CN108439422B - Method for preparing titanium boride alloy through aluminothermic reduction - Google Patents
Method for preparing titanium boride alloy through aluminothermic reduction Download PDFInfo
- Publication number
- CN108439422B CN108439422B CN201810203148.3A CN201810203148A CN108439422B CN 108439422 B CN108439422 B CN 108439422B CN 201810203148 A CN201810203148 A CN 201810203148A CN 108439422 B CN108439422 B CN 108439422B
- Authority
- CN
- China
- Prior art keywords
- titanium
- aluminum
- alloy
- sodium
- less
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/02—Boron; Borides
- C01B35/04—Metal borides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
- C22C1/1052—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites by mixing and casting metal matrix composites with reaction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
A method for preparing titanium boride alloy by aluminothermic reduction comprises a two-step method and a three-step method; the two-step method is to mix and press sodium fluotitanate, sodium fluoborate and aluminum powder into a briquette; placing the titanium boride into a reduction tank for vacuum thermal reduction, heating up for vacuum distillation, crystallizing the evaporated material, and cooling the residual material to obtain a titanium boride alloy; the three-step method is that sodium fluotitanate, aluminum powder and sodium fluoride are mixed and pressed into agglomerates, the mixture is heated up after vacuum thermal reduction and vacuum distillation is carried out, evaporated materials are crystallized, and the rest materials are aluminum-titanium alloy or metallic titanium; grinding, mixing with sodium fluoborate and sodium fluoride, and pressing into secondary blocks; vacuum distillation is carried out after two-stage vacuum thermal reduction, evaporated materials are crystallized, and the rest materials are titanium boride alloys. The titanium boride powder produced by the method has high purity, controllable granularity and low cost, and the by-products cryolite and the aluminum-titanium-boron alloy are products with more industrial applications.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for preparing a titanium boride alloy through aluminothermic reduction.
Background
Titanium diboride powder is a gray or gray black crystal, and because it has very high hardness, is resistant to oxidation in air, and is resistant to corrosion by molten metals, it is widely used for preparing composite ceramic articles, molten metal crucibles, and reinforcing agents for metal materials, and also can be used for manufacturing finishing tools, various dies, sealing elements, various high temperature parts, etc., and is a high value-added powder material.
The current production methods of titanium boride mainly comprise a direct synthesis method, a carbothermic method, a metallothermic method and a gas phase deposition method; the direct synthesis method is to synthesize titanium diboride by using titanium powder and high-purity boron powder, wherein Ti + 2B = TiB2The method has high cost and is only applied in laboratories; carbon (C)The thermal reduction method is characterized in that activated carbon is used as a reducing agent, boron oxide or boron carbide is used as a boron source, titanium dioxide is used as a titanium source, reduction is carried out at the high temperature of 1800-1900 ℃ to prepare titanium boride, most of equipment adopts a vacuum carbon tube furnace, and the method has the main problems that the produced product has larger granularity and lower purity; the metallothermic reduction method, namely the self-propagating high-temperature synthesis (SHS) process, is a method for producing titanium boride by using aluminum powder or magnesium powder as a reducing agent to reduce titanium dioxide and boron oxide, and the high temperature produced by the reduction reaction is utilized to ensure that the reaction can be automatically carried out after the initiation, an external heating source is not needed to complete the reaction, but the produced titanium diboride contains more aluminum or magnesium and has poor purity; the vapor deposition method is TiCl4And BCl3As raw material, H is adopted2Reducing and depositing titanium diboride powder at the deposition temperature of 800-; therefore, the current production method of the industrial titanium boride powder is high in cost or poor in purity, and further application of the titanium boride powder is influenced.
Disclosure of Invention
Aiming at the problems in the existing titanium boride generation technology, the invention provides a method for preparing titanium boride alloy by aluminothermic reduction, which takes aluminum powder as a reducing agent and sodium fluotitanate and sodium fluoborate as raw materials to prepare titanium boride alloy powder by vacuum thermic reduction; the cost is reduced, and simultaneously, high-purity titanium boride powder is obtained; the method comprises a two-step method or a three-step method, wherein sodium fluotitanate, sodium fluoborate and aluminum powder are mixed and agglomerated in the two steps, then titanium boride alloy and cryolite are directly prepared by vacuum thermal reduction, and in the three steps, the sodium fluotitanate is reduced in vacuum by using aluminothermic to prepare aluminum-titanium alloy powder, and then the sodium fluoborate is reduced by using the aluminum-titanium alloy powder as a reducing agent to prepare the titanium boride powder.
The method I of the invention is carried out according to the following steps:
1. uniformly mixing sodium fluotitanate, sodium fluoborate and aluminum powder, wherein the mass ratio of the sodium fluotitanate to the sodium fluoborate to the aluminum powder is 1 (1.05-1.06) to 0.40-0.43, and then pressing the mixture into briquettes by using a briquetting machine;
2. putting the block mass into a reduction tank for vacuum thermal reduction, wherein the temperature of the vacuum thermal reduction is 800-1000 ℃, the vacuum degree is 0.01-10 Pa, and the time is 2-8 h; after the vacuum thermal reduction is finished, heating to 900-1250 ℃, carrying out vacuum distillation, and enabling the evaporated material to enter a crystallizer for crystallization to form a crystallized product; after the vacuum distillation is finished, the residual materials are cooled to less than or equal to 50 ℃ along with the furnace, and the titanium boride alloy is obtained.
