Disclosure of Invention
The invention mainly aims to provide a powder metallurgy titanium or titanium alloy product and a short-flow preparation method thereof, wherein the preparation method comprises the steps of crushing a material into powder by utilizing the brittleness of the material after partial hydrogen absorption and combining a low-temperature crushing technology, then preparing titanium and titanium alloy materials by directly carrying out cold isostatic pressing forming and vacuum sintering densification on the powder, and omitting a dehydrogenation process so as to solve the technical problem of low efficiency caused by dehydrogenation treatment in the preparation process of the powder metallurgy titanium or titanium alloy product in the prior art.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a short-flow production method of a powder metallurgy titanium or titanium alloy article.
The short-process preparation method of the powder metallurgy titanium or titanium alloy comprises the following steps:
s1: preparing a raw material, namely selecting titanium or titanium alloy as the raw material, wherein the size of at least one dimension of the raw material is less than or equal to 5 mm;
s2: hydrogenation, namely, carrying out unsaturated hydrogenation treatment on the raw material in the step S1;
s3: crushing, namely performing low-temperature crushing treatment on the raw material subjected to the unsaturated hydrogenation treatment in the step S2 to obtain unsaturated titanium hydride powder;
s4: and (4) sequentially carrying out forming and sintering treatment on the unsaturated titanium hydride powder obtained in the step (S3) to obtain a titanium or titanium alloy product.
Further, in step S1, the raw material is in the form of a flat sheet, and the raw material is titanium chips, titanium alloy chips, or rolled titanium sponge sheets.
Further, in step S1, the rolled titanium sponge sheet has a thickness of 1 to 5 mm; the titanium alloy scraps are Ti-6Al-4V alloy scraps.
Further, in step S2, the hydrotreating process includes:
s2-1: vacuum pumping is carried out to 10-3~10-1Pa, heating to 450-550 ℃, and preserving heat for 30-60 min;
s2-2: introducing high-purity hydrogen and controlling the hydrogen absorption amount;
s2-3: and carrying out hydrogen homogenization treatment.
Further, in step S2-2, the hydrogen absorption amount is controlled to be 1.0 to 2.5 wt.%.
Further, in step S2-3, the hydrogen homogenization treatment specifically includes: after the hydrogen introduction is stopped, the temperature is raised to 550-850 ℃ again, and the temperature is kept for 2-5 h.
Further, in step S3, the cryogenic crushing treatment adopts a cryogenic mechanical crushing process, wherein the cryogenic medium is liquid argon.
Further, in step S3, the particle size of the unsaturated titanium hydride powder is 10 to 75 μm.
Further, in step S4, the forming process is performed by using a cold isostatic pressing process, wherein the pressing pressure is 150 to 200MPa, and the pressure maintaining time is 10 to 30S.
Further, in step S4, the sintering process specifically includes: and carrying out vacuum sintering densification on the blank obtained by the cold isostatic pressing forming process by adopting a sectional sintering process.
Further, the step sintering process specifically comprises the following steps:
the first section is heated to 550-750 ℃, the heating rate is 2 ℃/min, the temperature is kept for 2-10 h, and the removal of the residual hydrogen content is completed;
and heating the second section to 1150-1300 ℃, wherein the heating rate is 5 ℃/min, the sintering time is 2-5 h, and the densification is completed.
To achieve the above object, according to a second aspect of the present invention, there is provided a powder metallurgy titanium or titanium alloy article.
The titanium or titanium alloy product is prepared by the short-process preparation method of the powder metallurgy titanium or titanium alloy.
According to the invention, the flaky material is adopted to partially absorb hydrogen, the brittleness of the partially-absorbed material is utilized and the low-temperature crushing technology is combined to crush the material into powder, and then the powder is directly subjected to cold isostatic pressing forming and vacuum sintering densification to prepare the titanium and titanium alloy material, so that the dehydrogenation process is omitted.
