CN108439422A - A kind of method that aluminothermic reduction prepares boronation titanium alloy - Google Patents
A kind of method that aluminothermic reduction prepares boronation titanium alloy Download PDFInfo
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Abstract
A kind of method that aluminothermic reduction prepares boronation titanium alloy, is divided into two-step method and three-step approach；Two-step method is to mix titanium sodium fluoride, sodium fluoborate with aluminium powder to be pressed into agglomerate；It is placed in reductive jar after carrying out vacuum-thermal reduction to heat up and be evaporated in vacuo, the material crystallization of evaporation, surplus material cooling obtains boronation titanium alloy；Three-step approach is to mix titanium sodium fluoride, aluminium powder with sodium fluoride to be pressed into agglomerate, and heating up after vacuum-thermal reduction is evaporated in vacuo, and evaporation material crystallization, surplus material is aluminum titanium alloy or Titanium；It is mixed with sodium fluoborate and sodium fluoride after levigate and is pressed into secondary agglomerate；It is evaporated in vacuo after two sections of vacuum-thermal reductions, evaporation material crystallization, surplus material is boronation titanium alloy.Titanium boride powder purity produced by the invention is high, and granularity is controllable, at low cost, and by-product ice crystal and Al-Ti-B alloy are the more product of commercial Application.
Description
Technical field
The invention belongs to metallurgical technology field, more particularly to a kind of method of aluminothermic reduction preparation boronation titanium alloy.
Background technology
Titanium diboride powder is the crystal of grey or grey black, anti-oxidant in air since it has very high hardness,
Can resist melt corrosion of metal, therefore be widely used in preparing the strong of composite ceramic articles, molten metal crucible and metal material
Agent, it may also be used for manufacture finishing tool, various molds, sealing element, various high-temperature components etc., are a kind of high added values
Dusty material.
The production method of titanium boride mainly has direct synthesis technique, carbothermic method, metallothermic processes and gas phase heavy at present
Area method；Direct synthesis technique is using titanium valve and high purity boron powder synthesis titanium diboride:Ti+2B=TiB2, the method is of high cost, only in reality
Testing room has application；Carbothermic method is to use activated carbon as reducing agent, and using boron oxide or boron carbide as boron source, titanium source is adopted
With titanium dioxide, at a high temperature of 1800~1900 DEG C carrying out reduction prepares titanium boride, and equipment mostly uses greatly vacuum carbon tube furnace, should
Main problem existing for method is that the product granularity produced is larger, and purity is relatively low；Metallothermic processes, i.e. self propagating high temperature are closed
It is that aluminium powder or magnesium powder is used to restore the method that titanium dioxide and boron oxide produce titanium boride as reducing agent at (SHS) technique,
The high temperature generated using reduction reaction, makes reaction that can carry out automatically after initiation, is not necessarily to external heat source, you can reaction is completed,
But its product titanium diboride produced contains more aluminium or magnesium, and purity is poor；Vapour deposition process is with TiCl4And BCl3For original
Material, using H2Reduction deposition titanium diboride powder, depositing temperature are 800-1000 DEG C, and abrasive material grade and electronics can be made after deposition
Grade product, this method can get high-purity and ultra-fine titanium boride powder, but cost is higher；Therefore, the life of industrial titanium boride powder at present
Or production method cost is too high or purity is poor, its further application is affected.
Invention content
For the above problem existing for existing titanium boride generation technique, the present invention provides a kind of aluminothermic reductions to prepare boronation
The method of titanium alloy, using aluminium powder as reducing agent, using titanium sodium fluoride and sodium fluoborate as raw material, vacuum-thermal reduction prepares titanium boride conjunction
Bronze；While cost is reduced, high-purity powders of titanium boride is obtained；This method is divided into two-step method or three-step approach, and when two steps will
Titanium sodium fluoride and sodium fluoborate and aluminium powder mixing briquetting, then vacuum-thermal reduction directly prepare boronation titanium alloy and ice crystal, and three
Aluminum titanium alloy powder is produced using aluminothermy vacuum reduction titanium sodium fluoride when step, then restores fluoboric acid by reducing agent of aluminum titanium alloy powder
Sodium prepares titanium boride powder.
