CN119177415B - Preparation method of TC19 titanium alloy - Google Patents
Preparation method of TC19 titanium alloy Download PDFInfo
- Publication number
- CN119177415B CN119177415B CN202411677927.9A CN202411677927A CN119177415B CN 119177415 B CN119177415 B CN 119177415B CN 202411677927 A CN202411677927 A CN 202411677927A CN 119177415 B CN119177415 B CN 119177415B
- Authority
- CN
- China
- Prior art keywords
- titanium alloy
- rare earth
- titanium
- placing
- earth doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
- C23C8/30—Carbo-nitriding
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
The invention relates to the technical field of titanium alloy, and discloses a preparation method of TC19 titanium alloy, wherein after refinement, silicon carbide particles can generate grain boundaries with high volume density to prevent dislocation movement and dislocation expansion to adjacent grains, rare earth has the functions of purifying alloy liquid and effectively refining tissues, boron element can generate boron carbide with titanium element in the titanium alloy in situ, load can be transferred onto the boron carbide particles from a matrix in the process of stretching the titanium alloy, so that the matrix bears the energy of the load, the resistance of dislocation movement is increased, the strength and hardness of a titanium alloy material are improved, after carbonitriding of the TC19 titanium alloy, titanium carbide and titanium nitride ceramic wear-resistant phases can be generated on the surface of the titanium alloy, and simultaneously carbon and nitrogen can be dissolved into the titanium matrix to have the functions of solid solution strengthening, so that the wear resistance and corrosion resistance are improved, the mechanical property of the titanium alloy is further widened, and the application of the TC19 titanium alloy is further improved.
Description
Technical Field
The invention relates to the technical field of titanium alloy, in particular to a preparation method of TC19 titanium alloy.
Background
The titanium alloy has the remarkable characteristics of high specific strength, good corrosion resistance, high temperature resistance and the like, is widely applied to the fields of aerospace, chemical industry, medical treatment and the like, and meanwhile, more and more key rotating parts such as aeroengine compressor blisks and the like are selected from titanium alloy, so that the weight reduction purpose is realized, wherein the TC19 titanium alloy is a more typical brand in the titanium alloy, the nominal component of the TC19 titanium alloy is Ti-6Al-2Sn-4Zr-6Mo (mass percent), belongs to martensite alpha+beta type heat-strength titanium alloy, and has excellent physical properties and mechanical properties, however, the titanium alloy has low plastic shearing resistance and work hardening property, is insufficient to resist frictional wear (such as adhesion, abrasive particle wear and the like) caused by the mechanical property, and the wear resistance of the TC19 titanium alloy is poor, and meanwhile, the corrosion resistance is not high, so that the application of the TC19 titanium alloy is greatly limited, and therefore the TC19 titanium alloy is prepared to be a hot spot for current research.
TC19 titanium alloy is widely applied to various fields of aviation equipment, biopharmaceuticals, ships warships, petrochemical industry and the like due to the advantages of high biocompatibility, low corrosion degree, excellent mechanical strength, toughness and the like, but cannot meet requirements in practical application due to the defects of low surface hardness, poor wear resistance, low service life and the like of the titanium alloy, the most common smelting mode of TC19 titanium alloy is vacuum consumable arc furnace smelting, but the melting of electrodes is performed in the vacuum consumable arc smelting process, solidification is performed, a molten pool is relatively small, alloy elements cannot be fully diffused, so that component uniformity is improved, and the current smelting technology is difficult to achieve the level of non-reduction of solidification structure and component uniformity for the materials for engines with high alloying degree and particularly large difference of melting points of alloy elements.
The chemical vapor deposition and the physical vapor deposition can deposit a film with a certain thickness on the surface of a titanium alloy matrix, the hardness and the wear resistance of the surface layer of the titanium alloy can be improved, but the conventional chemical vapor deposition has higher requirements on temperature, the deposition rate is low, the method is difficult to deposit the film on part of the matrix or on one surface, the physical vapor deposition has smaller thermal influence on the matrix material, the obtained coating has poorer compactness, weaker bonding force with the matrix and easy falling-off of the coating, the requirement of the actual production process is not met, and the laser treatment is to fuse the prefabricated cladding layer and the titanium alloy matrix material together by utilizing an electron beam to form a composite coating with high strength and high hardness, but the technology is easy to cause uneven tissue distribution and uneven stress distribution and is high in price.