The reaction formula of the vacuum thermal reduction reaction of the method is as follows:
3Na2TiF6 + 6NaBF4 +10Al= 3TiB2 + Na3AlF6+ 9NaAlF4 （1）。
in the method, the pressure for pressing the briquette is 50-100 MPa.
In the method, the obtained crystallization product comprises 7-10% of cryolite, 75-90% of mono-cryolite, 1-5% of sodium fluorotitanate, 1-5% of sodium fluoroborate and less than or equal to 2% of other fluorides by weight.
Grinding the crystallized product until the granularity is less than or equal to 0.15mm, and then mixing the ground crystallized product with aluminum powder with the granularity less than or equal to 0.15mm and sodium fluoride with the granularity less than or equal to 0.15mm, wherein the mixing proportion is that the mass ratio of the crystallized product to the aluminum powder is (1-5) to 1, and the mass ratio of the crystallized product to the sodium fluoride is 1 (0.63-0.65), so as to obtain mixed powder; placing the mixed powder into a crucible and then placing the crucible into a heating furnace, or placing the mixed powder into a resistance furnace or a gas heating furnace with an alumina lining, preserving the heat for 1-3 h at 950-1100 ℃, allowing titanium and boron reduced by aluminum to enter an aluminum melt, and allowing the reacted material to consist of a cryolite (sodium fluoroaluminate) melt on the upper layer and an aluminum-titanium-boron alloy melt on the lower layer; grinding the titanium boride alloy to a granularity of less than or equal to 0.15mm, pouring out the cryolite melt on the upper layer, adding sponge titanium with the granularity of less than or equal to 1mm and titanium boride alloy with the granularity of less than or equal to 0.15mm into the aluminum-titanium-boron alloy melt, stirring uniformly and melting the sponge titanium and the titanium boride alloy to form a mixed melt, wherein the mass ratio of the sponge titanium to the titanium boride alloy is (27-29) = (0.7-0.9): 1; and pouring the mixed melt to form an ingot to obtain an aluminum-titanium-boron alloy product.
The single cryolite in the crystallization product reacts with sodium fluoride to form cryolite, and the reaction formula is as follows:
NaAlF4+2NaF= Na3AlF6 （2）。
when the crystallized product reacts with aluminum powder and sodium fluoride, the mass percent of titanium and the mass percent of boron in the aluminum-titanium-boron alloy melt are controlled to be 4.9-5.1%, and the mass percent of boron is controlled to be 0.9-1.1%; the mass percentages of titanium and boron in the obtained cryolite melt are both less than or equal to 0.02 percent.
The method II of the invention is carried out according to the following steps:
1. uniformly mixing sodium fluotitanate, aluminum powder and sodium fluoride, wherein the mass ratio of the sodium fluotitanate to the aluminum powder to the sodium fluoride is 2.50 (0.43-1.07): 1.00, and then pressing the mixture into briquettes by using a briquetting machine;
2. putting the block mass into a reduction tank for vacuum thermal reduction, wherein the temperature of the vacuum thermal reduction is 700-1000 ℃, the vacuum degree is 0.1-10 Pa, and the time is 2-8 h; after the vacuum thermal reduction is finished, heating to 1050-1250 ℃, carrying out vacuum distillation, and enabling the evaporated material to enter a crystallizer for crystallization to form a primary crystallization product; after the vacuum distillation is finished, cooling the residual materials to be less than or equal to 50 ℃ along with the furnace to obtain aluminum-titanium alloy or metal titanium;
3. grinding an aluminum-titanium alloy or metal titanium to the granularity of less than or equal to 0.15mm, then uniformly mixing with sodium fluoborate and sodium fluoride, wherein the mass ratio of the sodium fluoride to the sodium fluoborate is 0.76:1, the molar ratio of aluminum to the sodium fluoborate in all materials is 1:1, adding aluminum powder when the aluminum in all materials is insufficient, and pressing into secondary briquettes by using a briquetting machine; or crushing and grinding the aluminum-titanium alloy until the granularity is less than or equal to 0.15mm, then uniformly mixing the aluminum-titanium alloy with sodium fluoborate, uniformly mixing the aluminum-titanium alloy and the sodium fluoborate, wherein the molar ratio of the aluminum to the sodium fluoborate in all the materials is 1:1, adding aluminum powder when the aluminum in all the materials is insufficient, and pressing the mixture into secondary briquettes by using a briquetting machine;
4. placing the secondary block mass in a reduction tank for secondary vacuum thermal reduction, wherein the temperature of the secondary vacuum thermal reduction is 600-900 ℃, the vacuum degree is 0.1-10 Pa, the time is 2-8 h, after the secondary vacuum thermal reduction is finished, the temperature is raised to 900-1200 ℃, vacuum distillation is carried out, and the evaporated material enters a crystallizer for crystallization to form a secondary crystallization product; cooling the rest materials to less than or equal to 50 ℃ along with the furnace to obtain the titanium boride alloy.