The method one of the present invention carries out according to the following steps：
1, titanium sodium fluoride, sodium fluoborate are uniformly mixed dispensing, titanium sodium fluoride with aluminium powder:Sodium fluoborate:Aluminium powder dispensing
Ratio is 1 in mass ratio:(1.05~1.06):(0.40~0.43), is then pressed into agglomerate with briquetting machine；
2, agglomerate is placed in reductive jar and carries out vacuum-thermal reduction, the temperature of vacuum-thermal reduction is 800~1000 DEG C, vacuum
Degree is 0.01~10Pa, and the time is 2~8h；It is warming up to 900~1250 DEG C after vacuum-thermal reduction, is evaporated in vacuo, steams
The material of hair enters crystallizer crystallization, forms crystallized product；After the completion of vacuum distillation, remaining material cools to≤50 with the furnace
DEG C, obtain boronation titanium alloy.
The above method vacuum-thermal reduction reaction reaction equation be：
3Na2TiF6+6NaBF4+ 10Al=3TiB2+Na3AlF6+9NaAlF4 (1)。
In the above method, the pressure for suppressing agglomerate is 50~100MPa.
In the above method, the crystallized product of acquisition is ice crystal, single ice crystal, unreacted titanium sodium fluoride, unreacted
Sodium fluoborate and other fluorides, contain ice crystal 7~10% by weight percentage, single ice crystal 75~90%, and titanium sodium fluoride 1~
5%, sodium fluoborate 1~5%, other fluoride≤2%.
Above-mentioned crystallized product is levigate to granularity≤0.15mm, then with granularity≤0.15mm aluminium powders and granularity≤0.15mm
Sodium fluoride mixes, and mixed proportion is (1~5) by the mass ratio of crystallized product and aluminium powder:1, the quality of crystallized product and sodium fluoride
Than being 1:(0.63~0.65) obtains mixed-powder；Mixed-powder is placed in crucible and is then placed in heating furnace, or will mixing
Powder is placed in the resistance furnace or gas-fired furnace that liner is aluminum oxide, and 1~3h, quilt are kept the temperature under the conditions of 950~1100 DEG C
The titanium and boron of aluminium reducing enter aluminum melt, ice crystal (cryolite) melt and lower layer of the material after the completion of reacting by upper layer
Al-Ti-B alloy melt is constituted；Boronation titanium alloy is levigate to granularity≤0.15mm, the cryolite melts on upper layer are poured out, then
The boronation titanium alloy of the titanium sponge and granularity≤0.15mm of granularity≤1mm, in mass ratio aluminium are added into Al-Ti-B alloy melt
Ti-B alloy melt:Titanium sponge:Boronation titanium alloy=(27~29):(0.7~0.9):1, be stirred for uniformly and make titanium sponge and
Titanium boride alloy molten forms blend melt；Blend melt is poured into a mould to form ingot casting, obtains Al-Ti-B alloy product.
Single ice crystal is reacted to ice crystal with sodium fluoride in above-mentioned crystallized product, and reaction equation is：
NaAlF4+ 2NaF=Na3AlF6 (2)。
When above-mentioned crystallized product is reacted with aluminium powder and sodium fluoride, the quality hundred of titanium in Al-Ti-B alloy melt is controlled
Divide ratio 4.9~5.1%, the mass percent of boron is 0.9~1.1%；The quality hundred of titanium and boron in the cryolite melts of acquisition
Divide than≤0.02%.
