Forming agent, titanium alloy-based feeding and preparation method thereof, titanium alloy-based base substrate and its preparation
Method
Technical field
The present invention relates to metal powder injection molded technical field, more particularly to forming agent, titanium alloy-based feeding and its
Preparation method, titanium alloy-based base substrate and preparation method thereof.
Background technology
Titanium alloy has many advantages, such as, for example density is small as a kind of high-quality light metal structural material and functional material,
Specific strength, higher than fracture toughness, fatigue strength and resistance to crack extension ability are good, and biocompatibility is good, antioxidant, low-temperature flexibility
Well, etch resistant properties are excellent, and nonmagnetic, nontoxic, resistance damping properties are strong, and heat resistance is good, and pumping property is good etc..Therefore, titanium
Alloy has obtained extensively should in terms of the fields such as Aero-Space, navigation, oil, chemical industry, metallurgy, automobile, generating, biological medicine
With.But it is due to that its fusing point and hardness are high, melting is difficult, and machinability is poor so that its cost is always than other light metals
It is high.
Metal powder injection molding (MIM) is one kind that conventional powder metallurgy and injection molding of plastics technology are combined
Near-net-shape technology, is adapted to small-sized, complex shape part batch production, and the production of titanium or titanium alloy part is solved better
The problem of cost is high.However, the titanium alloy produced using Metal Injection Molding still suffers from the problem of consistency is low.
The content of the invention
Based on this, it is necessary to for Metal Injection Molding produce titanium alloy consistency it is low the problem of there is provided
A kind of forming agent, titanium alloy-based feeding and preparation method thereof, titanium alloy-based base substrate and preparation method thereof.
A kind of forming agent, for the injection moulding of titanium alloy powder, includes according to the mass fraction:
In wherein one embodiment, the high molecular polymerization wax is PE waxes.
A kind of titanium alloy-based feeding, including titanium alloy powder and above-mentioned forming agent.
In wherein one embodiment, the mass ratio of the forming agent and the titanium alloy powder is (18~22):(78
~92).
In wherein one embodiment, comprise the following steps:
Under protective gas atmosphere or vacuum condition, by titanium alloy powder heated to temperature be 155 DEG C~
165℃;
The titanium alloy powder is well mixed with forming agent and obtains mixture;
The mixture is plastified, extruded and granulation obtains titanium alloy-based feeding.
A kind of preparation method of titanium alloy-based base substrate, comprises the following steps:
Above-mentioned titanium alloy-based feeding be molded to obtain titanium alloy-based blank;
Ungrease treatment is carried out to the titanium alloy-based blank using oxalic acid;
The titanium alloy-based blank is sintered and obtains titanium alloy-based base substrate.
In wherein one embodiment, the temperature of the ungrease treatment is 120 DEG C~140 DEG C;The ungrease treatment
Time is 3h~5h.
In wherein one embodiment, the step of the ungrease treatment described in oxalic acid charging rate for 1g/min~
2.5g/min。
In wherein one embodiment, temperature when carrying out the sintering processes is 1230 DEG C~1250 DEG C, described to burn
The time of knot processing is 90min~120min;And/or, environmental pressure is 0.5MPa~2MPa during the sintering processes.
A kind of titanium alloy-based base substrate, is prepared according to the preparation method of above-mentioned titanium alloy-based base substrate.
Above-mentioned forming agent, using acetal resin as the main component of forming agent, and adds high molecular polymerization wax and cohune
Palmitic acid wax is used cooperatively, during for titanium alloy material, is conducive to the raising of the stabilization and consistency of the shrinkage factor of titanium alloy material.On
State titanium alloy-based feeding to prepare using above-mentioned forming agent, stable contraction rate, consistency is high.The preparation side of above-mentioned titanium alloy-based feeding
Method is simple, easy to operate, easily realizes industrialized production.The injection moulding method of above-mentioned titanium alloy-based base substrate, using oxalic acid to titanium
Alloy-based blank carries out ungrease treatment, is also beneficial to the raising that titanium alloy-based base substrate shrinks stability and consistency.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of the titanium alloy-based feeding of an embodiment;
Fig. 2 is the flow chart of the preparation method of the titanium alloy-based base substrate of an embodiment.
Embodiment
Below in conjunction with the drawings and the specific embodiments to forming agent, titanium alloy-based feeding and preparation method thereof, titanium alloy
Base base substrate and preparation method thereof is described in further detail.