In the second method, the reaction formula of the vacuum thermal reduction reaction in the step 2 is:
3Na2TiF6 + （3x+4）Al+6NaF= 3AlxTi + 4Na3AlF6 （3）；
wherein x = 0-2; when x =0, 3Al obtainedxTi is metallic titanium.
In the second method, when sodium fluoride is contained in the ingredients in step 3, the reaction formula of the second vacuum thermal reduction reaction in step 4 is as follows:
AlxTi+2NaBF4+(2-x)Al+4NaF=TiB2+2Na3AlF6 （4）；
wherein x = 0-2; when x =0, 3Al usedxTi is metallic titanium, and when x =2, aluminum powder is not added;
when the ingredients in the step 3 do not contain sodium fluoride, the reaction formula of the secondary vacuum thermal reduction reaction in the step 4 is as follows:
AlxTi+2NaBF4+(2-x)Al=TiB2+2NaAlF4 （5）；
wherein x = 0-2; when x =0, 3Al usedxTi is metallic titanium, and when x =2, no aluminum powder is added.
In the second method, the pressure for pressing the briquette is 50-100 MPa.
Mixing the primary crystallization product and the secondary crystallization product, grinding the mixture until the granularity is less than or equal to 0.15mm, and then mixing the mixture with aluminum powder with the granularity being less than or equal to 0.15mm to obtain mixed powder; wherein the mass ratio of the primary crystallization product to the secondary crystallization product is aluminum powder = (1-5): 1; when no sodium fluoride is added in the step 3, adding sodium fluoride into the mixed powder and then mixing, wherein the adding amount of the sodium fluoride is 0.65 times of the mass of the secondary crystallization product; placing the mixed powder into a crucible and then placing the crucible into a heating furnace, or placing the mixed powder into a resistance furnace or a gas heating furnace with an alumina lining, preserving the heat for 1-3 h at 950-1100 ℃, allowing titanium and boron reduced by aluminum to enter an aluminum melt, and allowing the reacted material to consist of a cryolite (sodium fluoroaluminate) melt on the upper layer and an aluminum-titanium-boron alloy melt on the lower layer; grinding a titanium boride alloy to a granularity of less than or equal to 0.15mm, grinding an aluminum-titanium alloy or metal titanium to a granularity of less than or equal to 0.15mm, pouring out the cryolite melt on the upper layer, adding the aluminum-titanium alloy or metal titanium with the granularity of less than or equal to 0.15mm into the aluminum-titanium-boron alloy melt, adding the titanium boride alloy with the granularity of less than or equal to 0.15mm, stirring uniformly, and melting the titanium boride alloy and the aluminum-titanium alloy or metal titanium boride to form a mixed melt, wherein the mass ratio of the aluminum-titanium-boron alloy melt to the aluminum-titanium alloy to the titanium boride alloy is (28-30) = (0.9-1.7): 1, or the mass ratio of the aluminum-titanium-boron alloy melt to the titanium boride alloy is (28-30) = (0.9-1.0): 1); and pouring the mixed melt to form an ingot to obtain an aluminum-titanium-boron alloy product.
In the second method, the single cryolite in the secondary crystallization product reacts with the sodium fluoride to form cryolite, and the reaction formula is the same as the reaction formula (2).
In the second method, the mass ratio of aluminum to titanium in the aluminum-titanium alloy obtained in step 2 is less than or equal to 1.125:1 (i.e. the molar ratio is less than or equal to 2: 1).
In the second method, the primary crystallization product is generated sodium fluoroaluminate, unreacted sodium fluorotitanate and other fluorides, and comprises 85-95% of cryolite, 1-5% of sodium fluorotitanate and less than or equal to 2% of other fluorides by mass percent.
In the second method, the aluminum-titanium alloy and the titanium boride alloy are added into the aluminum-titanium-boron alloy melt by blowing into the bottom of the alloy melt, and the carrier gas is argon gas when blowing.
When the primary crystallization product and the secondary crystallization product react with aluminum powder, the mass percent of titanium in the alloy melt is controlled to be 4.9-5.1%, and the mass percent of boron is controlled to be 0.9-1.1%; the mass percentages of titanium and boron in the obtained cryolite melt are both less than or equal to 0.02 percent.
The cryolite obtained after the cryolite melt obtained by the two methods is solidified can be used in the aluminum electrolysis industry, and the obtained byproduct aluminum-titanium-boron alloy product can be used as a grain refiner in the casting industry.
The titanium boride powder produced by the process has high purity, controllable granularity and low cost, and the by-products cryolite and the aluminum-titanium-boron alloy are products with more industrial applications; no waste gas, waste water and solid waste are generated in the production process, and the production process is a green production process.
Drawings
FIG. 1 is a schematic flow chart of a method for producing a titanium boride alloy by aluminothermic reduction in example 1 of the present invention;
FIG. 2 is a schematic flow chart of a method for preparing a titanium boride alloy by aluminothermic reduction in embodiment 2 of the present invention;
FIG. 3 is a schematic flow chart of a method for preparing a titanium boride alloy by aluminothermic reduction in embodiment 3 of the present invention;
FIG. 4 is an XRD pattern of a titanium boride product obtained in example 3 of the present invention.