The invention aims to smelt the titanium alloy with TC19 by adding rare earth boron element, synthesize boron carbide wear-resistant particles in situ, and simultaneously, the rare earth element has the effect of purifying alloy liquid, and the TC19 titanium alloy is obtained by a surface hydrogen-free carbonitriding process, thereby remarkably improving the wear resistance, corrosion resistance and tensile property of the titanium alloy.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of TC19 titanium alloy, wherein a modified layer with corrosion resistance, wear resistance and good stability is prepared by doping and surface modification of the TC19 titanium alloy, so that the application range of the modified layer can be effectively enlarged, and the service life of the modified layer is prolonged.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the TC19 titanium alloy comprises the following steps:
washing the rare earth doped titanium alloy with 20-40% of citric acid by mass fraction, polishing with 600-1000 # abrasive paper, placing in an ultrasonic processor, cleaning for 5-15min, then cleaning with acetone for degreasing, cleaning with alcohol, and drying to obtain the surface treated titanium alloy.
And (2) performing plasma carbonitriding experiments by adopting a double-glow ion metal-carrying furnace, placing the surface-treated titanium alloy and a heat-insulating cover on a cathode workbench of a vacuum chamber, placing graphite on a source ring, covering a steel cover, adjusting the distance between the center of the graphite source and the cathode workbench and keeping the graphite on the same vertical line, vacuumizing to 3X 10 -2-6×10-2 Pa, setting the air pressure of argon and nitrogen to 25-45Pa, adjusting the cathode voltage, performing discharge bombardment activation on the surface of the titanium alloy for 2-5min, adjusting the source voltage, heating to perform plasma carbonitriding treatment, and after the treatment is finished, sampling in a closed furnace, and cooling to room temperature to obtain the TC19 titanium alloy.
Further, the power of the ultrasonic processor in the step (1) is 500-800W.
Further, in the step (2), the cathode voltage is 300-450V, and the source voltage is 600-850V.
Further, in the step (2), the distance between the center of the graphite source stage and the cathode worktable is 10-20cm.
Further, the plasma carbonitriding treatment temperature in the step (2) is 700-900 ℃ and the treatment time is 1-3h.
Further, the preparation method of the rare earth doped titanium alloy in the step (1) comprises the following steps:
And S1, placing TC19 titanium alloy, silicon carbide particles and rare earth boride in a planetary ball mill, and ball milling by adopting GCr15 steel balls with the diameter of 2-4mm, wherein the ball mass ratio is (3-5): 1, the rotating speed of the ball mill is 300-500r/min, and the ball milling time is 4-8h, so as to obtain the rare earth doped titanium alloy mixed powder.
And S2, placing the rare earth doped titanium alloy mixed powder into a graphite mold, performing cold isostatic pressing under 200-300MPa, sintering by adopting a discharge plasma sintering furnace, adjusting the heating rate and the vacuum degree, firstly preserving heat for 1-3h under 1050-1200 ℃, then preserving heat for 20-40min under 850-950 ℃, finally preserving heat for 2-4h under 600-700 ℃, and performing air cooling to room temperature to obtain the rare earth doped titanium alloy.
Further, in step S1, the rare earth boride is any one of lanthanum hexaboride, cerium hexaboride or yttrium hexaboride.
Further, in the step S1, the weight portion of TC19 titanium alloy is 100 portions, the weight portion of silicon carbide particles is 0.1 to 0.5 portion, and the weight portion of rare earth boride is 0.3 to 1.5 portions.
Further, the temperature rising rate in the step S2 is 80-100 ℃ per minute, and the vacuum degree is 2X 10 -3-5×10-3 Pa.
By adopting the technical scheme, the invention has the beneficial effects that:
The method comprises the steps of ball milling TC19 titanium alloy powder, silicon carbide particles and rare earth boride by adopting a planetary ball mill, preparing rare earth doped titanium alloy by utilizing a discharge plasma sintering process, polishing and cleaning the rare earth doped titanium alloy, carrying out surface treatment on the rare earth doped titanium alloy by adopting a hydrogen-free carbonitriding process, and obtaining the TC19 titanium alloy through optimizing process parameters.
The rare earth boride contains rare earth and boron elements, wherein the rare earth has the functions of purifying alloy liquid and effectively refining tissues, the boron elements can generate boron carbide with the titanium elements in situ, and in the process of stretching the titanium alloy, load can be transferred from a matrix to the boron carbide particles, so that the matrix bears the energy of the load, the resistance of increasing dislocation movement is increased, and the strength and hardness of the titanium alloy material are improved.