The forming agent of one embodiment, for the injection moulding of titanium alloy powder, includes according to the mass fraction:
In wherein one embodiment, optothermal stabilizer be Wuhua new material the trade mark be KY-1010 stabilizer.Light
Heat stabilizer is used to suppress polyformaldehyde Polymer material in mixing because high temperature is decomposed.
In wherein one embodiment, high molecular polymerization wax is L-type macromolecule wax.It is preferred that, high molecular polymerization wax is
The trade mark of Wuhua new material is L912 PE waxes.In wherein one embodiment, the molecular weight of high molecular polymerization wax is 1500
~5000, viscosity of the high molecular polymerization wax at 140 DEG C is 300Pas~500Pas.
Used cooperatively using high molecular polymerization wax and Brazil wax, high molecular polymerization wax and Brazil wax can be made
For lubricant and plasticizer.The glossiness of titanium alloy material can also be improved by adding Brazil wax, play the effect of polishing material.
Meanwhile, both use cooperatively the raising of the stabilization and consistency of the shrinkage factor for being conducive to titanium alloy material.Compared to babassu
Wax, the price of high molecular polymerization wax is relatively low, is used cooperatively and can also be reduced using high molecular polymerization wax and Brazil wax
The consumption of Brazil wax, so as to reduce the cost of titanium alloy-based feeding.
In wherein one embodiment, polyformaldehyde is copolymerized methanal.
Above-mentioned forming agent, using acetal resin as the main component of forming agent, and adds high molecular polymerization wax and cohune
Palmitic acid wax is used cooperatively, and is on the one hand conducive to the raising of the stabilization and consistency of the shrinkage factor of titanium alloy material, on the other hand can be with
Reduce the cost of titanium alloy-based feeding.
The titanium alloy-based feeding of one embodiment, including titanium alloy powder and forming agent.
In wherein one embodiment, the mass ratio of forming agent and titanium alloy powder is (18~22):(78~92).
In wherein one embodiment, titanium alloy is commercially available titanium alloy TC 4 powder.The chemical formula of titanium alloy TC 4 is
Ti-6Al-4V.In wherein one embodiment, the composition of titanium alloy TC 4 include as mass fraction Fe≤0.30%, C≤
0.10%, N≤0.05%, H≤0.015%, O≤0.20%, Al are that 5.5%~6.8%, V is 3.5%~4.5%, and surplus is
Ti.In wherein one embodiment, titanium alloy TC 4 powder can be by the screen clothes of 500 mesh.It is preferred that, titanium alloy TC 4 powder
Particle diameter 100%<20μm.Certainly, in other embodiments, titanium alloy powder can also be titanium alloy T A5 or titanium alloy
TC11 etc..The tap density of titanium alloy TC 4 powder is 2.40g/cm3。
Referring to Fig. 1, the preparation method of the titanium alloy-based feeding of an embodiment, comprises the following steps:
S110, under protective gas atmosphere or vacuum condition, by titanium alloy powder heated to temperature be 155
DEG C~165 DEG C.
The heating of titanium alloy powder is carried out under protective gas atmosphere or vacuum condition primarily to preventing titanium
Alloy powder heating is oxidized.
In wherein one embodiment, protective gas atmosphere is at least one of nitrogen atmosphere and argon gas atmosphere.
S120, titanium alloy is well mixed with forming agent obtains mixture.
Forming agent is added to mix to walk shape in the titanium alloy after heating and obtains mixture.Temperature is maintained at during mixing
155 DEG C~165 DEG C.The rotating speed of mixing is 25r/min~35r/min, and the time of mixing is 10min~30min.One wherein
In embodiment, carried out in banbury the step of mixing.It is of course also possible to which hand operated mixing is carried out.
S130, mixture plastified, is extruded and granulation obtains titanium alloy-based feeding.
In wherein one embodiment, mixture is plastified and extrusion is carried out in double screw extruder, it is right
Mixture, which carries out granulation, to be carried out in comminutor.
The preparation method of above-mentioned titanium alloy-based feeding is simple, easy to operate, easily realizes industrialized production.
Referring to Fig. 2, the preparation method of the titanium alloy-based base substrate of an embodiment comprises the following steps:
S210, titanium alloy-based feeding carried out to be molded and obtain titanium alloy-based blank.
Choose product mold to be installed in injection device, carry out injection moulding and obtain the titanium alloy-based base with given shape
Part.
S220, using oxalic acid to titanium alloy-based blank carry out ungrease treatment.