Detailed Description
In the embodiment of the invention, the purity of the titanium sponge is more than 99.5%.
In the embodiment of the invention, the aluminum powder contains more than 99.5 percent of Al in percentage by weight.
In the embodiment of the invention, the granularity of the titanium boride powder is 0.010-0.15 mm, the purity is more than or equal to 99.5 percent, and the oxygen content is less than or equal to 0.2 percent.
In the embodiment of the invention, the purity of the sodium fluoborate and the purity of the sodium fluotitanate are both more than 99 percent.
In the embodiment of the invention, the diameter of the briquette is less than or equal to 50mm, and the length of the briquette is less than or equal to 60 mm.
The diameter of the secondary agglomerate in the embodiment of the invention is less than or equal to 50mm, and the length is 60 mm.
In the two-step method in the embodiment of the invention, the crystallization product is 7-10% of cryolite, 75-90% of mono-cryolite, 1-5% of sodium fluorotitanate, 1-5% of sodium fluoroborate and less than or equal to 2% of other fluorides by weight.
In the two-step method in the embodiment of the invention, when the crystallized product reacts with the aluminum powder and the sodium fluoride, the mass percent of titanium in the alloy melt is controlled to be 4.9-5.1%, and the mass percent of boron is controlled to be 0.9-1.1%.
In the embodiment of the invention, when the crystallized product is reacted, the mixed powder is placed in a crucible and then placed in a heating furnace, or the mixed powder is placed in a resistance furnace or a gas heating furnace with an aluminum oxide lining.
In the three-step method in the embodiment of the invention, the mass ratio of aluminum to titanium in the aluminum-titanium alloy is less than or equal to 1.125: 1.
In the three-step method in the embodiment of the invention, the primary crystallization product is generated sodium fluoroaluminate, unreacted sodium fluorotitanate and other fluorides, and comprises 85-95% of cryolite, 1-5% of sodium fluorotitanate and less than or equal to 2% of other fluorides by mass percent.
In the three-step method in the embodiment of the invention, the aluminum-titanium alloy and the titanium boride alloy are added into the aluminum-titanium-boron alloy melt by blowing into the bottom of the alloy melt, and the carrier gas is argon gas when blowing.
In the three-step method provided by the embodiment of the invention, when the primary crystallization product and the secondary crystallization product react with aluminum powder, the mass percent of titanium in the alloy melt is controlled to be 4.9-5.1%, and the mass percent of boron is controlled to be 0.9-1.1%.
In the embodiment of the invention, when the primary crystallization product and the secondary crystallization product react, the mixed powder is placed in a crucible and then is placed in a heating furnace, or the mixed powder is placed in a resistance furnace or a gas heating furnace with an alumina lining.
The structure of the reduction tank adopted in the embodiment of the invention is the same as that of the reduction tank for smelting magnesium by a Pidgeon method, and the reduction tank is heated by coal gas or resistance.
Example 1
The flow chart is shown in figure 1, and a two-step method is adopted;
210 g of sodium fluotitanate, 230 g of sodium fluoborate and 90 g of aluminum powder are uniformly mixed and proportioned, and then the mixture is pressed into a briquette by a briquette machine; wherein the pressure of the pressed briquette is 100MPa;
putting the block mass into a reduction tank for vacuum thermal reduction at 800 ℃ under the vacuum degree of 0.1Pa for 4 hours; after the vacuum thermal reduction is finished, heating to 1200 ℃, carrying out vacuum distillation for 3h, and enabling the evaporated material to enter a crystallizer for crystallization to form a crystallized product; after the vacuum distillation is finished, cooling the residual materials to be less than or equal to 50 ℃ along with the furnace to obtain 60 g of titanium boride alloy and 470 g of crystallized product;
grinding the crystallized product to a granularity of less than or equal to 0.15mm, and then mixing with aluminum powder with a granularity of less than or equal to 0.15mm and sodium fluoride with a granularity of less than or equal to 0.15mm, wherein 352 g of sodium fluoride and 300 g of aluminum powder are mixed to obtain mixed powder;
keeping the temperature of the mixed powder at 1050 ℃ for 2h, wherein the material after the reaction is formed by 812 g of cryolite melt at the upper layer and 310 g of aluminum-titanium-boron alloy melt at the lower layer; the mass percentages of titanium and boron in the cryolite melt are both less than or equal to 0.02 percent;
grinding the titanium boride alloy to the granularity of less than or equal to 0.15mm, pouring the cryolite melt on the upper layer out of the cast ingot, adding 7 g of sponge titanium with the granularity of less than or equal to 1mm and 0.5 g of titanium boride alloy with the granularity of less than or equal to 0.15mm into the aluminum-titanium-boron alloy melt, stirring uniformly, and melting the sponge titanium and the titanium boride alloy to form a mixed melt; and pouring the mixed melt to form an ingot to obtain an aluminum-titanium-boron alloy product, wherein the titanium content is 5.10%, and the boron content is 1.02%.