Compared with titanium hydride powder, the powder partially absorbing hydrogen has better formability, and the problem of cracking of a large-size sintered blank is avoided; compared with hydrogenated dehydrogenated titanium powder, the hydrogenated dehydrogenated titanium powder has the advantages that the sintering density is improved, the oxygen content of a sintered blank is reduced, and the microstructure of the material is obviously refined.
Therefore, the invention realizes the short-process preparation of the powder titanium alloy product, and has the advantages of high yield, low cost and excellent product performance.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below. While exemplary embodiments of the present disclosure have been shown, it should be understood that the present disclosure may be embodied in various forms and should not be limited by 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 discloses a short-process preparation method of a powder metallurgy titanium or titanium alloy product, which comprises the following steps:
s1: preparing a raw material, namely selecting titanium or titanium alloy as the raw material, wherein the size of at least one dimension of the raw material is less than or equal to 5 mm; wherein: the selected raw materials are in a flat sheet shape, and the raw materials are preferably titanium chips, titanium alloy chips or rolled titanium sponge sheets; the thickness of the rolled titanium sponge sheet is 1-5 mm; the titanium alloy chips include Ti-6Al-4V alloy chips.
S2: hydrogenation, namely loading the selected raw materials into a rotary hydrogenation furnace for unsaturated hydrogenation treatment; the specific process comprises the following steps:
vacuum pumping is carried out to 10-3~10-1Pa, heating to 450-550 ℃, and preserving heat for 30-60 min; then introducing high-purity hydrogen, starting to absorb hydrogen, controlling the hydrogen absorption amount to be 1.0-2.5 wt.%, and stopping introducing hydrogen when the set hydrogen absorption amount is reached; and then raising the temperature to 550-850 ℃, and preserving the heat for 2-5 hours to carry out hydrogen homogenization treatment.
S3: crushing, namely crushing the raw material subjected to the unsaturated hydrogenation treatment in the step S2 by adopting a low-temperature mechanical crushing process to obtain unsaturated titanium hydride powder; wherein the low-temperature medium is liquid argon; the particle size of the unsaturated titanium hydride powder is 10 to 75 μm.
S4: forming, namely filling the unsaturated titanium hydride powder obtained in the step S3 into a rubber sleeve, and forming by adopting a cold isostatic pressing forming process; wherein the pressing pressure is 150-200 MPa, and the pressure maintaining time is 10-30 s, so that the cold isostatic pressing blank is obtained.
S5: and sintering, namely performing vacuum sintering densification on the cold isostatic pressing blank obtained in the step S4, wherein the sintering treatment adopts a sectional sintering process, and specifically comprises the following steps: the first section is heated to 550-750 ℃, the heating rate is 2 ℃/min, the temperature is kept for 2-10 h, and the removal of the residual hydrogen content is completed; and heating the second section to 1150-1300 ℃, wherein the heating rate is 5 ℃/min, the sintering time is 2-5 h, and densification is completed to obtain the titanium or titanium alloy product.
The short-flow preparation method of the powder metallurgy titanium or titanium alloy product in the application is described in detail by specific examples.
Example 1:
s1: the method comprises the steps of preparing raw materials, weighing 100kg of flat sheet raw materials with the thickness of 5mm formed by cold rolling of high-quality sponge titanium, cleaning and drying in vacuum to avoid oil pollution.
S2: hydrogenation, putting the raw materials into a hydrogenation furnace, and vacuumizing to 10 DEG-3~10-1Pa, heating to 500 ℃, keeping the temperature for 30min, and then stopping heating; then introducing high-purity hydrogen, starting hydrogen absorption, controlling the hydrogen absorption amount to be 2.5 wt.%, and stopping introducing hydrogen; raising the temperature to 600 ℃ again, and preserving the heat for 2h for hydrogen homogenization treatment.
S3: crushing, namely performing low-temperature mechanical crushing on the raw material treated in the step S2, wherein a low-temperature medium is liquid argon, and sealing and screening the crushed raw material to obtain powder particles with the particle size of less than or equal to 75 microns; preference is given to powder particles having a particle size of <30 μm.