The method two of the present invention carries out according to the following steps：
1, titanium sodium fluoride, aluminium powder are uniformly mixed dispensing, titanium sodium fluoride with sodium fluoride:Aluminium powder:The ratio of sodium fluoride presses matter
Amount is than being 2.50:(0.43~1.07):1.00, then agglomerate is pressed into briquetting machine；
2, agglomerate is placed in reductive jar and carries out vacuum-thermal reduction, the temperature of vacuum-thermal reduction is 700~1000 DEG C, vacuum
Degree is 0.1~10Pa, and the time is 2~8h；It is warming up to 1050~1250 DEG C after vacuum-thermal reduction, is evaporated in vacuo, steams
The material of hair enters crystallizer crystallization, forms primary crystallization product；After the completion of vacuum distillation, remaining material cools to the furnace≤
50 DEG C, obtain aluminum titanium alloy or Titanium；
3, aluminum titanium alloy or Titanium is levigate to granularity≤0.15mm, then it is uniformly mixed with sodium fluoborate and sodium fluoride
The mass ratio of dispensing, wherein sodium fluoride and sodium fluoborate is 0.76:1, the molar ratio of aluminium and sodium fluoborate in whole materials is
1:1, aluminium powder is added when aluminium deficiency in whole materials, then secondary agglomerate is pressed into briquetting machine；Or aluminum titanium alloy is crushed
It is levigate that dispensing is then uniformly mixed with sodium fluoborate to granularity≤0.15mm, mole of aluminium and sodium fluoborate in whole materials
Than being 1:1, aluminium powder is added when aluminium deficiency in whole materials, then secondary agglomerate is pressed into briquetting machine；
4, secondary agglomerate is placed in reductive jar two sections of vacuum-thermal reductions of progress, the temperature 600 of two sections of vacuum-thermal reductions~
900 DEG C, 0.1~10Pa of vacuum degree, 2~8h of time, it is warming up to 900~1200 DEG C after two sections of vacuum-thermal reductions, carries out true
The material of sky distillation, evaporation enters crystallizer crystallization, forms secondary crystallization product；Remaining material cools to≤50 DEG C with the furnace,
Obtain boronation titanium alloy.
In the above method two, the reaction equation of the vacuum-thermal reduction reaction of step 2 is：
3Na2TiF6+ (3x+4) Al+6NaF=3AlxTi+4Na3AlF6(3)；
Wherein x=0~2；As x=0, the 3Al of acquisitionxTi is Titanium.
In the above method two, when having sodium fluoride in the dispensing of step 3, secondary vacuum thermal reduction reaction is anti-in step 4
Ying Shiwei：
AlxTi+2NaBF4+ (2-x) Al+4NaF=TiB2+2Na3AlF6(4)；
Wherein x=0~2；As x=0, the 3Al that usesxTi is Titanium, as x=2, does not add aluminium powder；
When not having sodium fluoride in the dispensing of step 3, the reaction equation of secondary vacuum thermal reduction reaction is in step 4：
AlxTi+2NaBF4+ (2-x) Al=TiB2+2NaAlF4(5)；
Wherein x=0~2；As x=0, the 3Al that usesxTi is Titanium, as x=2, does not add aluminium powder.
In the above method two, the pressure for suppressing agglomerate is 50~100MPa.
Above-mentioned primary crystallization product and secondary crystallization product mixing, it is levigate to granularity≤0.15mm, then with granularity≤
The aluminium powder of 0.15mm mixes, and obtains mixed-powder；Wherein primary crystallization product in mass ratio:Secondary crystallization product:Aluminium powder=(1-
5):(1-5):1；It when step 3 is without being added sodium fluoride, is remixed after being additionally added sodium fluoride in mixed-powder, sodium fluoride adds
Enter 0.65 times that amount is secondary crystallization product quality；Mixed-powder is placed in crucible and is then placed in heating furnace, or will mixing
Powder is placed in the resistance furnace or gas-fired furnace that liner is aluminum oxide, and 1~3h, quilt are kept the temperature under the conditions of 950~1100 DEG C
The titanium and boron of aluminium reducing enter aluminum melt, ice crystal (cryolite) melt and lower layer of the material after the completion of reacting by upper layer
Al-Ti-B alloy melt is constituted；Boronation titanium alloy is levigate to granularity≤0.15mm, aluminum titanium alloy or Titanium is levigate to grain
Degree≤0.15mm pours out the cryolite melts on upper layer, and the aluminium of granularity≤0.15mm is then added into Al-Ti-B alloy melt
Titanium alloy or Titanium, and the boronation titanium alloy of granularity≤0.15mm, in mass ratio Al-Ti-B alloy melt is added:Aluminium titanium closes
Gold:Boronation titanium alloy=(28~30):(0.9~1.7):1, or Al-Ti-B alloy melt in mass ratio:Titanium:Titanium boride
Alloy=(28~30):(0.9~1.0):1, it is stirred for uniformly and make boronation titanium alloy and aluminum titanium alloy or Titanium to melt
Form blend melt；Blend melt is poured into a mould to form ingot casting, obtains Al-Ti-B alloy product.
In above-mentioned method two, single ice crystal is reacted to ice crystal with sodium fluoride in secondary crystallization product, and reaction equation is same
Reaction equation (2).