Example 2
The flow is shown in figure 2, and a three-step method is adopted;
uniformly mixing 210 g of sodium fluotitanate, 90 g of aluminum powder and 84 g of sodium fluoride, and pressing into briquettes by using a briquetting machine; the pressure of the pressed briquette is 100MPa;
putting the block mass into a reduction tank for vacuum thermal reduction at 800 ℃ under the vacuum degree of 0.1Pa for 4 hours; after the vacuum thermal reduction is finished, heating to 1200 ℃, carrying out vacuum distillation for 3h, and enabling the evaporated material to enter a crystallizer for crystallization to form 282 g of a primary crystallization product; after the vacuum distillation is finished, cooling the residual materials to be less than or equal to 50 ℃ along with the furnace to obtain 102 g of aluminum-titanium alloy (the alloy phases are AlTi and Al3Ti, and the molar ratio of aluminum to titanium in the alloy is 2: 1);
grinding the aluminum-titanium alloy until the granularity is less than or equal to 0.15mm, then uniformly mixing the aluminum-titanium alloy with 230 g of sodium fluoborate for batching, pressing the mixture into a secondary briquette by using a briquette machine, wherein the pressure for pressing the secondary briquette is 100MPa;
placing the secondary agglomerates in a reduction tank for secondary vacuum thermal reduction, wherein the temperature of the secondary vacuum thermal reduction is 700 ℃, the vacuum degree is 1Pa, the time is 5h, after the secondary vacuum thermal reduction is finished, heating to 1100 ℃, performing vacuum distillation for 3h, and feeding the evaporated material into a crystallizer for crystallization to form 262 g of secondary crystallization product; cooling the rest materials to less than or equal to 50 ℃ along with the furnace to obtain 70 g of titanium boride alloy;
mixing the primary crystallization product and the secondary crystallization product, grinding the mixture until the granularity is less than or equal to 0.15mm, then mixing the mixture with 300 g of aluminum powder with the granularity less than or equal to 0.15mm, adding 168 g of sodium fluoride, uniformly mixing the mixture to prepare mixed powder, preserving the temperature of the mixed powder for 2h at 1000 ℃, enabling titanium and boron reduced by aluminum to enter an aluminum melt, and enabling the material after the reaction to be composed of 704 g of cryolite melt on the upper layer and 308 g of aluminum-titanium-boron alloy melt on the lower layer; grinding the titanium boride alloy to the granularity of less than or equal to 0.15mm, grinding the aluminum titanium alloy to the granularity of less than or equal to 0.15mm, and pouring the cryolite melt on the upper layer out of the ingot;
adding 15 g of aluminum-titanium alloy with the granularity less than or equal to 0.15mm into the aluminum-titanium-boron alloy melt, adding 2.4 g of titanium boride alloy with the granularity less than or equal to 0.15mm into the aluminum-titanium-boron alloy melt, stirring uniformly, and melting the aluminum-titanium alloy and the titanium boride alloy to form a mixed melt; and pouring the mixed melt to form an ingot, wherein the titanium content in the obtained aluminum-titanium-boron alloy product is 5.10%, and the boron content is 1.02%.
Example 3
The flow is shown in figure 3, and a three-step method is adopted;
uniformly mixing 210 g of sodium fluotitanate, 36 g of aluminum powder and 84 g of sodium fluoride, and pressing into briquettes by using a briquetting machine; the pressure of the pressed briquette is 100MPa;
putting the block mass into a reduction tank for vacuum thermal reduction at 800 ℃ under the vacuum degree of 0.1Pa for 4 hours; after the vacuum thermal reduction is finished, heating to 1100 ℃, carrying out vacuum distillation for 3h, and enabling the evaporated material to enter a crystallizer for crystallization to form 284 g of a primary crystallization product; after the vacuum distillation is finished, cooling the residual materials to less than or equal to 50 ℃ along with the furnace to obtain 46 g of metal titanium (alloy phase Ti);
grinding metal titanium to the granularity of less than or equal to 0.15mm, then uniformly mixing with 230 g of sodium fluoborate, 168 g of sodium fluoride and 54 g of aluminum powder for blending, and pressing into secondary briquettes by using a briquetting machine; the pressure of the pressed briquette is 100MPa;
placing the secondary agglomerate in a reduction tank for secondary vacuum thermal reduction, wherein the temperature of the secondary vacuum thermal reduction is 700 ℃, the vacuum degree is 1Pa, and the time is 5h, after the secondary vacuum thermal reduction is finished, heating to 1100 ℃, carrying out vacuum distillation for 3h, and feeding the evaporated material into a crystallizer for crystallization to form 430 g of secondary crystallization product; cooling the rest materials to less than or equal to 50 ℃ along with the furnace to obtain 68 g of titanium boride alloy; the XRD pattern of the titanium boride alloy is shown in figure 4;
mixing the primary crystallization product and the secondary crystallization product, grinding the mixture until the granularity is less than or equal to 0.15mm, and then mixing the mixture with 300 g of aluminum powder with the granularity being less than or equal to 0.15mm to obtain mixed powder;
placing the mixed powder into a crucible and then placing the crucible into a heating furnace, or placing the mixed powder into an aluminum oxide lined resistance furnace or a coal gas heating furnace, preserving the heat for 1h at the temperature of 100 ℃, enabling titanium and boron reduced by aluminum to enter an aluminum melt, and enabling a material after the reaction to be composed of 707 grams of cryolite melt on the upper layer and 307 grams of aluminum-titanium-boron alloy melt on the lower layer;
grinding titanium boride alloy to the granularity of less than or equal to 0.15mm, grinding metal titanium to the granularity of less than or equal to 0.15mm, pouring the cryolite melt on the upper layer out of the cast ingot, adding 9 g of metal titanium with the granularity of less than or equal to 0.15mm into the aluminum-titanium-boron alloy melt, adding 3 g of titanium boride alloy with the granularity of less than or equal to 0.15mm, stirring uniformly, and melting the metal titanium and the titanium boride alloy to form a mixed melt; and pouring the mixed melt to form an ingot, wherein the titanium content in the obtained aluminum-titanium-boron alloy product is 5.10%, and the boron content is 1.02%.