S4: and (4) forming, namely filling the unsaturated titanium hydride powder obtained in the step (S3) into a rubber sheath, and forming by adopting cold isostatic pressing, wherein the pressing pressure is 200MPa, and the pressure maintaining time is 10S.
S5: and sintering, namely performing vacuum sintering densification on the cold isostatic pressing blank obtained in the step S4, wherein the sintering process adopts sectional sintering. Wherein: the first stage is heated to 700 ℃, the heating rate is 2 ℃/min, the temperature is kept for 10h, and the removal of the residual hydrogen content is completed; the second stage is heated to 1200 ℃, the heating rate is 5 ℃/min, and the sintering time is 2 h.
Example 2:
s1: preparing raw materials, weighing 100kg of high-quality Ti-6Al-4V titanium chips, cleaning, and drying in vacuum to avoid oil pollution.
S2: hydrogenation, putting the raw materials into a hydrogenation furnace, and vacuumizing to 10 DEG-3~10-1Pa, heating to 500 ℃, keeping the temperature for 30min, and then stopping heating; then introducing high-purity hydrogen, starting hydrogen absorption, controlling the hydrogen absorption amount to be 2 wt.%, and stopping introducing hydrogen; raising the temperature to 650 ℃ again, preserving the heat for 2 hours, and carrying out hydrogen homogenization treatment;
s3: crushing, namely performing low-temperature mechanical crushing on the raw material treated in the step S2, wherein a low-temperature medium is liquid argon, and sealing and screening the crushed raw material to obtain powder particles with the particle size of less than or equal to 75 microns; preference is given to powder particles having a particle size of < 20 μm.
S4: and (4) forming, namely filling the unsaturated titanium hydride powder obtained in the step (S3) into a rubber sheath, and forming by adopting cold isostatic pressing, wherein the pressing pressure is 180MPa, and the pressure maintaining time is 10S.
S5: and sintering, namely performing vacuum sintering densification on the cold isostatic pressing blank obtained in the step S4, wherein the sintering process adopts sectional sintering. Wherein: the first stage is heated to 650 ℃, the heating rate is 2 ℃/min, the temperature is kept for 10h, and the removal of the residual hydrogen content is completed; the second stage is heated to 1250 ℃, the heating rate is 5 ℃/min, and the sintering time is 2 h.
Example 3:
s1: preparing raw materials, weighing 100kg of high-quality Ti-6Al-4V titanium chips, cleaning, and drying in vacuum to avoid oil pollution.
S2: hydrogenation, putting the raw materials into a hydrogenation furnace, and vacuumizing to 10 DEG-3~10-1Pa, heating to 550 ℃, and stopping heating after keeping the temperature for 60 min; then introducing high-purity hydrogen, starting hydrogen absorption, controlling the hydrogen absorption amount to be 1 wt.%, and stopping introducing hydrogen; raising the temperature to 850 ℃ again, preserving the heat for 5 hours, and carrying out hydrogen homogenization treatment;
s3: crushing, namely performing low-temperature mechanical crushing on the raw material treated in the step S2, wherein a low-temperature medium is liquid argon, and sealing and screening the crushed raw material to obtain powder particles with the particle size of less than or equal to 75 microns; preference is given to powder particles having a particle size of <30 μm.
S4: and (4) forming, namely filling the unsaturated titanium hydride powder obtained in the step (S3) into a rubber sheath, and forming by adopting cold isostatic pressing, wherein the pressing pressure is 150MPa, and the pressure maintaining time is 30S.
S5: and sintering, namely performing vacuum sintering densification on the cold isostatic pressing blank obtained in the step S4, wherein the sintering process adopts sectional sintering. Wherein: the first stage is heated to 550 ℃, the heating rate is 2 ℃/min, the temperature is kept for 5h, and the removal of the residual hydrogen content is completed; the second stage is heated to 1250 ℃, the heating rate is 5 ℃/min, and the sintering time is 5 h.
Example 4:
s1: preparing raw materials, weighing 100kg of flat sheet raw materials with the thickness of 2mm formed by cold rolling of high-quality sponge titanium, cleaning, and drying in vacuum to avoid oil pollution.