In wherein one embodiment, oxalic acid crystal concentration is>99.5%.Oxalic acid starts distillation at 100 DEG C, after distillation
Oxalic acid be imported into place product space.Forming agent in titanium alloy-based blank is sent out at a temperature of 120 DEG C or so with oxalic acid
Raw catalytic reaction, is broken down into rapidly the gases such as formaldehyde and is excluded.It can be sloughed 70%~75% in blank by ungrease treatment
The forming agent of mass fraction.
In wherein one embodiment, titanium alloy-based blank is placed in the reactor, and heated, is kept
Environment temperature is 120 DEG C~140 DEG C.By oxalic acid import reactor in after, oxalic acid is sublimed into oxalic acid gas so that oxalic acid gas with
Titanium alloy-based blank is fully contacted.In wherein one embodiment, the charging rate for carrying out oxalic acid during ungrease treatment is 1g/
Min~2.5g/min.
In wherein one embodiment, the time for carrying out ungrease treatment is 3h~5h.
In wherein one embodiment, ungrease treatment is carried out in debinding furnace.
Ungrease treatment is carried out to titanium alloy-based blank using oxalic acid, on the one hand, be conducive to the contraction of titanium alloy product stable
The raising of property and the raising of consistency;On the other hand, oxalic acid is relatively small to the corrosivity of titanium alloy;Moreover, oxalic acid has also
Originality, does not react with formaldehyde gas, can avoid the danger exploded;Carrying out ungrease treatment using oxalic acid will not produce
Photochemical fog, or even acid rain is produced, cause the pollution of environment.
S230, titanium alloy-based blank is sintered.
In wherein one embodiment, titanium alloy-based blank is sintered using pressure sintering technique.Sintering
The environment temperature of processing is 1230 DEG C~1250 DEG C;The time of sintering is 90min~120min.Sintering processes keep environmental pressure
In 0.5MPa~2MPa.
The preparation method of above-mentioned titanium alloy-based base substrate, ungrease treatment, titanium alloy are carried out using oxalic acid to titanium alloy-based blank
Product contraction stability is good, consistency is improved, and the corrosivity of oxalic acid is small, and is not reacted using oxalic acid with formaldehyde gas, can
To avoid the danger exploded, photochemical fog will not be also produced, or even produces acid rain, the pollution of environment is caused, with more
Excellent security and the feature of environmental protection.
The titanium alloy-based base substrate of one embodiment is prepared according to the preparation method of above-mentioned titanium alloy-based base substrate.
Here is the explanation of specific embodiment, and following examples are not contained except inevitably miscellaneous unless otherwise specified, then
The component pointed out is not known in other beyond matter.
Embodiment 1
Weigh 7Kg formaldehyde, 0.1Kg stearic acid, 0.3Kg optothermal stabilizer, 0.7Kg L-type high molecular polymerization wax,
The Brazil wax of 0.5Kg high density polyethylene (HDPE), 0.3Kg polyethylene-acetic acid esters and 0.2Kg is well mixed to be molded
Agent.The titanium alloy powder for weighing 46Kg is added in banbury, banbury vacuumize process.Titanium alloy powder is carried out to be heated to temperature
Spend for 165 DEG C.Above-mentioned forming agent is added into banbury, 165 DEG C is maintained the temperature at and is kneaded to forming uniform walk shape
Mixture.The rotating speed of banbury is set to 35r/min, and the time kneaded in banbury is 10min.Mixture is put into double spiral shells
Plastified and extruded in bar extruder, then carry out in comminutor granulating and obtaining titanium alloy-based feeding.
Choose product mold to be installed in injection forming equipment, titanium alloy-based feeding is injected in injection forming equipment and injected
Shaping obtains titanium alloy-based blank.Ungrease treatment is carried out to titanium alloy-based blank using oxalic acid.Titanium alloy-based blank is placed in de-
In fat stove, it is 120 DEG C to keep the temperature in debinding furnace, oxalic acid is added into debinding furnace with 1g/min charging rate, oxalic acid exists
Oxalic acid gas is sublimed into debinding furnace.Oxalic acid gas fully reacts with the forming agent in titanium alloy-based blank.Carry out ungrease treatment
Time be 5h.Blank is sintered again and obtains titanium alloy base substrate.The temperature of sintering processes is 1230 DEG C, sintering processes
Time be 90min, pressure during sintering processes is 0.5MPa.
