10 ℃/min, preserving heat for 0.5-2 h, and performing second-stage sintering; and then heating to 1200-1350 ℃ at the speed of 1-3 ℃/min, and keeping the temperature for 1-4 h, and carrying out third-stage sintering.
In order to achieve the above object, according to a second aspect of the present invention, a titanium substrate is provided.
The titanium base part prepared by the method has the structure that the base phase and the reinforcing phase are dispersed and distributed on the base phase; wherein the content of the first and second substances,
the matrix phase is a fine uniform equiaxial grain structure, and the grain size is 20-60 mu m;
the reinforced phase is at least one of Ca-Ti-O particles and TiC and TiB particles, or the reinforced phase is TiB and La2O3Particles, or the reinforcing phase being CeO2Particles; the grain diameter of the Ca-Ti-O particles is 50-300 nm, the grain diameters of the TiC and TiB particles are both 3-8 mu m, and the La is2O3、CeO2The particle size of the particles is 1-3 μm.
The invention adopts the powder injection molding technology to realize the high-efficiency recycling of the micro spherical titanium-based powder. The powder injection molding technology combines plastic injection molding and powder metallurgy technology, can realize the utilization rate of raw materials by nearly 100 percent, can also prepare a titanium product with a complex shape, uniform tissue, fine crystal grains, excellent mechanical property and high size precision, fills the application blank of a powder byproduct, namely fine spherical titanium-based powder, for additive manufacturing, brings great economic benefit and promotes the healthy development of the powder metallurgy titanium industry.
In general, the smaller the particle size of the powder, the larger the specific surface area, the higher the surface energy, and the more the agglomeration tendency becomes severe. The specific surface area of 0-20 μm fine titanium-based powder for additive manufacturing is 0.457m relative to the titanium alloy coarse particle powder with a median diameter of 150 μm2Per g, over coarse-grained powder (0.0414 m)2More than 10 times per gram) leads to a considerable increase in powder adhesion. In the mixing process, under the action of external force such as friction between powders and between the powders and the inner wall of the mixer, the fine powders absorb a large amount of mechanical energy or heat energy, so that the surface energy of the fine powders is further increased and the fine powders are in an unstable state. In order to reduce the surface energy, the powder particles tend to reach a stable state by aggregating or closing each other, thereby causing powder agglomeration, resulting in non-uniform injection feed components and deteriorating the mechanical properties of the final titanium product. Therefore, the thermoplastic acrylic resin with hydrophilic oleophobic carboxyl groups and oleophilic hydrophobic alkyl groups is introduced into a traditional binder system, the metal surface can interact with the hydrophilic groups to form hydrogen bonds or van der Waals force, the surface energy of powder is effectively reduced, and agglomeration among powder particles is avoided; in addition, the acrylic resin has hydrophobic groups, and can form a good blending system with other thermoplastic binder components according to the principle of similarity and intermiscibility, so that uniform feeding is prepared, and a guarantee is provided for the preparation of high-performance titanium workpieces.
The addition amount of the acrylic resin is 0.5-3.0 wt.%, and if the content is too low, the reduction of the surface energy of powder particles is limited, so that the problem of powder agglomeration in the mixing process is difficult to effectively solve; if the content is too high, the feeding fluidity is deteriorated, and the injection molding process cannot be smoothly completed, resulting in difficulty in material molding.
Interstitial oxygen content is an important indicator of powdered titanium parts. With increasing oxygen content, the strength of titanium alloys increases, but the plasticity decreases significantly and severe brittle fracture occurs once a critical value is exceeded. In order to synergistically improve the strength and plasticity of an injection-molded titanium product, CaC is utilized in the invention2、CaB6、LaB6、CeSi2The multilevel multi-scale particle reinforced powder titanium product is prepared by using the iso-oxygen adsorbent, not onlyThe oxygen content in the matrix is reduced, the matrix is purified, and Ca-Ti-O, TiC, TiB and La are generated in situ2O3、CeO2And the ceramic reinforcing phase particles are equal, so that the titanium product has good strength and plasticity.
Oxygen adsorbent powder CaC of the invention2/CaB6/LaB6/CeSi2The addition amount of (2) is 0.4-1.5 wt.%, and if the addition amount is too much, the generated strengthening phase is easy to agglomerate to influence sintering and deteriorate the mechanical property of the material; if the amount of the additive is too small, the effects of purifying the substrate and improving the mechanical properties cannot be achieved. Experiments prove that the process can obtain the titanium product with uniform reinforcing phase distribution, fine grains, uniform structure and excellent performance.