S2: hydrogenation, putting the raw materials into a hydrogenation furnace, and vacuumizing to 10 DEG-3~10-1Pa, heating to 450 ℃, keeping the temperature for 50min, and then stopping heating; then introducing high-purity hydrogen, starting hydrogen absorption, controlling the hydrogen absorption amount to be 1.5 wt.%, and stopping introducing hydrogen; raising the temperature to 550 ℃ again, preserving the heat for 3.5 hours, and carrying out hydrogen homogenization treatment;
s3: crushing, namely performing low-temperature mechanical crushing on the raw material treated in the step S2, wherein a low-temperature medium is liquid argon, and sealing and screening the crushed raw material to obtain powder particles with the particle size of less than or equal to 75 microns; preference is given to powder particles having a particle size of < 20 μm.
S4: and (4) forming, namely filling the unsaturated titanium hydride powder obtained in the step (S3) into a rubber sheath, and forming by adopting cold isostatic pressing, wherein the pressing pressure is 150MPa, and the pressure maintaining time is 20S.
S5: and sintering, namely performing vacuum sintering densification on the cold isostatic pressing blank obtained in the step S4, wherein the sintering process adopts sectional sintering. Wherein: in the first stage, the temperature is heated to 750 ℃, the heating rate is 2 ℃/min, and the temperature is kept for 2h, so that the removal of the residual hydrogen content is completed; the second stage is heated to 1300 ℃, the heating rate is 5 ℃/min, and the sintering time is 3.5 h.
The following performance comparison experiments were performed on the titanium or titanium alloy products prepared by the preparation methods of examples 1 to 4 and the titanium or titanium alloy products prepared by the conventional preparation process.
First, experimental object
The titanium or titanium alloy articles prepared in examples 1-4 and the titanium or titanium alloy articles prepared in comparative examples 1-3, wherein:
comparative example 1:
the raw material in the comparative example 1 is non-rolled sponge titanium with the granularity of 0.83-25.4 mm; the remaining preparation process was carried out according to the preparation process in example 1.
Comparative example 2:
in comparative example 2, a block titanium material with the thickness of more than 5mm is selected as the raw material; the remaining preparation process was carried out according to the preparation process in example 1.
Comparative example 3:
the crushing treatment process in comparative example 3 was normal temperature mechanical crushing; the remaining preparation process was carried out according to the preparation process in example 1.
Second, Experimental methods
The performance of the products prepared in examples 1 to 4 and comparative examples 1 to 3 was measured by a conventional inspection method of the prior art.
And (3) testing the relative density: the relative density measurements were performed on the products prepared in examples 1 to 4 and comparative examples 1 to 3.
Third, test results
The experimental results of examples 1 to 4 and comparative examples 1 to 3 are summarized in tables 1 to 3.
TABLE 1 summary of the properties of the preparation processes and articles of examples 1-4
As can be seen from Table 1, the titanium or titanium alloy products obtained by the preparation method in the embodiments 1 to 4 of the present application have high compactness, and the yield of the fine powder with the particle size of less than 30 μm after the crushing treatment in the embodiments 1 to 4 is high.
TABLE 2 comparison of the properties of the articles of example 1 and comparative examples 1-2
As can be seen from Table 2, in comparative example 1 and comparative example 2, since the titanium sponge and the bulk titanium material which were not rolled were used as the raw materials, hydrogen was not sufficiently absorbed, the core portions of the titanium sponge and the bulk titanium material did not reach the brittleness required for crushing, the crushing was extremely difficult to perform, the yield of fine powder with a particle size of less than 30 μm was less than 50%, and the density of the finally obtained pure titanium and Ti-6Al-4V alloy was less than 95%.
Table 3 comparison of the preparation and article properties of example 1 and comparative example 3
As can be seen from table 3, since the normal temperature mechanical crushing process is adopted in comparative example 3, the material has the phenomena of cold welding, adhesion and the like during the crushing process, the service life of the crushing equipment is reduced, the yield of the fine powder is low, and the density of the finally obtained pure titanium is lower than 95%.
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.