In above-mentioned method two, in the aluminum titanium alloy that step 2 obtains, mass ratio≤1.125 of aluminium and titanium:1 (i.e. molar ratio
≤2:1)。
In above-mentioned method two, primary crystallization product is cryolite, unreacted sodium fluoborate and the other fluorine generated
Compound contains ice crystal 85~95%, sodium fluoborate 1~5%, other fluoride≤2% by mass percentage.
In above-mentioned method two, aluminum titanium alloy and boronation titanium alloy are added into Al-Ti-B alloy melt to be closed by being blown into
The mode of golden melt bottom is added, and carrier gas is argon gas when being blown into.
When above-mentioned primary crystallization product, secondary crystallization product are reacted with aluminium powder, the matter of titanium in alloy melt is controlled
Percentage is measured 4.9~5.1%, the mass percent of boron is 0.9~1.1%；The matter of titanium and boron in the cryolite melts of acquisition
Measure percentage≤0.02%.
The ice crystal obtained after the cryolite melts solidification that above two method obtains can be used for aluminium electroloysis industry, acquisition
By-product Al-Ti-B alloy product can be used as grain refiner for casting industry.
The titanium boride powder purity of technique productions is high through the invention, and granularity is controllable, at low cost, by-product ice crystal and aluminium titanium
Boron alloy is the more product of commercial Application；It is generated without any exhaust gas, waste water and solid waste in production process, is one
The production technology of kind green.
Description of the drawings
Fig. 1 is that the aluminothermic reduction of the embodiment of the present invention 1 prepares the method flow schematic diagram of boronation titanium alloy；
Fig. 2 is that the aluminothermic reduction of the embodiment of the present invention 2 prepares the method flow schematic diagram of boronation titanium alloy；
Fig. 3 is that the aluminothermic reduction of the embodiment of the present invention 3 prepares the method flow schematic diagram of boronation titanium alloy；
Fig. 4 is the XRD diagram for the boronation titanium products that the embodiment of the present invention 3 obtains.
Specific implementation mode
99.5% or more titanium sponge purity in the embodiment of the present invention.
Aluminium powder contains 99.5% or more Al by weight percentage in the embodiment of the present invention.
Titanium boride powder granularity is in 0.010~0.15mm, purity >=99.5%, oxygen content≤0.2% in the embodiment of the present invention.
The purity of sodium fluoborate and titanium sodium fluoride is all higher than 99% in the embodiment of the present invention.
Agglomerate diameter≤50mm of method one and method two in the embodiment of the present invention, length≤60mm.
Secondary agglomerate diameter≤50mm, length 60mm in the embodiment of the present invention.
Crystallized product is ice crystal, single ice crystal, unreacted titanium sodium fluoride, unreacted fluorine boron in the embodiment of the present invention
Sour sodium and other fluorides, contain ice crystal 7~10% by weight percentage, single ice crystal 75~90%, titanium sodium fluoride 1~5%,
Sodium fluoborate 1~5%, other fluoride≤2%.
When crystallized product is reacted with aluminium powder and sodium fluoride in the embodiment of the present invention, the quality of titanium in alloy melt is controlled
Percentage is 4.9~5.1%, and the mass percent of boron is 0.9~1.1%.
When crystallized product reacts in the embodiment of the present invention, mixed-powder is placed in crucible and is then placed in heating furnace, or will
Mixed-powder is placed in the resistance furnace or gas-fired furnace that liner is aluminum oxide.
In the embodiment of the present invention when three-step approach, mass ratio≤1.125 of aluminium and titanium in aluminum titanium alloy:1.
In the embodiment of the present invention when three-step approach, primary crystallization product is the cryolite generated, unreacted sodium fluoborate
And other fluorides, contain ice crystal 85~95%, sodium fluoborate 1~5%, other fluoride≤2% by mass percentage.
In the embodiment of the present invention when three-step approach, it is logical that aluminum titanium alloy and boronation titanium alloy, which is added, into Al-Ti-B alloy melt
It crosses and is blown into the mode of alloy melt bottom and is added, carrier gas is argon gas when being blown into.
In the embodiment of the present invention when three-step approach, when primary crystallization product, secondary crystallization product are reacted with aluminium powder, control
The mass percent of titanium is 4.9~5.1% in alloy melt, and the mass percent of boron is 0.9~1.1%.