The invention has the beneficial effects that:
(1) the powder injection molding technology is adopted, so that the high-efficiency recycling of the superfine spherical titanium-based powder serving as a by-product of the powder for titanium additive manufacturing is realized, and compared with the existing recycling technology, the method has the advantages of high material utilization rate and high added value, and shows great economic potential.
(2) The high-dispersion and high-efficiency degreasing polyformaldehyde-based binder adaptive to the superfine spherical titanium-based powder is independently researched and developed, the problem that the superfine titanium powder is easy to agglomerate in the injection molding process can be effectively solved by introducing the thermoplastic acrylic resin, the compatibility of the powder and the binder is improved, and the injection feed with uniform components is prepared.
(3) High purity fine CaC2/CaB6/LaB6/CeSi2The oxygen adsorbent powder and the titanium powder surface oxide film are subjected to adsorption and oxygen fixation reaction, and TiC, TiB and La which are distributed in a multi-scale dispersion mode are generated in situ while a matrix is purified2O3、CeO2And Ca-Ti-O reinforced phase particles, which synergistically improve the strength and plasticity of the titanium product.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a scanning electron microscope image of Ti-6Al-4V alloy raw material powder in example 1 of the present invention;
FIG. 2 is a schematic representation of the organization of the article of example 1 of the present invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The invention provides a high-quality near-net-shape recycling technology of fine spherical titanium-based powder, namely a titanium-based product prepared on the basis of the fine spherical titanium-based powder.
The method for preparing the titanium-based product based on the fine spherical titanium-based powder specifically comprises the following steps:
(1) obtaining pure dry fine spherical titanium-based powder:
and drying the fine spherical titanium-based powder by using a vacuum constant-temperature drying oven at the drying temperature of 70-100 ℃ for 6-12 h.
The particle size of the fine spherical titanium-based powder is 0-20 mu m, and the oxygen content is 0.08-0.15 wt.%.
Wherein, the superfine spherical titanium-based powder comprises alloy powder and pure titanium powder, the alloy powder can be Ti-6Al-4V powder, and the shape image of the Ti-6Al-4V alloy powder is shown in figure 1 by a scanning electron microscope.
(2) Obtaining high-purity fine oxygen adsorbent powder:
weighing zirconia grinding balls and oxygen adsorbent particles in an argon atmosphere protective glove box according to a ball-to-material ratio of 2-8: 1, and filling the zirconia grinding balls and the oxygen adsorbent particles into a ball grinding tank, wherein the oxygen adsorbent particles are CaC2、CaB6、LaB6、CeSi2Adding n-hexane protective liquid into the ball milling tank to immerse the powder and the milling balls, then filling argon protective gas into the ball milling tank and sealing,and finally, filling the sealed ball mill tank into a ball mill for ball milling treatment, wherein the rotating speed of the ball milling treatment is 800-1200 r/min, the ball mill is stopped for 2-6 min after running for 2-4 min, and the oxygen adsorbent slurry is obtained after ball milling for 6-10 h.
And (3) putting the ball milling tank into an argon protective glove box or a vacuum environment, opening, taking out the oxygen adsorbent slurry, drying for 1-4 h at 40-80 ℃, and finally grinding and screening to obtain oxygen adsorbent powder with the purity of more than or equal to 99.8% and the particle size of less than or equal to 10 microns.
(3) Obtaining a composite powder:
and (2) placing the fine spherical titanium-based powder and the oxygen adsorbent powder into a roller mill tank in an argon atmosphere protective glove box, wherein the mass percentage of the oxygen adsorbent powder to the total mass of the oxygen adsorbent powder and the fine spherical titanium-based powder is 0.4-1.5%, then sealing, taking out, placing the mixture into a roller mill, mixing, operating the roller mill at the rotating speed of 80-120 r/min for 6-12 h, taking down the roller mill tank, placing the roller mill tank into the glove box, taking out the mixed powder in the tank, sealing and storing to obtain the composite powder.
(4) Obtaining a feed:
the composite powder is used as a raw material, the loading capacity is 60-68 vol.%, and then 75-85% of polyformaldehyde, 3-8% of high-density polyethylene, 3-8% of ethylene-vinyl acetate copolymer, 5-10% of stearic acid and 0.5-3% of acrylic resin are respectively weighed to form a binder system.