The TC19 titanium alloy is subjected to carbonitriding, titanium carbide and titanium nitride ceramic wear-resistant phases can be generated on the surface of the titanium alloy, carbon and nitrogen can be dissolved in a titanium matrix, the effect of solid solution strengthening is achieved, the wear resistance is improved, the wear rate is reduced, a hydrogen-free carbonitriding process is adopted, a uniform, compact and crack-free corrosion-resistant coating with smooth surface can be formed on the surface of the titanium alloy, the problem of hydrogen evolution caused by the common carbonitriding process is avoided, the damage to the mechanical property of the matrix material is avoided, a surface hardening treatment layer with a certain thickness can be obtained in a short time, the efficiency of titanium alloy surface modification treatment is improved, the wear resistance and the corrosion resistance of the titanium alloy are remarkably improved, the mechanical property of the titanium alloy is enhanced, and the further application of the TC19 titanium alloy is widened.
The preparation of the rare earth doped titanium alloy by adopting the gradient slow cooling process mainly has the advantages that (1) the difference of cooling rates enables the grain growth speed of different areas of the titanium alloy to be different, the accurate control of the microstructure of the titanium alloy is realized, and further, a gradient grain structure is formed, so that grains are refined, the strength and toughness of the titanium alloy are improved, the hardness of the titanium alloy also shows gradient distribution due to the existence of a temperature gradient, the adaptability and durability of the titanium alloy under different stress conditions are improved, and (3) a cooperative strengthening effect can be generated between rare earth doped elements and a titanium alloy matrix in the gradient slow cooling process, so that the mechanical property of the titanium alloy is further improved. Therefore, the gradient temperature control process has obvious influence in the titanium alloy manufacturing process, can optimize the tissue structure and mechanical property of the titanium alloy material, reduce defect formation, and improve the overall quality and service performance of the material.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) 100 Parts of TC19 titanium alloy, 0.1 part of silicon carbide particles and 0.3 part of lanthanum hexaboride in parts by weight are placed in a planetary ball mill, ball milling is carried out by adopting GCr15 steel balls with the diameter of 3mm, the ball mass ratio is 4:1, the rotation speed of the ball mill is 400r/min, and the ball milling time is 5h, so that the rare earth doped titanium alloy mixed powder is obtained.
(2) And (3) placing the rare earth doped titanium alloy mixed powder into a graphite mold, performing cold isostatic pressing forming at 250MPa, sintering by adopting a discharge plasma sintering furnace, adjusting the temperature rising rate to 90 ℃ per minute and the vacuum degree to 3X 10 -3 Pa, firstly preserving heat at 1150 ℃ for 2h, then preserving heat at 900 ℃ for 30min, finally preserving heat at 650 ℃ for 3h, and performing air cooling to room temperature to obtain the rare earth doped titanium alloy.
Example 2
(1) 100 Parts of TC19 titanium alloy, 0.2 part of silicon carbide particles and 0.6 part of cerium hexaboride in parts by weight are placed in a planetary ball mill, ball milling is carried out by adopting GCr15 steel balls with the diameter of 4mm, the mass ratio of the balls is 3:1, the rotating speed of the ball mill is 500r/min, and the ball milling time is 4 hours, so that the rare earth doped titanium alloy mixed powder is obtained.
(2) And (3) placing the rare earth doped titanium alloy mixed powder into a graphite mold, performing cold isostatic pressing forming under 300MPa, sintering by adopting a discharge plasma sintering furnace, adjusting the temperature rising rate to 100 ℃ per minute and the vacuum degree to 5 multiplied by 10 -3 Pa, firstly preserving heat at 1200 ℃ for 1h, then preserving heat at 950 ℃ for 20min, finally preserving heat at 700 ℃ for 2h, and performing air cooling to room temperature to obtain the rare earth doped titanium alloy.
Example 3
(1) 100 Parts of TC19 titanium alloy, 0.3 part of silicon carbide particles and 0.9 part of yttrium hexaboride in parts by weight are placed in a planetary ball mill, ball milling is carried out by adopting GCr15 steel balls with the diameter of 2mm, the mass ratio of the balls is 5:1, the rotating speed of the ball mill is 300r/min, and the ball milling time is 8 hours, so that the rare earth doped titanium alloy mixed powder is obtained.
(2) And (3) placing the rare earth doped titanium alloy mixed powder into a graphite mold, performing cold isostatic pressing forming under 200MPa, sintering by adopting a discharge plasma sintering furnace, adjusting the temperature rising rate to 80 ℃ per minute and the vacuum degree to 2X 10 -3 Pa, firstly preserving heat for 3 hours under 1050 ℃, then preserving heat for 40 minutes under 850 ℃, finally preserving heat for 2 hours under 600 ℃, and performing air cooling to room temperature to obtain the rare earth doped titanium alloy.