When primary crystallization product and secondary crystallization product react in the embodiment of the present invention, then mixed-powder is placed in crucible
It is put into heating furnace, or mixed-powder is placed in the resistance furnace or gas-fired furnace that liner is aluminum oxide.
The structure of the reductive jar used in the embodiment of the present invention is identical as the reduction jar structure of production of magnesium by pidgeonprocess, and reductive jar adds
Thermal recovery heated by gas or resistance heating.
Embodiment 1
Flow is as shown in Figure 1, using two-step method；
210 grams of titanium sodium fluoride, 230 grams of sodium fluoborate are uniformly mixed dispensing for 90 grams with aluminium powder, then suppressed with briquetting machine
At agglomerate；The pressure of wherein compacting agglomerate is 100MPa；
Agglomerate is placed in reductive jar and carries out vacuum-thermal reduction, the temperature of vacuum-thermal reduction is 800 DEG C, and vacuum degree is
0.1Pa, time 4h；It is warming up to 1200 DEG C after vacuum-thermal reduction, carries out vacuum distillation 3h, the material of evaporation enters crystallization
Device crystallizes, and forms crystallized product；After the completion of vacuum distillation, remaining material cools to≤50 DEG C with the furnace, obtains boronation titanium alloy
60 grams, 470 grams of crystallized product；
Crystallized product is levigate to granularity≤0.15mm, then with granularity≤0.15mm aluminium powders and granularity≤0.15mm sodium fluorides
Mixing, wherein 300 grams of 352 grams of sodium fluoride and aluminium powder, obtain mixed-powder；
Mixed-powder is kept the temperature into 2h under the conditions of 1050 DEG C, the material after the completion of reacting is melted by 812 grams of ice crystals on upper layer
310 grams of compositions of body and the Al-Ti-B alloy melt of lower layer；In cryolite melts the mass percent of titanium and boron≤0.02%；
Boronation titanium alloy is levigate to granularity≤0.15mm, the cryolite melts on upper layer are poured out into ingot casting, then to aluminium titanium
0.5 gram of the boronation titanium alloy of 7 grams of the titanium sponge and granularity≤0.15mm of granularity≤1mm is added in B alloy melt, is stirred for
It is even and titanium sponge and titanium boride alloy molten is made to form blend melt；Blend melt is poured into a mould to form ingot casting, aluminium titanium boron is obtained and closes
Golden product, Ti content 5.10%, boron content 1.02%.
Embodiment 2
Flow is as shown in Fig. 2, using three-step approach；
210 grams of titanium sodium fluoride, 90 grams of aluminium powder are uniformly mixed dispensing for 84 grams with sodium fluoride, then suppressed with briquetting machine agglomerating
Block；The pressure for suppressing agglomerate is 100MPa；
Agglomerate is placed in reductive jar and carries out vacuum-thermal reduction, the temperature of vacuum-thermal reduction is 800 DEG C, and vacuum degree is
0.1Pa, time 4h；It is warming up to 1200 DEG C after vacuum-thermal reduction, carries out vacuum distillation 3h, the material of evaporation enters crystallization
Device crystallizes, and forms 282 grams of primary crystallization product；After the completion of vacuum distillation, remaining material cools to≤50 DEG C with the furnace, obtains aluminium
(alloy object is mutually AlTi and Al3Ti to 102 grams of titanium alloy, and the molar ratio of Aluminum in Alloy and titanium is 2:1)；
Aluminum titanium alloy is levigate to granularity≤0.15mm, it then is uniformly mixed dispensing with 230 grams of sodium fluoborates, uses briquetting machine
It is pressed into secondary agglomerate, the pressure for suppressing secondary agglomerate is 100MPa；
Secondary agglomerate is placed in reductive jar and carries out two sections of vacuum-thermal reductions, 700 DEG C of the temperature of two sections of vacuum-thermal reductions, very
Reciprocal of duty cycle 1Pa, time 5h are warming up to 1100 DEG C after two sections of vacuum-thermal reductions, carry out vacuum distillation 3h, and the material of evaporation enters
Crystallizer crystallizes, and forms 262 grams of secondary crystallization product；Remaining material cools to≤50 DEG C with the furnace, obtains boronation titanium alloy 70
Gram；
Primary crystallization product and secondary crystallization product mixing, it is levigate to granularity≤0.15mm, then with granularity≤0.15mm
The mixing of 300 grams of aluminium powder, add 168 grams of sodium fluoride and be uniformly mixed mixed-powder is made, by mixed-powder in 1000 DEG C of conditions
Lower heat preservation 2h enters aluminum melt by the titanium of aluminium reducing and boron, the material after the completion of reacting by upper layer 704 grams of cryolite melts and
308 grams of compositions of Al-Ti-B alloy melt of lower layer；Boronation titanium alloy is levigate to granularity≤0.15mm, aluminum titanium alloy is levigate extremely
The cryolite melts on upper layer are poured out ingot casting by granularity≤0.15mm；
15 grams of the aluminum titanium alloy of granularity≤0.15mm is added into Al-Ti-B alloy melt, and is added granularity≤0.15mm's
2.4 grams of boronation titanium alloy is stirred for uniformly and makes aluminum titanium alloy and titanium boride alloy molten to form blend melt；By blend melt
Cast forms ingot casting, and Ti content is 5.10% in the Al-Ti-B alloy product of acquisition, boron content 1.02%.