And mixing the composite powder and the binder at the temperature of 170-200 ℃ at the rotating speed of 10-30 r/min for 1-2 h.
And taking out the feed after the mixing is finished and cooling to room temperature, and cutting the feed into granular feed by using a crusher.
(5) Injection molding:
heating the granular feed to 170-200 ℃ and carrying out injection molding on the granular feed on an injection machine, wherein the injection pressure is 50-100 MPa, the pressure maintaining pressure is 40-100 MPa, the pressure maintaining time is 5-25 s, the mold temperature is 50-100 ℃, and the injection speed is 50-80% of the maximum injection speed of the injection machine, so that an injection green body is obtained.
(6) Degreasing treatment:
and (3) putting the injection molded blank into a nitric acid degreasing furnace for nitric acid catalytic degreasing, wherein the degreasing temperature is 80-130 ℃, the acid feeding rate is 0.8-1.5 g/min, and the degreasing time is 6-12 h.
(7) Sintering treatment:
after the catalytic degreasing is finished, the obtained degreased green body is placed under the protection of a high-purity argon atmosphere or is sintered under a vacuum condition, wherein the vacuum degree is 10-2～10-4Pa, heating to 450-600 ℃ from room temperature at a speed of 2-5 ℃/min, preserving heat for 0.5-2 h, and carrying out first-stage sintering treatment; heating to 800-1100 ℃ at the speed of 2-10 ℃/min, preserving heat for 0.5-2 h, and performing second-stage sintering treatment; and then heating to 1200-1350 ℃ at the speed of 1-3 ℃/min, keeping the temperature for 1-4 h, carrying out third-stage sintering treatment, and cooling along with the furnace to obtain the high-performance titanium-based workpiece.
The method for preparing titanium base articles based on finely divided spherical titanium base powder will be described in detail below by way of specific examples.
Example 1:
taking fine spherical Ti-6Al-4V alloy powder with the median particle size of 14.5 mu m and the oxygen content of 0.14 wt.% as a raw material, and putting the raw material into a vacuum constant-temperature drying oven at 80 ℃ for drying treatment for 8h to obtain pure dry fine spherical Ti-6Al-4V alloy powder.
Weighing zirconia grinding balls and CaC in an argon atmosphere protective glove box according to a ball-to-material ratio of 5:12Putting the powder into a ball milling tank, and adding n-hexane protective liquid into the ball milling tank to immerse the CaC2And (2) filling argon gas into the ball milling tank, sealing, filling the sealed ball milling tank into a ball mill for ball milling treatment, wherein the rotation speed of the ball milling treatment is 1000r/min, stopping the ball mill for 2min after the ball mill runs for 2min, and performing ball milling for 8h to obtain the oxygen adsorbent slurry. Placing the ball milling tank into an argon protective glove box or a vacuum environment, opening, taking out the oxygen adsorbent slurry, drying at 60 ℃ for 2h, and then grinding and screening to obtain CaC with the median particle size of about 2 micrometers2And (3) powder.
0.4 wt.% CaC was weighed2Putting the powder and fine spherical Ti-6Al-4V alloy powder into a roller mill tank in an argon atmosphere protective glove box, sealing, taking out and putting into the roller mill tankAnd (4) carrying out mixing treatment on the roller mill, wherein the rotating speed of the roller mill is 100r/min, taking down the roller mill tank after running for 8 hours, placing the roller mill tank in a glove box, and taking out the mixed powder in the tank, sealing and storing.
The composite powder is used as a raw material, 65% of solid powder loading capacity is selected, and then 85% of polyformaldehyde, 3% of high-density polyethylene, 4% of ethylene-vinyl acetate copolymer, 7% of stearic acid and 1% of acrylic resin in percentage by mass are respectively weighed as binders.
And (3) uniformly mixing the mixed powder and acrylic resin in an argon protective atmosphere internal mixer for 20min, and then adding other components of the binder, wherein the mixing temperature is 185 ℃, the rotating speed is 30r/min, and the mixing time is 2 h. Taking out the feed after mixing is finished, and obtaining granular feed by a crusher.