Example 4
(1) 100 Parts of TC19 titanium alloy, 0.4 part of silicon carbide particles and 1.2 parts of lanthanum hexaboride in parts by weight are placed in a planetary ball mill, ball milling is carried out by adopting GCr15 steel balls with the diameter of 3.5mm, the mass ratio of the balls is 4:1, the rotating speed of the ball mill is 350r/min, and the ball milling time is 7h, so that the rare earth doped titanium alloy mixed powder is obtained.
(2) And (3) placing the rare earth doped titanium alloy mixed powder into a graphite mold, performing cold isostatic pressing forming under 280MPa, sintering by adopting a discharge plasma sintering furnace, adjusting the temperature rising rate to 95 ℃ per minute and the vacuum degree to 4 multiplied by 10 -3 Pa, firstly preserving heat for 2 hours under 1100 ℃, then preserving heat for 35 minutes under 920 ℃, finally preserving heat for 3 hours under 660 ℃, and performing air cooling to room temperature to obtain the rare earth doped titanium alloy.
Example 5
(1) 100 Parts of TC19 titanium alloy, 0.5 part of silicon carbide particles and 1.5 parts of cerium hexaboride in parts by weight are placed in a planetary ball mill, ball milling is carried out by adopting GCr15 steel balls with the diameter of 3mm, the mass ratio of the balls is 5:1, the rotating speed of the ball mill is 450r/min, and the ball milling time is 5h, so that the rare earth doped titanium alloy mixed powder is obtained.
(2) And (3) placing the rare earth doped titanium alloy mixed powder into a graphite mold, performing cold isostatic pressing forming at 220MPa, sintering by adopting a discharge plasma sintering furnace, adjusting the temperature rising rate to be 85 ℃ per minute and the vacuum degree to be 5 multiplied by 10 -3 Pa, firstly preserving heat at 1200 ℃ for 3h, then preserving heat at 900 ℃ for 30min, finally preserving heat at 700 ℃ for 3h, and performing air cooling to room temperature to obtain the rare earth doped titanium alloy.
Comparative example 1
(1) 100 Parts of TC19 titanium alloy calculated according to parts by weight is placed in a planetary ball mill, ball milling is carried out by adopting GCr15 steel balls with the diameter of 3mm, the ball mass ratio is 4:1, the rotation speed of the ball mill is 400r/min, and the ball milling time is 5 hours, so that TC19 titanium alloy powder is obtained.
(2) Placing TC19 titanium alloy powder into a graphite mold, performing cold isostatic pressing forming under 250MPa, sintering by adopting a discharge plasma sintering furnace, adjusting the temperature rising rate to 90 ℃ per minute and the vacuum degree to 3X 10 -3 Pa, firstly preserving heat for 2h under 1150 ℃, then preserving heat for 30min under 900 ℃, finally preserving heat for 3h under 650 ℃, and performing air cooling to room temperature to obtain the TC19 titanium alloy.
And (3) tensile strength test, namely, testing the room-temperature tensile property of the titanium alloy by adopting an electronic universal testing machine according to the standard GB/T228-2002, wherein the tensile rate is 0.5mm/min.
Vickers hardness test, namely, referring to standard GB/T4340.1-1999, a digital display microhardness tester is adopted to test microhardness of the titanium alloy, the material of a pressing head is diamond, the load is 4.9N, and the pressure maintaining time is 15s.
TABLE 1 mechanical property test
As shown in the test results of the table, with the increase of the contents of silicon carbide particles and rare earth boride, the tensile strength and hardness of the titanium alloy are gradually increased, wherein the tensile strength in the embodiment 4 is 1083MPa, the Vickers hardness is 917.0HV, and the increase amplitude is obvious compared with the comparative example 1 without adding the silicon carbide particles and the rare earth boride, because on one hand, the thinned silicon carbide particles can generate crystal boundaries with high volume density to prevent the movement of dislocation and the expansion of the dislocation to adjacent crystal grains so as to strengthen the titanium alloy material, and on the other hand, the rare earth boride contains rare earth and boron elements, wherein the rare earth has the functions of purifying alloy liquid and effectively refining tissues, the boron element can generate boron carbide with the titanium element in the titanium alloy in situ, and in the process of stretching the titanium alloy, the load can be transferred from a matrix to the boron carbide particles, so that the matrix bears the energy of the load, and the resistance of dislocation movement is increased, and the strength and the hardness of the titanium alloy material are improved.