Claims (6)
1. A method for preparing titanium boride alloy by aluminothermic reduction is characterized by comprising the following steps:
(1) uniformly mixing sodium fluotitanate, sodium fluoborate and aluminum powder, wherein the mass ratio of the sodium fluotitanate to the sodium fluoborate to the aluminum powder is 1 (1.05-1.06) to 0.40-0.43, and then pressing the mixture into briquettes by using a briquetting machine; the pressure for pressing the briquette is 50-100 MPa;
(2) putting the block mass into a reduction tank for vacuum thermal reduction, wherein the temperature of the vacuum thermal reduction is 800-1000 ℃, the vacuum degree is 0.01-10 Pa, and the time is 2-8 h; after the vacuum thermal reduction is finished, heating to 900-1250 ℃, carrying out vacuum distillation, and enabling the evaporated material to enter a crystallizer for crystallization to form a crystallized product; after the vacuum distillation is finished, cooling the residual materials to be less than or equal to 50 ℃ along with the furnace to obtain titanium boride alloy; the crystallization product comprises 7-10% of cryolite, 75-90% of cryolite, 1-5% of sodium fluorotitanate, 1-5% of sodium fluoroborate and less than or equal to 2% of other fluorides by weight.
2. A method for preparing titanium boride alloy by aluminothermic reduction is characterized by comprising the following steps:
(1) uniformly mixing sodium fluotitanate, aluminum powder and sodium fluoride, wherein the mass ratio of the sodium fluotitanate to the aluminum powder to the sodium fluoride is 2.50 (0.43-1.07): 1.00, and then pressing the mixture into briquettes by using a briquetting machine; the pressure for pressing the briquette is 50-100 MPa;
(2) putting the block mass into a reduction tank for vacuum thermal reduction, wherein the temperature of the vacuum thermal reduction is 700-1000 ℃, the vacuum degree is 0.1-10 Pa, and the time is 2-8 h; after the vacuum thermal reduction is finished, heating to 1050-1250 ℃, carrying out vacuum distillation, and enabling the evaporated material to enter a crystallizer for crystallization to form a primary crystallization product; after the vacuum distillation is finished, cooling the residual materials to be less than or equal to 50 ℃ along with the furnace to obtain aluminum-titanium alloy or metal titanium; the primary crystallization product is generated sodium fluoroaluminate, unreacted sodium fluorotitanate and other fluorides, and comprises 85-95% of cryolite, 1-5% of sodium fluorotitanate and less than or equal to 2% of other fluorides by mass percent;
(3) grinding an aluminum-titanium alloy or metal titanium to the granularity of less than or equal to 0.15mm, then uniformly mixing with sodium fluoborate and sodium fluoride, wherein the mass ratio of the sodium fluoride to the sodium fluoborate is 0.76:1, the molar ratio of aluminum to the sodium fluoborate in all materials is 1:1, adding aluminum powder when the aluminum in all materials is insufficient, and pressing into secondary briquettes by using a briquetting machine; or crushing and grinding the aluminum-titanium alloy until the granularity is less than or equal to 0.15mm, then uniformly mixing the aluminum-titanium alloy with sodium fluoborate, uniformly mixing the aluminum-titanium alloy and the sodium fluoborate, wherein the molar ratio of the aluminum to the sodium fluoborate in all the materials is 1:1, adding aluminum powder when the aluminum in all the materials is insufficient, and pressing the mixture into secondary briquettes by using a briquetting machine;
(4) placing the secondary block mass in a reduction tank for secondary vacuum thermal reduction, wherein the temperature of the secondary vacuum thermal reduction is 600-900 ℃, the vacuum degree is 0.1-10 Pa, the time is 2-8 h, after the secondary vacuum thermal reduction is finished, the temperature is raised to 900-1200 ℃, vacuum distillation is carried out, and the evaporated material enters a crystallizer for crystallization to form a secondary crystallization product; cooling the rest materials to less than or equal to 50 ℃ along with the furnace to obtain the titanium boride alloy.