And (3) heating the feed material in an injection machine to 180 ℃, and then injecting, wherein the injection pressure is 90MPa, the pressure maintaining pressure is 80MPa, the pressure maintaining time is 15s, the mold temperature is 80 ℃, and the injection speed is 50% of the maximum injection speed of the injection machine, so that an injection green body is obtained.
And (3) putting the blank into a degreasing furnace for nitric acid catalytic degreasing, wherein the degreasing temperature is 120 ℃, the acid feeding rate is 0.8g/min, and the degreasing time is 10 h.
Putting the degreased blank into a vacuum furnace for sintering, wherein the vacuum degree is 10-3Pa; heating from room temperature to 450 deg.C at a rate of 2 deg.C/min, maintaining for 2h, and sintering at the first stage; heating to 950 ℃ at the speed of 8 ℃/min, preserving heat for 2 hours, and carrying out second-stage sintering; and then heating to 1300 ℃ at the speed of 2 ℃/min, keeping the temperature for 3 hours, carrying out third-stage sintering, and then cooling along with the furnace to obtain the titanium-based part.
Examples 2 to 10 adopt the same preparation method as in example 1, except that the process parameters used in the process of preparing the composite powder, the designed binder components, and the parameters of the powder injection molding process, etc., and the preparation method of the composite powder, the binder components, and the process parameters of the powder injection molding in examples 1 to 10 are summarized as shown in tables 1 to 4.
TABLE 1 Process parameters for preparing the fine spherical titanium-based powder of examples 1-10
TABLE 2 oxygen adsorbent powder and process parameters for its preparation in examples 1-10
TABLE 3 preparation Process parameters of composite powder and Binder in examples 1-10
TABLE 4 summary of powder injection Molding Process parameters in examples 1-10
The titanium substrates prepared in examples 1 to 10 and those prepared in comparative examples 1 to 9 were subjected to performance comparison experiments.
First, experimental object
Titanium base parts prepared in examples 1 to 10 and titanium base parts prepared in comparative examples 1 to 9, wherein:
comparative example 1:
titanium substrates were prepared using the same preparation process as in example 1, except that the feedstock consisted of the following components: the powder raw material was a fine spherical Ti-6Al-4V alloy powder having a single median particle size of 16 μm and an oxygen content of 0.14 wt.%.
Comparative example 2:
titanium substrates were prepared using the same preparation process as in example 1, except that the feedstock consisted of the following components: the powder raw materials are fine spherical Ti-6Al-4V alloy powder with the median particle size of 13 mu m and the oxygen content of 0.15 wt.% and 0.1 wt.% of CaC2A mixture of powders.
Comparative example 3:
the same preparation process as in example 1 was used to prepare titanium substrates, except that the feed consisted of the following components: the powder raw materials are Ti-6Al-4V alloy powder with the median particle size of 14 mu m and the oxygen content of 0.15 wt.% and 2.0 wt.% CaC2A mixture of powders.
Comparative example 4:
the same preparation process as in example 3 was used to prepare titanium parts, except that the feed consisted of the following components: the powder feed was pure titanium powder with a single median particle size of 13 μm and an oxygen content of 0.13 wt.%.
Comparative example 5:
titanium parts were prepared using the same preparation process as in example 3, except that the feedstock consisted of the following components: the powder raw materials are fine spherical pure titanium powder with the median particle size of 13 mu m and the oxygen content of 0.15 wt.% and 0.1 wt.% CaB6A mixture of powders.
Comparative example 6:
titanium parts were prepared using the same preparation procedure as in example 3, except that the feedstock consisted of the following components: the powder raw materials are fine spherical pure titanium powder with the median particle size of 14 mu m and the oxygen content of 0.15 wt.% and 2.0 wt.% CaB6A mixture of powders.
Comparative example 7:
the titanium product was prepared by the same preparation process as in example 5, except that the binder system was composed of different components, the loading of the solid powder was selected to be 65%, and the binder system was composed of 85% polyoxymethylene, 3% high density polyethylene, 5% ethylene-vinyl acetate copolymer, and 7% stearic acid, respectively.
Comparative example 8:
the titanium product was prepared by the same preparation process as in example 5, except that the binder system was composed of different components, 67% of the solid powder was loaded, and 83% of polyoxymethylene, 3% of high density polyethylene, 7% of ethylene-vinyl acetate copolymer, 6.9% of stearic acid, and 0.1% of acrylic resin were weighed to constitute the binder system.