Embodiment 3
Flow is as shown in figure 3, using three-step approach；
210 grams of titanium sodium fluoride, 36 grams of aluminium powder are uniformly mixed dispensing for 84 grams with sodium fluoride, then suppressed with briquetting machine agglomerating
Block；The pressure for suppressing agglomerate is 100MPa；
Agglomerate is placed in reductive jar and carries out vacuum-thermal reduction, the temperature of vacuum-thermal reduction is 800 DEG C, and vacuum degree is
0.1Pa, time 4h；It is warming up to 1100 DEG C after vacuum-thermal reduction, carries out vacuum distillation 3h, the material of evaporation enters crystallization
Device crystallizes, and forms 284 grams of primary crystallization product；After the completion of vacuum distillation, remaining material cools to≤50 DEG C with the furnace, obtains gold
Belong to 46 grams of titanium (alloy object phase Ti)；
Titanium is levigate to granularity≤0.15mm, then with 54 grams of 230 grams of sodium fluoborate, 168 grams of sodium fluoride and aluminium powder
It is uniformly mixed dispensing, then secondary agglomerate is pressed into briquetting machine；The pressure for suppressing agglomerate is 100MPa；
Secondary agglomerate is placed in reductive jar and carries out two sections of vacuum-thermal reductions, 700 DEG C of the temperature of two sections of vacuum-thermal reductions, very
Reciprocal of duty cycle 1Pa, time 5h are warming up to 1100 DEG C after two sections of vacuum-thermal reductions, carry out vacuum distillation 3h, and the material of evaporation enters
Crystallizer crystallizes, and forms 430 grams of secondary crystallization product；Remaining material cools to≤50 DEG C with the furnace, obtains boronation titanium alloy 68
Gram；Boronation titanium alloy XRD diagram is as shown in Figure 4；
Primary crystallization product and secondary crystallization product mixing, it is levigate to granularity≤0.15mm, then with granularity≤0.15mm
The mixing of 300 grams of aluminium powder, obtain mixed-powder；
Mixed-powder is placed in crucible and is then placed in heating furnace, or it is aluminum oxide that mixed-powder, which is placed in liner,
In resistance furnace or gas-fired furnace, 1h is kept the temperature under the conditions of 100 DEG C, aluminum melt is entered by the titanium of aluminium reducing and boron, reaction is completed
Material afterwards is made of 307 grams of the Al-Ti-B alloy melt of 707 grams of the cryolite melts on upper layer and lower layer；
Boronation titanium alloy is levigate to granularity≤0.15mm, Titanium is levigate to granularity≤0.15mm, by the ice on upper layer
Spar melt pours out ingot casting, and 9 grams of the Titanium of granularity≤0.15mm is then added into Al-Ti-B alloy melt, and granularity is added
3 grams of the boronation titanium alloy of≤0.15mm is stirred for uniformly and makes Titanium and titanium boride alloy molten to form blend melt；It will mix
It closes melt cast and forms ingot casting, Ti content is 5.10% in the Al-Ti-B alloy product of acquisition, boron content 1.02%.