The abrasion resistance test comprises the steps of carrying out ball disc friction test by adopting a friction and abrasion tester, wherein a friction piece is made of TC19 titanium alloy, a friction pair is made of GCr15 balls with the diameter of 5mm, the surface hardness is 60HRC, the test condition is dry friction, the load is 50gf, the speed is 1300r/min, and the time is 30min.
Table 2 wear resistance test
As shown in the test data of the table, as the content of the silicon carbide particles and the rare earth boride increases, the volume fraction of the refined carbide is larger, the hardness is higher, and the wear resistance is better, because the silicon carbide and the boron carbide have better abrasive particle wear resistance and can transfer load, when the titanium alloy is subjected to external friction, a friction pair can form larger nicks or grooves on the surface of the titanium alloy, and for the carbide particles with smaller content, the carbide particles can be 'plowed' during one sliding pass, and for the carbide with larger content, the carbide particles can be crushed or 'plowed' through for multiple times, so that the wear resistance of the titanium alloy is enhanced.
Example 6
(1) The rare earth doped titanium alloy (prepared in example 4) is washed by 30% of citric acid by mass, polished by No. 800 sand paper, placed in an ultrasonic processor with power of 600W for cleaning for 10min, then cleaned by acetone for degreasing, cleaned by alcohol and dried to obtain the surface treated titanium alloy.
(2) Plasma carbonitriding experiments are carried out by adopting a double-glow ion metal-cementation furnace, placing the surface-treated titanium alloy and a heat-insulating cover on a cathode workbench of a vacuum chamber, placing graphite on a source ring, covering a steel cover, adjusting the distance between the center of the graphite source and the cathode workbench and keeping the distance on the same vertical line, vacuumizing to 4X 10 -2 Pa, setting the air pressure of argon and nitrogen to 40Pa, adjusting the cathode voltage to 400V, carrying out discharge bombardment activation on the surface of the titanium alloy for 3min, adjusting the source voltage to 750V, carrying out plasma carbonitriding treatment for 2h at 800 ℃, ensuring that the thickness of a cementation layer is 50 mu m, closing the furnace, sampling, and cooling to room temperature to obtain the TC19 titanium alloy.
Example 7
(1) Washing rare earth doped titanium alloy (prepared in example 4) with 40% citric acid, grinding with 600 # abrasive paper, cleaning in an ultrasonic processor with power of 800W for 5min, cleaning with acetone for degreasing, cleaning with alcohol, and drying to obtain the surface treated titanium alloy.
(2) Plasma carbonitriding experiments are carried out by adopting a double-glow ion metal-cementation furnace, placing the surface-treated titanium alloy and a heat-insulating cover on a cathode workbench of a vacuum chamber, placing graphite on a source ring, covering a steel cover, adjusting the distance between the center of the graphite source and the cathode workbench and keeping the distance on the same vertical line, vacuumizing to 6X 10 -2 Pa, setting the air pressure of argon and nitrogen to 45Pa, adjusting the cathode voltage to 450V, carrying out discharge bombardment activation on the surface of the titanium alloy for 2min, adjusting the source voltage to 850V, carrying out plasma carbonitriding treatment for 1h at 900 ℃, ensuring that the thickness of a cementation layer is 100 mu m, closing the furnace, sampling, and cooling to room temperature to obtain the TC19 titanium alloy.
Example 8
(1) Washing the rare earth doped titanium alloy (prepared in example 4) with 20% of citric acid by mass fraction, polishing with 1000 # abrasive paper, cleaning in an ultrasonic processor with power of 500W for 15min, then cleaning with acetone for degreasing, cleaning with alcohol, and drying to obtain the surface treated titanium alloy.
(2) Plasma carbonitriding experiments are carried out by adopting a double-glow ion metal-cementation furnace, placing the surface-treated titanium alloy and a heat-insulating cover on a cathode workbench of a vacuum chamber, placing graphite on a source ring, covering a steel cover, adjusting the distance between the center of the graphite source and the cathode workbench and keeping the distance on the same vertical line, vacuumizing to 3X 10 -2 Pa, setting the air pressure of argon and nitrogen to 25Pa, adjusting the cathode voltage to 300V, carrying out discharge bombardment activation on the surface of the titanium alloy for 5min, adjusting the source voltage to 600V, carrying out plasma carbonitriding treatment for 3h at 700 ℃, ensuring that the thickness of a cementation layer is 150 mu m, closing the furnace, sampling, and cooling to room temperature to obtain the TC19 titanium alloy.