Comparative example 9:
the titanium product was prepared by the same preparation process as in example 5, except that the binder system was composed of different components, 67% of the solid powder was loaded, and 83% of polyoxymethylene, 3% of high density polyethylene, 4% of ethylene-vinyl acetate copolymer, 5% of stearic acid, and 5% of acrylic resin were weighed to form the binder system.
Second, Experimental methods
The titanium base parts prepared in the examples 1-10 and the comparative examples 1-9 are subjected to performance measurement by adopting a conventional detection method in the prior art.
And (3) performance detection:
(1) and (3) testing the relative density: the relative density measurements were performed on the parts prepared in examples 1 to 10 and comparative examples 1 to 9, respectively.
(2) And (3) testing mechanical properties: the parts prepared in examples 1 to 10 and comparative examples 1 to 9 were subjected to room temperature tensile strength and elongation measurement, respectively.
Third, experimental results
The experimental results of examples 1-10 and comparative examples 1-9 are summarized in Table 5.
TABLE 5 comparison of the Properties of injection-molded articles prepared in examples 1 to 10 and comparative examples 1 to 9
Through detection, the workpiece prepared in the embodiment 1-10 has fine crystal grains and uniform tissue, and is Ca-Ti-O and TiC or TiB; TiB and La2O3；CeO2Fine-grained equiaxial structures of the reinforced phase, wherein the grain size is 20-60 mu m; wherein, Ca-Ti-O is a nano-scale reinforcing phase, and the particle size is 50-300 nm; TiC and TiB are micron-sized reinforcing phases, and the particle sizes of the TiC and the TiB are both 3-8 mu m; la2O3And CeO2The nano-grade reinforcing phase has the particle size of 1-3 microns, the density of a workpiece is more than or equal to 96.5%, the room-temperature tensile strength is more than or equal to 500MPa, and the elongation is more than or equal to 5%.
Through data comparison, the parts prepared in the comparative example 1 and the comparative example 4 have a large amount of cracks and holes, have poor surface quality and do not meet the use requirements; in examples 1 to 4 of the present invention, CaC was introduced2/CaB6The multilevel multi-scale particle reinforced titanium-based composite material is prepared from the equal oxygen absorption type calcium compound, so that the oxygen content in the matrix is reduced, the matrix lattice is purified, and TiC and TiB reinforced phase particles are generated in situ, so that the injection-molded titanium product has good strength and plasticity. In addition, the oxygen adsorbent can also perform adsorption and oxygen fixation reaction with an oxide film on the surface of the powder to generate a nano Ca-Ti-O particle strengthening phase, thereby playing a role in strengthening and plasticizing.
Comparative example 7 because the powder is seriously agglomerated in the mixing process, the injection feeding is not uniform, the two-phase separation defect is generated between the binder and the raw material powder during the injection, and finally, a large number of defects such as cracks, holes and the like are generated in the sintered body, so the size precision is low, and the mechanical property is poor. In embodiments 5 to 7 of the invention, the acrylic resin is added to the polyformaldehyde binder, so that the surface energy of the fine powder is effectively reduced, the problem of powder agglomeration in the mixing process is avoided, the injection molding feed with uniform components is prepared, and the preparation of the high-performance titanium alloy part is guaranteed.
In addition, the parts prepared in comparative examples 2-3, 5-6 and 8-9 have fine crystal grains and uniform structures, but Ca-Ti-O, TiC, TiB and La2O3The particle size of the equal strengthening phase is larger, so that the sintering densification of the green body is influenced, and the density, the room-temperature tensile strength and the elongation of a sintered body are relatively lower; it can also be seen that the composite powder of the invention has a combination of constituentsThe change of the content of any composition component directly influences the tissue structure of an injection molding part; in addition, the lack or change of any component in the binder of the present invention, and the change of the mixture ratio of the components, can not successfully prepare high performance injection molded parts.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A method for preparing a titanium substrate product based on micro spherical titanium substrate powder is characterized by comprising the following steps:
mixing the composite powder and a binder according to a certain proportion, and crushing into granular feed;
sequentially carrying out injection molding, degreasing and sintering treatment on the granular feed to prepare a titanium-based part;
wherein the composite powder is prepared by uniformly mixing micro spherical titanium-based powder and oxygen adsorbent powder; the oxygen adsorbent powder is CaC2、CaB6、LaB6、CeSi2At least one of;
the adhesive comprises the following components in percentage by mass: 75-85% of polyformaldehyde, 3-8% of high-density polyethylene, 3-8% of ethylene-vinyl acetate copolymer, 5-10% of stearic acid and 0.5-3% of thermoplastic acrylic resin.