3. The aluminothermic reduction method for preparing titanium boride alloy according to claim 1, wherein the crystallized product of step (2) is ground to a particle size of 0.15mm or less, and then mixed with aluminum powder having a particle size of 0.15mm or less and sodium fluoride having a particle size of 0.15mm or less, the mixing ratio is (1-5): 1, the mass ratio of the crystallized product to the aluminum powder is 1 (0.63-0.65), and mixed powder is obtained; placing the mixed powder into a crucible and then placing the crucible into a heating furnace, or placing the mixed powder into an aluminum oxide lined resistance furnace or a coal gas heating furnace, preserving the heat for 1-3 h at 950-1100 ℃, allowing titanium and boron reduced by aluminum to enter an aluminum melt, and allowing the reacted material to consist of a cryolite melt at the upper layer and an aluminum-titanium-boron alloy melt at the lower layer; grinding the titanium boride alloy to a granularity of less than or equal to 0.15mm, pouring out the cryolite melt on the upper layer, adding sponge titanium with the granularity of less than or equal to 1mm and titanium boride alloy with the granularity of less than or equal to 0.15mm into the aluminum-titanium-boron alloy melt, stirring uniformly and melting the sponge titanium and the titanium boride alloy to form a mixed melt, wherein the mass ratio of the sponge titanium to the titanium boride alloy is (27-29) = (0.7-0.9): 1; and pouring the mixed melt to form an ingot to obtain an aluminum-titanium-boron alloy product.
4. The method for preparing the titanium boride alloy through the aluminothermic reduction according to claim 3, wherein the mass percent of titanium in the aluminum-titanium-boron alloy melt is 4.9-5.1%, and the mass percent of boron is 0.9-1.1%; the mass percentages of titanium and boron in the cryolite melt are both less than or equal to 0.02 percent.
5. The aluminothermic reduction method for producing a titanium boride alloy according to claim 2, wherein the primary crystallized product of step (2) and the secondary crystallized product of step (4) are mixed, ground to a particle size of 0.15mm or less, and then mixed with aluminum powder having a particle size of 0.15mm or less to obtain a mixed powder; wherein the mass ratio of the primary crystallization product to the secondary crystallization product is aluminum powder = (1-5): 1; when no sodium fluoride is added in the step 3, adding sodium fluoride into the mixed powder and then mixing, wherein the adding amount of the sodium fluoride is 0.65 times of the mass of the secondary crystallization product; placing the mixed powder into a crucible and then placing the crucible into a heating furnace, or placing the mixed powder into an aluminum oxide lined resistance furnace or a coal gas heating furnace, preserving the heat for 1-3 h at 950-1100 ℃, allowing titanium and boron reduced by aluminum to enter an aluminum melt, and allowing the reacted material to consist of a cryolite melt at the upper layer and an aluminum-titanium-boron alloy melt at the lower layer; grinding a titanium boride alloy to a granularity of less than or equal to 0.15mm, grinding an aluminum-titanium alloy or metal titanium to a granularity of less than or equal to 0.15mm, pouring out the cryolite melt on the upper layer, adding the aluminum-titanium alloy or metal titanium with the granularity of less than or equal to 0.15mm into the aluminum-titanium-boron alloy melt, adding the titanium boride alloy with the granularity of less than or equal to 0.15mm, stirring uniformly, and melting the titanium boride alloy and the aluminum-titanium alloy or metal titanium boride to form a mixed melt, wherein the mass ratio of the aluminum-titanium-boron alloy melt to the aluminum-titanium alloy to the titanium boride alloy is (28-30) = (0.9-1.7): 1, or the mass ratio of the aluminum-titanium-boron alloy melt to the titanium boride alloy is (28-30) = (0.9-1.0): 1); and pouring the mixed melt to form an ingot to obtain an aluminum-titanium-boron alloy product.
6. The method for preparing the titanium boride alloy through the aluminothermic reduction according to claim 5, wherein the mass percent of titanium in the aluminum-titanium-boron alloy melt is 4.9-5.1%, and the mass percent of boron is 0.9-1.1%; the mass percentages of titanium and boron in the cryolite melt are both less than or equal to 0.02 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810203148.3A CN108439422B (en) | 2018-03-13 | 2018-03-13 | Method for preparing titanium boride alloy through aluminothermic reduction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810203148.3A CN108439422B (en) | 2018-03-13 | 2018-03-13 | Method for preparing titanium boride alloy through aluminothermic reduction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108439422A CN108439422A (en) | 2018-08-24 |
| CN108439422B true CN108439422B (en) | 2021-10-15 |
Family
ID=63194820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810203148.3A Active CN108439422B (en) | 2018-03-13 | 2018-03-13 | Method for preparing titanium boride alloy through aluminothermic reduction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108439422B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109179444B (en) * | 2018-10-11 | 2020-08-25 | 武汉科技大学 | Preparation method of amorphous boron powder |
| CN111498849B (en) * | 2020-06-08 | 2021-11-02 | 长江师范学院 | Aluminothermic reduction preparation of Ti2Method for preparing AlC ceramic powder |