Claims (10)
1. a kind of method that aluminothermic reduction prepares boronation titanium alloy, it is characterised in that carry out according to the following steps：
(1) titanium sodium fluoride, sodium fluoborate are uniformly mixed dispensing, titanium sodium fluoride with aluminium powder:Sodium fluoborate:The ratio of aluminium powder dispensing
It is 1 in mass ratio:(1.05~1.06):(0.40~0.43), is then pressed into agglomerate with briquetting machine；
(2) agglomerate is placed in reductive jar and carries out vacuum-thermal reduction, the temperature of vacuum-thermal reduction is 800~1000 DEG C, vacuum degree
For 0.01~10Pa, the time is 2~8h；It is warming up to 900~1250 DEG C after vacuum-thermal reduction, is evaporated in vacuo, evaporates
Material enter crystallizer crystallization, formed crystallized product；After the completion of vacuum distillation, remaining material cools to≤50 DEG C with the furnace,
Obtain boronation titanium alloy.
2. a kind of method that aluminothermic reduction prepares boronation titanium alloy, it is characterised in that carry out according to the following steps：
(1) titanium sodium fluoride, aluminium powder are uniformly mixed dispensing, titanium sodium fluoride with sodium fluoride:Aluminium powder:The ratio of sodium fluoride is in mass ratio
It is 2.50:(0.43~1.07):1.00, then agglomerate is pressed into briquetting machine；
(2) agglomerate is placed in reductive jar and carries out vacuum-thermal reduction, the temperature of vacuum-thermal reduction is 700~1000 DEG C, vacuum degree
For 0.1~10Pa, the time is 2~8h；It is warming up to 1050~1250 DEG C after vacuum-thermal reduction, is evaporated in vacuo, evaporates
Material enter crystallizer crystallization, formed primary crystallization product；After the completion of vacuum distillation, remaining material cools to≤50 with the furnace
DEG C, obtain aluminum titanium alloy or Titanium；
(3) aluminum titanium alloy or Titanium is levigate to granularity≤0.15mm, it is then uniformly mixed and matches with sodium fluoborate and sodium fluoride
Material, the wherein mass ratio of sodium fluoride and sodium fluoborate are 0.76:1, the molar ratio of aluminium and sodium fluoborate in whole materials is 1:
1, aluminium powder is added when aluminium deficiency in whole materials, then secondary agglomerate is pressed into briquetting machine；Or aluminum titanium alloy is crushed mill
Carefully to granularity≤0.15mm, dispensing is then uniformly mixed with sodium fluoborate, the molar ratio of aluminium and sodium fluoborate in whole materials
It is 1:1, aluminium powder is added when aluminium deficiency in whole materials, then secondary agglomerate is pressed into briquetting machine；
(4) secondary agglomerate is placed in two sections of vacuum-thermal reductions of progress, the temperature 600~900 of two sections of vacuum-thermal reductions in reductive jar
DEG C, 0.1~10Pa of vacuum degree, 2~8h of time are warming up to 900~1200 DEG C after two sections of vacuum-thermal reductions, carry out vacuum steaming
It evaporates, the material of evaporation enters crystallizer crystallization, forms secondary crystallization product；Remaining material cools to≤50 DEG C with the furnace, obtains
Boronation titanium alloy.
3. the method that a kind of aluminothermic reduction according to claim 1 prepares boronation titanium alloy, it is characterised in that in step (1)
The pressure for suppressing agglomerate is 50~100MPa.
4. the method that a kind of aluminothermic reduction according to claim 1 prepares boronation titanium alloy, it is characterised in that the knot
Brilliant product is ice crystal, single ice crystal, unreacted titanium sodium fluoride, unreacted sodium fluoborate and other fluorides, by weight
Percentage contains ice crystal 7~10%, single ice crystal 75~90%, titanium sodium fluoride 1~5%, sodium fluoborate 1~5%, other fluorinations
Object≤2%.