Embodiment 2
Weigh 8.5Kg formaldehyde, 0.25Kg stearic acid, 0.6Kg optothermal stabilizer, 0.3Kg L-type high molecular polymerization
Wax, 1Kg high density polyethylene (HDPE), 0.15Kg polyethylene-acetic acid esters and 0.4Kg Brazil wax well mixed are molded
Agent.The titanium alloy powder for weighing 35Kg is added in banbury, banbury vacuumize process.Titanium alloy powder is carried out to be heated to temperature
Spend for 155 DEG C.Above-mentioned forming agent is added into banbury, 155 DEG C is maintained the temperature at and is kneaded to forming uniform walk shape
Mixture.The rotating speed of banbury is set to 25r/min, and the time kneaded in banbury is 30min.Mixture is put into double spiral shells
Plastified and extruded in bar extruder, then carry out in comminutor granulating and obtaining titanium alloy-based feeding.
Choose product mold to be installed in injection forming equipment, titanium alloy-based feeding is injected in injection forming equipment and injected
Shaping obtains titanium alloy-based blank.Ungrease treatment is carried out to titanium alloy-based blank using oxalic acid.Titanium alloy-based blank is placed in de-
In fat stove, it is 140 DEG C to keep the temperature in debinding furnace, and oxalic acid, oxalic acid are added into debinding furnace with 2.5g/min charging rate
Oxalic acid gas is sublimed into debinding furnace.Oxalic acid gas fully reacts with the forming agent in titanium alloy-based blank.Carry out at degreasing
The time of reason is 3h.Blank is sintered again and obtains titanium alloy base substrate.The temperature of sintering processes is 1250 DEG C, at sintering
The time of reason is 120min, and pressure during sintering processes is 2MPa.
Embodiment 3
Weigh 8Kg formaldehyde, 0.2Kg stearic acid, 0.4Kg optothermal stabilizer, 0.5Kg L-type high molecular polymerization wax,
The Brazil wax of 0.7Kg high density polyethylene (HDPE), 0.2Kg polyethylene-acetic acid esters and 0.3Kg is well mixed to be molded
Agent.The titanium alloy powder for weighing 40Kg is added in banbury, banbury vacuumize process.Titanium alloy powder is carried out to be heated to temperature
Spend for 160 DEG C.Above-mentioned forming agent is added into banbury, 160 DEG C is maintained the temperature at and is kneaded to forming uniform walk shape
Mixture.The rotating speed of banbury is set to 25r/min, and the time kneaded in banbury is 20min.Mixture is put into double spiral shells
Plastified and extruded in bar extruder, then carry out in comminutor granulating and obtaining titanium alloy-based feeding.
Choose product mold to be installed in injection forming equipment, titanium alloy-based feeding is injected in injection forming equipment and injected
Shaping obtains titanium alloy-based blank.Ungrease treatment is carried out to titanium alloy-based blank using oxalic acid.Titanium alloy-based blank is placed in de-
In fat stove, it is 130 DEG C to keep the temperature in debinding furnace, oxalic acid is added into debinding furnace with 2g/min charging rate, oxalic acid exists
Oxalic acid gas is sublimed into debinding furnace.Oxalic acid gas fully reacts with the forming agent in titanium alloy-based blank.Carry out ungrease treatment
Time be 4h.Blank is sintered again and obtains titanium alloy base substrate.The temperature of sintering processes is 1240 DEG C, sintering processes
Time be 100min, pressure during sintering processes is 1MPa.
Embodiment 4
Weigh 7.5Kg formaldehyde, 0.15Kg stearic acid, 0.5Kg optothermal stabilizer, 0.6Kg L-type high molecular polymerization
Wax, 0.6Kg high density polyethylene (HDPE), 0.25Kg polyethylene-acetic acid esters and 0.15Kg Brazil wax well mixed are obtained
Forming agent.The titanium alloy powder for weighing 42Kg is added in banbury, banbury vacuumize process.Titanium alloy powder is heated
It it is 160 DEG C to temperature.Above-mentioned forming agent is added into banbury, 160 DEG C is maintained the temperature at and is kneaded to forming uniform mud
Doughy mix.The rotating speed of banbury is set to 25r/min, and the time kneaded in banbury is 30min.Mixture is put into
Plastified and extruded in double screw extruder, then carry out in comminutor granulating and obtaining titanium alloy-based feeding.