| CN115321589B (en) * | 2022-09-16 | 2023-09-12 | 东北大学 | Comprehensive utilization method of byproducts in process of preparing titanium or titanium alloy by aluminothermic reduction of fluorotitanate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583421A (en) * | 2012-03-07 | 2012-07-18 | 深圳市新星轻合金材料股份有限公司 | Circulated preparation method for producing titanium boride and sodium cryolite synchronously by adopting mixture of sodium-based titanium boron villiaumite as intermediate raw material |
| CN102583422A (en) * | 2012-03-07 | 2012-07-18 | 深圳市新星轻合金材料股份有限公司 | Cyclic preparation method for producing titanium boride by taking potassium-based titanium boron villiaumite mixture as intermediate raw material and synchronously producing potassium cryolite |
| CN102689907A (en) * | 2012-05-30 | 2012-09-26 | 深圳市新星轻合金材料股份有限公司 | Preparing method and application of transition metal boride |
| CN104911376A (en) * | 2015-07-17 | 2015-09-16 | 东北大学 | Method of preparing titanium or titanium-aluminum alloy and additionally producing titanium-free cryolite through two-stage aluminothermic reduction |
| CN105441695A (en) * | 2015-11-25 | 2016-03-30 | 东北大学 | Method for preparing titanium or titanium-aluminum alloy with high-titanium aluminum-titanium alloy as reducing agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63140059A (en) * | 1986-12-03 | 1988-06-11 | Nippon Light Metal Co Ltd | High-strength aluminum alloy |
-
2018
- 2018-03-13 CN CN201810203148.3A patent/CN108439422B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583421A (en) * | 2012-03-07 | 2012-07-18 | 深圳市新星轻合金材料股份有限公司 | Circulated preparation method for producing titanium boride and sodium cryolite synchronously by adopting mixture of sodium-based titanium boron villiaumite as intermediate raw material |
| CN102583422A (en) * | 2012-03-07 | 2012-07-18 | 深圳市新星轻合金材料股份有限公司 | Cyclic preparation method for producing titanium boride by taking potassium-based titanium boron villiaumite mixture as intermediate raw material and synchronously producing potassium cryolite |
| CN102689907A (en) * | 2012-05-30 | 2012-09-26 | 深圳市新星轻合金材料股份有限公司 | Preparing method and application of transition metal boride |
| CN104911376A (en) * | 2015-07-17 | 2015-09-16 | 东北大学 | Method of preparing titanium or titanium-aluminum alloy and additionally producing titanium-free cryolite through two-stage aluminothermic reduction |
| CN105441695A (en) * | 2015-11-25 | 2016-03-30 | 东北大学 | Method for preparing titanium or titanium-aluminum alloy with high-titanium aluminum-titanium alloy as reducing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108439422A (en) | 2018-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109536751B (en) | Method for producing magnesium-lithium alloy and by-product magnesium aluminate spinel by aluminothermic reduction | |
| CA2992502C (en) | Method for producing titanium or titanium aluminum alloys through two-stage aluminothermic reduction and obtaining titanium-free cryolite as byproducts | |
| CN108439422B (en) | Method for preparing titanium boride alloy through aluminothermic reduction | |
| JP6810243B2 (en) | Manufacturing method of titanium alloy based on thermite self-propagation gradient reduction and slag cleaning refining | |
| CN112593110B (en) | Preparation method of nano-carbide reinforced aluminum matrix composite welding wire | |
| US10202701B2 (en) | Potassium cryolite for aluminum electrolysis industry and preparation method thereof | |
| CN104789811A (en) | Preparation method of aluminum-titanium-boron intermediate alloy | |
| CN100516262C (en) | Method for preparing magnesium and magnesium alloy composite grain refiner | |
| Zhao et al. | Mechanism and kinetic analysis of vacuum aluminothermic reduction for preparing TiAl intermetallics powder | |
| US20090311123A1 (en) | Method for producing metal alloy and intermetallic products | |
| CN111020300B (en) | Preparation method of thermal cracking resistant binary nanoparticle reinforced aluminum matrix composite | |
| CN109554570B (en) | Method for strengthening aluminum alloy by in-situ multiphase mixed scale ceramic in melt | |
| CN110205652B (en) | Preparation method and application of copper-scandium intermediate alloy | |
| CN114427048B (en) | Aluminum-based grain refiner containing high-entropy boride and preparation method thereof | |
| CN112919470B (en) | Production process of titanium silicon carbide | |
| US6908599B2 (en) | Process for the production of zirconium boride powder | |
| Amosov et al. | Fabrication of Al-AlN nanocomposites | |
| CN111455207B (en) | Method for preparing magnesium-scandium alloy by precursor process and magnesium-scandium alloy prepared by method | |
| CN109019625B (en) | Method for preparing titanium boride powder | |
| CN108796261B (en) | In-situ self-generated TiB2Particle reinforced aluminum-based composite material and preparation method thereof | |
| CN109811161B (en) | Large-volume-number nanoscale Al-TiB2Intermediate alloy and preparation method thereof | |
| CN111910092A (en) | Preparation method of aluminum-niobium-boron intermediate alloy and aluminum-niobium-boron intermediate alloy | |
| RU2754862C1 (en) | Method for producing silumins using amorphous microsilica | |
| CN113913629B (en) | Purification slag for metal chromium smelting and smelting method of metal chromium | |
| CN101008053B (en) | Method for preparing ferrotitanium and silicon ferrotitanium using high magnesium and low titanium concentrate |
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 |