Example 9
(1) Washing the rare earth doped titanium alloy (prepared in example 4) with 35% of citric acid by mass fraction, polishing with 900 # abrasive paper, cleaning in an ultrasonic processor with power of 600W for 12min, then cleaning with acetone for degreasing, cleaning with alcohol, and drying to obtain the surface treated titanium alloy.
(2) Plasma carbonitriding experiments are carried out by adopting a double-glow ion metal-cementation furnace, placing the surface-treated titanium alloy and a heat-insulating cover on a cathode workbench of a vacuum chamber, placing graphite on a source ring, covering a steel cover, adjusting the distance between the center of the graphite source and the cathode workbench and keeping the distance on the same vertical line, vacuumizing to 4X 10 -2 Pa, setting the air pressure of argon and nitrogen to 30Pa, adjusting the cathode voltage to 350V, carrying out discharge bombardment activation on the surface of the titanium alloy for 4min, adjusting the source voltage to 750V, carrying out plasma carbonitriding treatment for 2h at 850 ℃, ensuring that the thickness of a cementation layer is 200 mu m, closing the furnace, sampling, and cooling to room temperature to obtain the TC19 titanium alloy.
Example 10
(1) Washing rare earth doped titanium alloy (prepared in example 4) with 25% citric acid, polishing with 700 # abrasive paper, cleaning in an ultrasonic processor with power of 600W for 10min, cleaning with acetone for degreasing, cleaning with alcohol, and drying to obtain the surface treated titanium alloy.
(2) Plasma carbonitriding experiments are carried out by adopting a double-glow ion metal-cementation furnace, placing the surface-treated titanium alloy and a heat-insulating cover on a cathode workbench of a vacuum chamber, placing graphite on a source ring, covering a steel cover, adjusting the distance between the center of the graphite source and the cathode workbench and keeping the distance on the same vertical line, vacuumizing to 5X 10 -2 Pa, setting the air pressure of argon and nitrogen to 40Pa, adjusting the cathode voltage to 400V, carrying out discharge bombardment activation on the surface of the titanium alloy for 5min, adjusting the source voltage to 800V, carrying out plasma carbonitriding treatment for 2h at 850 ℃, ensuring that the thickness of a cementation layer is 250 mu m, closing the furnace, sampling, and cooling to room temperature to obtain the TC19 titanium alloy.
Comparative example 2
(1) Washing rare earth doped titanium alloy (prepared by comparative example 1) with 30% citric acid, polishing with 800 # abrasive paper, cleaning in an ultrasonic processor with power of 600W for 10min, cleaning with acetone for degreasing, cleaning with alcohol, and drying to obtain the surface treated titanium alloy.
(2) Plasma carbonitriding experiments are carried out by adopting a double-glow ion metal-cementation furnace, placing the surface-treated titanium alloy and a heat-insulating cover on a cathode workbench of a vacuum chamber, placing graphite on a source ring, covering a steel cover, adjusting the distance between the center of the graphite source and the cathode workbench and keeping the distance on the same vertical line, vacuumizing to 4X 10 -2 Pa, setting the air pressure of argon and nitrogen to 40Pa, adjusting the cathode voltage to 400V, carrying out discharge bombardment activation on the surface of the titanium alloy for 3min, adjusting the source voltage to 750V, carrying out plasma carbonitriding treatment for 2h at 800 ℃, ensuring that the thickness of a cementation layer is 50 mu m, closing the furnace, sampling, and cooling to room temperature to obtain the TC19 titanium alloy.
Comparative example 3
Washing rare earth doped titanium alloy (prepared in example 6) with 30% citric acid, polishing with 800 # abrasive paper, cleaning in an ultrasonic processor with power of 600W for 10min, cleaning with acetone for degreasing, cleaning with alcohol, and drying to obtain the surface treated titanium alloy.
And (3) testing corrosion resistance, namely drying the surface of the prepared titanium alloy cleaned by alcohol, weighing the initial weight m 1, soaking the titanium alloy in an aqueous solution of sulfuric acid with the mass fraction of 80%, taking out the titanium alloy after 168 hours, weighing the titanium alloy m 2, and calculating the corrosion rate.
The abrasion resistance test comprises the steps of carrying out ball disc friction test by adopting a friction and abrasion tester, wherein a friction piece is made of TC19 titanium alloy, a friction pair is made of GCr15 balls with the diameter of 5mm, the surface hardness is 60HRC, the test condition is dry friction, the load is 50gf, the speed is 1300r/min, and the time is 30min.