Choose product mold to be installed in injection forming equipment, titanium alloy-based feeding is injected in injection forming equipment and injected
Shaping obtains titanium alloy-based blank.Ungrease treatment is carried out to titanium alloy-based blank using oxalic acid.Titanium alloy-based blank is placed in de-
In fat stove, it is 140 DEG C to keep the temperature in debinding furnace, and oxalic acid, oxalic acid are added into debinding furnace with 2.5g/min charging rate
Oxalic acid gas is sublimed into debinding furnace.Oxalic acid gas fully reacts with the forming agent in titanium alloy-based blank.Carry out at degreasing
The time of reason is 5h.Blank is sintered again and obtains titanium alloy base substrate.The temperature of sintering processes is 1250 DEG C, at sintering
The time of reason is 100min, and pressure during sintering processes is 2MPa.
Embodiment 5
Weigh 7Kg formaldehyde, 0.1Kg stearic acid, 0.3Kg optothermal stabilizer, 0.9Kg L-type high molecular polymerization wax,
0.5Kg high density polyethylene (HDPE) and 0.3Kg polyethylene-acetic acid esters, which are well mixed, obtains forming agent.Weigh 46Kg titanium alloy
Powder is added in banbury, banbury vacuumize process.To titanium alloy powder be heated to temperature for 165 DEG C.To banbury
It is middle to add above-mentioned forming agent, maintain the temperature at 165 DEG C and kneaded to forming uniform mud doughy mix.The rotating speed of banbury
35r/min is set to, the time kneaded in banbury is 10min.Mixture is put into double screw extruder and plastified
And extrusion, then carry out in comminutor granulating and obtaining titanium alloy-based feeding.
Choose product mold to be installed in injection forming equipment, titanium alloy-based feeding is injected in injection forming equipment and injected
Shaping obtains titanium alloy-based blank.Ungrease treatment is carried out to titanium alloy-based blank using oxalic acid.Titanium alloy-based blank is placed in de-
In fat stove, it is 120 DEG C to keep the temperature in debinding furnace, oxalic acid is added into debinding furnace with 1g/min charging rate, oxalic acid exists
Oxalic acid gas is sublimed into debinding furnace.Oxalic acid gas fully reacts with the forming agent in titanium alloy-based blank.Carry out ungrease treatment
Time be 5h.Blank is sintered again and obtains titanium alloy base substrate.The temperature of sintering processes is 1230 DEG C, sintering processes
Time be 90min, pressure during sintering processes is 0.5MPa.
Embodiment 6
Weigh 7Kg formaldehyde, 0.1Kg stearic acid, 0.3Kg optothermal stabilizer, 0.7Kg L-type high molecular polymerization wax,
The Brazil wax of 0.5Kg high density polyethylene (HDPE), 0.3Kg polyethylene-acetic acid esters and 0.2Kg is well mixed to be molded
Agent.The titanium alloy powder for weighing 46Kg is added in banbury, banbury vacuumize process.Titanium alloy powder is carried out to be heated to temperature
Spend for 165 DEG C.Above-mentioned forming agent is added into banbury, 165 DEG C is maintained the temperature at and is kneaded to forming uniform walk shape
Mixture.The rotating speed of banbury is set to 35r/min, and the time kneaded in banbury is 10min.Mixture is put into double spiral shells
Plastified and extruded in bar extruder, then carry out in comminutor granulating and obtaining titanium alloy-based feeding.
Choose product mold to be installed in injection forming equipment, titanium alloy-based feeding is injected in injection forming equipment and injected
Shaping obtains titanium alloy-based blank.Ungrease treatment is carried out to blank using the nitric acid of 98% concentration, the charging rate of concentrated nitric acid is
2g/min.The temperature for carrying out ungrease treatment is 120 DEG C, and the time for carrying out ungrease treatment is 5h.Blank is sintered again
Obtain titanium alloy base substrate.The temperature of sintering processes is 1230 DEG C, and the time of sintering processes is 90min, pressure during sintering processes
For 0.5MPa.
It is as shown in table 1 that the performance of the titanium alloy base substrate prepared to embodiment 1~6 carries out test result.Titanium alloy base substrate
Size is 100mm*10mm* (1~3) mm.Wherein, melt index is obtained using fusion index instrument measurement;Constriction coefficient is using mark
Part sintering anteroposterior dimension is obtained than calculating;Density is obtained using densimeter measurement;Hardness is obtained using Vickers hardness instrument measurement;Cause
Density is worth to using density after sintering with standard density ratio.
Table 1
It can be seen from the data in Table 1 that the titanium alloy base substrate that 1~embodiment of embodiment 4 is prepared is compared to embodiment 5
And embodiment 6 shrinks stability more preferably, and the hardness and consistency of obtained titanium alloy base substrate are higher.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.