2. The method for preparing a titanium substrate product based on fine spherical titanium-based powder according to claim 1, wherein the mass percentage of the oxygen adsorbent powder to the total mass of the oxygen adsorbent powder and the fine spherical titanium-based powder is 0.4 to 1.5 wt.% when mixing the powders;
preferably, a roller mill is used for powder mixing, the rotating speed is 80-120 r/min, and the time is 6-12 h.
3. The method for preparing titanium substrates based on spherical titanium based fine powder according to claim 1, wherein the spherical titanium based fine powder has a particle size of 0 to 20 μm and an oxygen content of 0.08 to 0.15 wt.%;
preferably, the superfine spherical titanium-based powder is dried under the constant temperature of 70-100 ℃ for 6-12 hours.
4. The method for preparing titanium base products based on the fine spherical titanium base powder as claimed in claim 1, wherein the oxygen adsorbent powder is obtained by wet high energy vibration ball milling and dry milling;
preferably, the purity of the oxygen adsorbent powder is more than or equal to 99.8 percent, and the particle size is less than or equal to 10 mu m.
5. The method for preparing titanium base products based on the fine spherical titanium base powder as claimed in claim 4, wherein the technological parameters of the wet high-energy vibration ball milling treatment are as follows: the ball-material ratio of the grinding balls to the oxygen adsorbent particles is 2-8: 1, the ball milling rotating speed is 800-1200 r/min, the ball milling time is 6-12 h, the ball mill runs for 2-4 min, and the machine is stopped for 2-6 min;
and (3) drying under protective gas after ball milling at the drying temperature of 40-80 ℃ for 1-4 h, and grinding and screening to obtain the oxygen adsorbent powder.
6. The method for preparing titanium substrate based on fine spherical titanium-based powder as claimed in claim 1, wherein the composite powder is present in the feed material in an amount of 60 to 68 vol.%;
preferably, the mixing temperature is 170-200 ℃, the rotating speed is 10-30 r/min, and the time is 1-2 h.
7. Process for the preparation of titanium substrates based on microfine spherical titanium-based powder according to claim 1, characterized in that said injection moulding consists in particular in: heating the feed to 170-200 ℃, wherein the injection pressure is 60-110 MPa, the pressure maintaining pressure is 60-100 MPa, the pressure maintaining time is 5-25 s, the mold temperature is 70-120 ℃, and the injection speed is 50-80% of the maximum injection speed of the injection machine.
8. The method for preparing titanium-based products based on the fine spherical titanium-based powder as claimed in claim 1, wherein the degreasing treatment is nitric acid catalyzed degreasing, the degreasing temperature is 80-130 ℃, the acid feeding rate is 0.8-1.5 g/min, and the degreasing time is 6-12 h.
9. The process for the preparation of titanium substrates based on finely divided spherical titanium-based powder according to claim 1, wherein the sintering process is carried out under inert gas protection or under vacuum with a vacuum of 10 degrees-2～10-4Pa; heating to 450-600 ℃ from room temperature at a speed of 1-5 ℃/min, preserving heat for 0.5-2 h, and sintering at a first stage; heating to 800-1000 ℃ at a speed of 5-10 ℃/min, preserving heat for 0.5-2 h, and performing second-stage sintering; and then heating to 1200-1350 ℃ at the speed of 1-3 ℃/min, and keeping the temperature for 1-4 h, and carrying out third-stage sintering.
10. The titanium substrate prepared by the method of any one of claims 1-9, wherein the titanium substrate has a structure comprising a matrix phase and a reinforcing phase dispersed in the matrix phase; wherein the content of the first and second substances,
the matrix phase is a fine uniform equiaxial grain structure, and the grain size is 20-60 mu m;
the reinforced phase is at least one of Ca-Ti-O particles and TiC and TiB particles, or the reinforced phase is TiB and La2O3Particles, or the reinforcing phase being CeO2Particles; the grain diameter of the Ca-Ti-O particles is 50-300 nm, the grain diameters of the TiC and TiB particles are both 3-8 mu m, and the La is2O3、CeO2The particle size of the particles is 1-3 μm.
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