TABLE 3 abrasion and Corrosion resistance testing
As shown by the test results of the table, with the increase of the thickness of the carbonitriding layer on the surface of the titanium alloy, the corrosion resistance and the wear resistance of the titanium alloy are gradually enhanced, wherein the wear rate in the example 9 is 0.0020g/h, and the corrosion rate is 1.852mm/a, which shows that on one hand, the wear rate of the titanium alloy can be reduced after carbonitriding, because the titanium carbide and the titanium nitride ceramic wear-resistant phase is generated on the surface of the titanium alloy after carbonitriding, and simultaneously carbon and nitrogen can be dissolved into a titanium substrate, the effect of solid solution strengthening is achieved, the wear resistance is improved, and the wear rate is reduced, on the other hand, the hydrogen-free carbonitriding process is adopted, so that a uniform, compact, crack-free and smooth corrosion-resistant coating can be formed on the surface of the titanium alloy, and the damage to the mechanical property of the substrate material per se caused by the hydrogen evolution problem of the common carbonitriding process is avoided, on the surface of the titanium alloy is not modified by silicon carbide particles and rare earth boride, but the surface of the titanium alloy is better in the comparative example 2, and the surface is modified by silicon carbide particles and rare earth boride, but the surface is not subjected to the hydrogen-free carbon and the wear resistance process.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for preparing a TC19 titanium alloy, said method comprising the steps of:
washing the rare earth doped titanium alloy with 20-40% of citric acid by mass fraction, polishing with 600-1000 # abrasive paper, placing in an ultrasonic processor, cleaning for 5-15min, then cleaning with acetone for degreasing, cleaning with alcohol, and drying to obtain the surface treated titanium alloy;
Performing plasma carbonitriding experiments by adopting a double-glow ion metal-carrying furnace, placing the surface-treated titanium alloy and a heat-insulating cover on a cathode workbench of a vacuum chamber, placing graphite on a source ring, covering a steel cover, adjusting the distance between the center of the graphite source and the cathode workbench and keeping the distance on the same vertical line, vacuumizing to 3X 10 -2-6×10-2 Pa, setting the air pressure of argon and nitrogen to 25-45Pa, adjusting the cathode voltage, performing discharge bombardment activation on the surface of the titanium alloy for 2-5min, adjusting the source voltage, heating for performing plasma carbonitriding treatment, after the treatment is finished, the thickness of a carburized layer is 50-250 mu m, closing the furnace, sampling, and cooling to room temperature to obtain TC19 titanium alloy;
the preparation method of the rare earth doped titanium alloy in the step (1) comprises the following steps:
Step S1, placing TC19 titanium alloy, silicon carbide particles and rare earth boride in a planetary ball mill, and performing ball milling by adopting GCr15 steel balls with the diameter of 2-4mm, wherein the mass ratio of the balls is (3-5): 1, the rotating speed of the ball mill is 300-500r/min, and the ball milling time is 4-8h, so as to obtain rare earth doped titanium alloy mixed powder;
s2, placing the rare earth doped titanium alloy mixed powder into a graphite mold, performing cold isostatic pressing at 200-300MPa, sintering by adopting a discharge plasma sintering furnace, adjusting the heating rate and the vacuum degree, firstly preserving heat for 1-3h at 1050-1200 ℃, then preserving heat for 20-40min at 850-950 ℃, finally preserving heat for 2-4h at 600-700 ℃, and performing air cooling to room temperature to obtain the rare earth doped titanium alloy;
In the step S1, the weight portion is 100 portions of TC19 titanium alloy, 0.1 to 0.5 portion of silicon carbide particles and 0.3 to 1.5 portions of rare earth boride.
2. The method for producing a TC19 titanium alloy according to claim 1, wherein power of said ultrasonic processor in said step (1) is 500 to 800W.
3. The method for producing a TC19 titanium alloy according to claim 1, wherein in said step (2), a cathode voltage is 300 to 450V and a source voltage is 600 to 850V.
4. The method for producing TC19 titanium alloy according to claim 1, wherein a distance between a graphite source center and a cathode table in said step (2) is 10-20cm.
5. The method for producing a TC19 titanium alloy according to claim 1, wherein the plasma carbonitriding treatment temperature in the step (2) is 700 to 900 ℃ and the treatment time is 1 to 3 hours.
6. The method for preparing TC19 titanium alloy according to claim 1, wherein said rare earth boride in step S1 is any one of lanthanum hexaboride, cerium hexaboride or yttrium hexaboride.