5. the method that a kind of aluminothermic reduction according to claim 1 prepares boronation titanium alloy, it is characterised in that step (2)
Crystallized product is levigate to granularity≤0.15mm, is then mixed with granularity≤0.15mm aluminium powders and granularity≤0.15mm sodium fluorides, mixes
Composition and division in a proportion example is (1~5) by the mass ratio of crystallized product and aluminium powder:1, the mass ratio of crystallized product and sodium fluoride is 1:(0.63~
0.65) mixed-powder, is obtained；Mixed-powder is placed in crucible and is then placed in heating furnace, or mixed-powder is placed in liner
For in the resistance furnace or gas-fired furnace of aluminum oxide, 1~3h is kept the temperature under the conditions of 950~1100 DEG C, by the titanium of aluminium reducing and
Boron enters aluminum melt, and the material after the completion of reacting is made of the Al-Ti-B alloy melt of the cryolite melts on upper layer and lower layer；It will
Boronation titanium alloy is levigate to granularity≤0.15mm, and the cryolite melts on upper layer are poured out, and then adds into Al-Ti-B alloy melt
Enter the titanium sponge of granularity≤1mm and the boronation titanium alloy of granularity≤0.15mm, in mass ratio Al-Ti-B alloy melt:Titanium sponge:
Boronation titanium alloy=(27~29):(0.7~0.9):1, it is stirred for uniformly and so that titanium sponge and titanium boride alloy molten is formed mixed
Close melt；Blend melt is poured into a mould to form ingot casting, obtains Al-Ti-B alloy product.
6. the method that a kind of aluminothermic reduction according to claim 5 prepares boronation titanium alloy, it is characterised in that the aluminium
The mass percent of titanium is 4.9~5.1% in Ti-B alloy melt, and the mass percent of boron is 0.9~1.1%；The ice
In spar melt the mass percent of titanium and boron≤0.02%.
7. the method that a kind of aluminothermic reduction according to claim 2 prepares boronation titanium alloy, it is characterised in that step (1) and
(3) pressure of compacting agglomerate is 50~100MPa in.
8. the method that a kind of aluminothermic reduction according to claim 2 prepares boronation titanium alloy, it is characterised in that by step (2)
In primary crystallization product and step (4) in secondary crystallization product mixing, it is levigate to granularity≤0.15mm, then with granularity≤
The aluminium powder of 0.15mm mixes, and obtains mixed-powder；Wherein primary crystallization product in mass ratio:Secondary crystallization product:Aluminium powder=(1-
5):(1-5):1；It when step 3 is without being added sodium fluoride, is remixed after being additionally added sodium fluoride in mixed-powder, sodium fluoride adds
Enter 0.65 times that amount is secondary crystallization product quality；Mixed-powder is placed in crucible and is then placed in heating furnace, or will mixing
Powder is placed in the resistance furnace or gas-fired furnace that liner is aluminum oxide, and 1~3h, quilt are kept the temperature under the conditions of 950~1100 DEG C
The titanium and boron of aluminium reducing enter aluminum melt, and the material after the completion of reacting is by the cryolite melts on upper layer and the Al-Ti-B alloy of lower layer
Melt is constituted；Boronation titanium alloy is levigate to granularity≤0.15mm, aluminum titanium alloy or Titanium is levigate to granularity≤0.15mm,
The cryolite melts on upper layer are poured out, the aluminum titanium alloy or metal of granularity≤0.15mm are then added into Al-Ti-B alloy melt
Titanium, and the boronation titanium alloy of granularity≤0.15mm, in mass ratio Al-Ti-B alloy melt is added:Aluminum titanium alloy:Boronation titanium alloy
=(28~30):(0.9~1.7):1, or Al-Ti-B alloy melt in mass ratio:Titanium:Boronation titanium alloy=(28~
30):(0.9~1.0):1, be stirred for uniformly and so that boronation titanium alloy and aluminum titanium alloy or Titanium is melted to form mixing molten
Body；Blend melt is poured into a mould to form ingot casting, obtains Al-Ti-B alloy product.
9. the method that a kind of aluminothermic reduction according to claim 2 prepares boronation titanium alloy, it is characterised in that described one
Secondary crystallized product is cryolite, unreacted sodium fluoborate and the other fluoride generated, contains ice crystal by mass percentage
85~95%, sodium fluoborate 1~5%, other fluoride≤2%.
10. the method that a kind of aluminothermic reduction according to claim 8 prepares boronation titanium alloy, it is characterised in that the aluminium
The mass percent of titanium is 4.9~5.1% in Ti-B alloy melt, and the mass percent of boron is 0.9~1.1%；The ice
In spar melt the mass percent of titanium and boron≤0.02%.
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