7. The method for producing a TC19 titanium alloy according to claim 1, wherein the temperature rise rate in the step S2 is 80 to 100℃per minute, and the vacuum degree is 2X 10 -3-5×10-3 Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411677927.9A CN119177415B (en) | 2024-11-22 | 2024-11-22 | Preparation method of TC19 titanium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411677927.9A CN119177415B (en) | 2024-11-22 | 2024-11-22 | Preparation method of TC19 titanium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN119177415A CN119177415A (en) | 2024-12-24 |
| CN119177415B true CN119177415B (en) | 2025-03-14 |
Family
ID=93899992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411677927.9A Active CN119177415B (en) | 2024-11-22 | 2024-11-22 | Preparation method of TC19 titanium alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN119177415B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1390976A (en) * | 2002-03-20 | 2003-01-15 | 太原理工大学 | Non-hydrogen carbonizing equipment and technology by dual-glow diocharge |
| CN101871086A (en) * | 2010-05-24 | 2010-10-27 | 广州有色金属研究院 | A kind of preparation method of infiltration plasma nitrocarburizing and diamond-like composite film layer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6024915A (en) * | 1993-08-12 | 2000-02-15 | Agency Of Industrial Science & Technology | Coated metal particles, a metal-base sinter and a process for producing same |
-
2024
- 2024-11-22 CN CN202411677927.9A patent/CN119177415B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1390976A (en) * | 2002-03-20 | 2003-01-15 | 太原理工大学 | Non-hydrogen carbonizing equipment and technology by dual-glow diocharge |
| CN101871086A (en) * | 2010-05-24 | 2010-10-27 | 广州有色金属研究院 | A kind of preparation method of infiltration plasma nitrocarburizing and diamond-like composite film layer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN119177415A (en) | 2024-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113652659B (en) | Preparation method of high-entropy alloy nitride coating metallurgically bonded with substrate | |
| CN110565047B (en) | Titanium alloy surface nitriding process | |
| CN112813399B (en) | High-entropy metal glass protective coating and preparation method thereof | |
| CN112981320B (en) | Titanium alloy surface composite coating and preparation method thereof | |
| CN105839049A (en) | High-temperature-oxidation-resistant and abrasion-resistant AlCrN coating on surface of titanium-aluminum alloy and preparation method thereof | |
| CN109913796A (en) | TiAlN composite coating on surface of titanium alloy and preparation method thereof | |
| CN111321381B (en) | AlCrNbSiTiBN-based nano composite coating of hard alloy blade and preparation method thereof | |
| CN114262872B (en) | Chromium-aluminum-boron alloy composite target material and preparation method thereof | |
| CN114231906A (en) | Thermal barrier coating of high-pressure turbine blade of marine gas turbine and preparation method thereof | |
| CN112779533B (en) | Method for preparing metal-based composite coating on surface of stainless steel | |
| CN109434119A (en) | A kind of preparation method of high tenacity MXene phase dipping molybdenum alloy | |
| CN110373628B (en) | In-situ reaction self-generated high temperature diffusion barrier on refractory metal surface and preparation method thereof | |
| CN119177415B (en) | Preparation method of TC19 titanium alloy | |
| CN112962065B (en) | Nickel-based alloy surface composite structure coating and preparation method thereof | |
| CN111804907B (en) | A kind of modified ceramic particle reinforced iron-based composite material and preparation method thereof | |
| CN117867447A (en) | A hard high entropy alloy nitride film material and preparation method thereof | |
| CN105568211B (en) | A kind of method that reinforcing is oozed in aluminum alloy surface plasma expansion | |
| CN117802452A (en) | A Ti/TiN/(TiN+TiAlN)/TiAlN nanocomposite coating and preparation method thereof | |
| CN114672805B (en) | Preparation method of high-temperature oxidation resistant coating on surface of niobium alloy | |
| CN113186505B (en) | Method for preparing WC coating on surface of gamma-TiAl alloy | |
| CN114934247A (en) | Surface high-frequency induction treatment hardening method suitable for regular-profile TC4 titanium alloy | |
| CN116219376B (en) | A tantalum surface high temperature ablation resistant coating and preparation method thereof | |
| CN115287596B (en) | Preparation method of chromium alloy layer on stainless steel | |
| CN116121707B (en) | TiCrAlSiX coating on titanium alloy surface and preparation method thereof | |
| CN107400864A (en) | AlMoC/AlMoCN laminated coatings cutter and its preparation technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |