It is a kind of to be used to produce titanium agent of aluminium alloy and preparation method thereof
Technical field
The invention belongs to the additive agent field of aluminium alloy, and in particular to a kind of aluminium alloy titanium additive and preparation method thereof.
Background technology
As aluminium processing and aluminium alloy industry continue to develop, the development of aluminium alloy is listed in the technology given priority to, alloy
Change is a ring important in aluminum alloy production process flow.Dissolving of the alloy addition element in molten aluminum is the important of alloying
Process.The dissolving of element has substantial connection with its property, and the destruction and atom by addition element solid-state structure adhesion are in aluminium liquid
In diffusion velocity control.The conventional alloying element of aluminium alloy has:Silicon, iron, copper, magnesium, nickel, zinc, vanadium etc..Some low melting points are molten
The big alloying element of solution degree such as magnesium, copper can be directly added into aluminum melt, and the high alloying element such as iron of most of fusing point,
Nickel, manganese etc., due to too big with the fusing point gap of aluminium, can not directly it be added, it is necessary to be added by way of intermediate alloy
Enter.Because such as by iron, nickel, manganese metal molten, then temperature of smelting furnace must reach more than 1000 DEG C, and the fusing point of aluminium only has
660 DEG C, if at a temperature of more than 1000 DEG C, aluminum melt can vaporize, and aluminium liquid unboiled in smelting furnace is in such high temperature
Under oxygen easily with surrounding, hydrogen gas and water etc. chemically react, form the impurity for being difficult to remove, the aluminium alloy melt of generation
Alloy content and actually required alloy content deviation it is excessive, so as to cause alloy mechanical performance can not meet to require, cause
The wasting of resources.
In order to avoid above-mentioned deficiency, people's temperature required when alloying element melting process is reduced by the way of intermediate alloy
Degree.The production technology of intermediate alloy is such:The metal that content in the alloy refined is maximum, fusing point is relatively low is melted first
Change.Then the element that fusing point is higher and content is less is added, dissolves and alloy is made., it is necessary to add during melting intermediate alloy
Add a small amount of flux protection, in order to avoid gas enters alloy, go back part that can be removed impurity.To be sufficiently stirred after fusing, make composition uniform
Ingot casting afterwards.The intermediate alloys of some high quality needs in a vacuum or melting and casting under protective atmosphere.Judge the product of aluminium alloy
The main standard of matter quality be in alloy whether containing impurity or impurity content number, preferable aluminium alloy is no impurity
, therefore impurity is more few better, thus it is high for the quality requirements of the intermediate alloy used in aluminium alloy, it is necessary in a vacuum
Or casting is burnt in melting under protective atmosphere, manufacturing condition requires high, and production cost is high, and efficiency substantially reduces.Further, since
Alloying element content contained by intermediate alloy is relatively low, and when weighing calculates, intermediate alloy amount used will be larger, in order to ensure
The temperature of intermediate alloy is melted, the amount for launching intermediate alloy every time can not be excessive, and dosage can excessively cause the reduction of aluminum melt temperature,
Intermediate alloy can not be melted, so when producing the aluminium alloy of same model, carrying out alloying with intermediate alloy just needs using more
Secondary a small amount of mode is added dispensing in aluminum melt, so may result in and produces following problem:1st, melt needed for intermediate alloy
Overlong time;2nd, aluminum melt reacts generation with other materials such as the oxygen in air, hydrogen, carbon, moisture for a long time
Impurity level increases, and causes the quality of aluminium alloy to reduce;3rd, fusing time length can increase energy consumption, can increase scaling loss and the suction of aluminum melt
Gas.
Due to intermediate alloy above shortcomings, gradually it is eliminated, people start to use metal dust in recent years
The mode being sufficiently mixed with fluxing agent in compressing rear addition aluminum melt enters the alloying of row metal.During implementation, aluminium alloy melts
The temperature of casting is usually 710 DEG C or so, for the big alloying element of low melting point or melting degree directly with the shape of elemental metals powder
Formula, which is added in aluminium liquid, to be melted, but for the small alloying element of the high-melting-points such as manganese, iron, chromium, titanium or melting degree, elemental metals powder
End is just difficult to be melted in aluminium liquid, if the temperature of aluminium liquid smelting furnace to be increased to the temperature of manganese, iron, chromium, titanium, in smelting furnace
Aluminium liquid will gasify, therefore solution is at a temperature of aluminium will not gasify, and quickly melts the metals such as manganese, iron, chromium, titanium
Solution, in order to reach this purpose, people have contemplated that manganese, iron, chromium, titanium valve is broken, and add fluxing agent in the powder, and be made solid
Shape shape, i.e. our usually said manganese agent, chalybeate, chromium agent, titanium agent, when manganese agent, chalybeate, chromium agent, titanium agent are put into aluminium liquid
In smelting furnace, fluxing agent reacts rapidly in aluminium liquid, and caused heat can reach within a period of time makes manganese, iron, chromium, titanium
The temperature melted Deng metal, melted so as to reach.But such a mode needs substantial amounts of fluxing agent to realize, therefore every piece
In additive product, manganese, iron, the content of chromium or titanium only up to reach 85% or so, if by the manganese in additive product,
The content of iron, chromium or titanium brings up to more than 90%, then the amount of corresponding fluxing agent is then reduced, after product is added in aluminium liquid,
Manganese, iron, chromium or titanium in additive can not melt completely;In addition, in order to avoid additive product in transportation it is loose, lead to
Additive product is often pressed into density higher pie or spherical, density is typically larger than 5.0g/cm3, but for density
Higher additive product, there is the problem of following, by taking titanium additives as an example:1st, melt it is slower, melt the time be usually
More than 20min, melt time length;2nd, the additive for adding aluminum melt is easily sunk to the bottom, once sinking to the bottom, on the one hand titanium valve can be caused to melt
Solution speed slows down, and titanium valve on the other hand can be caused to disperse after dissolving uneven;3rd, more closely knit additive product is in fusion processes
Middle surface can form the diaphragm of densification, so as to cause inside can not continue to melt, can thus make that the rate of recovery is relatively low, and highest is only
90% or so can be reached.
The content of the invention
Melt that the time is short, titanium recovery rate is high is used to produce aluminium alloy the technical problem to be solved in the present invention is to provide a kind of
Titanium agent.
It is an object of the invention to provide following base case:A kind of titanium agent for being used to produce aluminium alloy, mainly by titanium
The pie or American football shape that powder, aluminium powder, fluxing agent compacting form, the titanium valve, aluminium powder crush under inert gas shielding respectively,
Also include surfactant, the mass percent of each component is respectively:It is titanium valve 85%-95%, aluminium powder 4%-14.49%, fluxing
Agent 0.01%-5%, surfactant 0.5%-2%, the density after each component is compressing are:2.8-5.0g/cm3, wherein:
a:The particle size distribution of titanium valve is 10-700 mesh, and the titanium valve of wherein 325-700 mesh accounts for the 35%- of titanium valve total content
The titanium valve of 40%, 100-325 mesh accounts for the 40%-45% of titanium valve total content, and the titanium valve of 60-100 mesh accounts for the 5%- of titanium valve total content
The titanium valve of 15%, 10-60 mesh accounts for the 0-5% of titanium valve total content, and the purity of described titanium metal powder is more than or equal to 98%;
b:The particle size distribution of aluminium powder is 60-300 mesh, and the purity of aluminium powder is more than or equal to 98%;
c:Fluxing agent particle size distribution is 60-300 mesh.
Technical solution of the present invention has advantages below:
1st, the content of titanium valve is high in the titanium agent of this programme, and up to 85-95%, when aluminium alloy casting is molten, its in additive is led
What is acted on is titanium valve, so in the molten equivalent aluminium alloy of casting, this programme can add less amount, reach identical effect,
Can thus save raw material, and fluxing agent fuse into aluminium liquid after be a kind of impurity, so fluxing agent is fewer, cast the aluminium alloy melted out
Quality is better.
2nd, because the particle size distribution of the titanium valve of the present invention is larger, overall particle mean size is small, in relatively low temperature
Just can quickly it be melted under degree, during using additive product of the present invention, aluminum melt temperature can be with as little as 670 DEG C, so as to reduce
Fuel when casting is molten uses, and saves the energy;
3rd, preparation method of the invention has used surfactant, on the one hand, surfactant has suspending effect, uses
After surfactant so that even the product that additive density of the invention is larger, suspension can be also in aluminum melt
State, it will not sink to the bottom, during melting, additive product can fluctuate in aluminum melt, and fusing speed is accelerated, and contracts significantly
Short additive melts the time, in addition, additive is suspended in aluminium liquid, and additive product can fluctuate, so can make
Disperse evenly after titanium valve dissolving;On the other hand, the hydrophobic group of surfactant can be by the surface aggregate of metal dust one
Rise so that the chance of metal dust contact oxygen is reduced, so as to reduce the formation of titanium and aluminum metal oxide-film;Another further aspect
Due to the polymerization of surfactant, additive product is in state loosely, but not scatters in transit, such titanium
Density after powder and aluminium powder shaping can be done smaller, quickly can be dissolved in aluminum melt;The factor of above-mentioned several respects is significantly
The speed of additive melting is improved, shortens and melts the time, the rate of recovery is high.
4th, titanium valve size distribution is 10-700 mesh in the present invention, and the titanium valve of 325-700 mesh accounts for the 35%- of titanium valve total content
The titanium valve of 40%, 100-325 mesh accounts for the 40%-45% of titanium valve total content, and the distribution of titanium valve granularity is very big, compressing
Afterwards, the titanium valve particle surface of larger granularity is wrapped up by the titanium valve of smaller particle size completely, after product is added in aluminium liquid, due to smaller
The specific surface area of granularity titanium valve is bigger, and surface energy is big, so heating is very fast, smaller particle size titanium valve is while melting, also by heat
Amount passes to the titanium valve particle of larger granularity, and the titanium valve that just can so greatly speed up larger granularity melts, so as to shorten addition aluminium
The melting time of the additive of liquid.
Drawn by melting experiment, the titanium valve rate of recovery of the invention can just reach 100% in 10min or so, and titanium valve returns
Yield is very high.
Prioritization scheme 1, the further optimization to base case, the titanium valve 85%, aluminium powder 10%, fluxing agent 3%, surface
Activating agent 2%, the density after above-mentioned composition is compressing are 2.6g/cm3.Inventor is through experiment discovery, said ratio and density
Additive product to melt time, titanium recovery rate more excellent.
Prioritization scheme 2, the further optimization to base case, the titanium valve 90%, aluminium powder 5%, fluxing agent 3%, surface
Activating agent 2%, the density after above-mentioned composition is compressing are 3.0g/cm3.Inventor is through experiment discovery, said ratio and density
Additive product to melt time, titanium recovery rate more excellent.
Prioritization scheme 3, the further optimization to base case, the titanium valve 95%, aluminium powder 4%, fluxing agent 0.01%, table
Face activating agent 0.99%, the density after above-mentioned composition is compressing are 3.4g/cm3.Inventor through experiment find, said ratio and
The additive product melting time of density, titanium recovery rate are more excellent.
Prioritization scheme 4, the further optimization to any one of base case, prioritization scheme 1,2,3, in addition to binding agent, are pressed
Mass percentage, binding agent account for 0-3%.Binding agent effectively can condense together titanium metal powder, therefore for grain
The meticulous powder in footpath is readily formed agglomerating effect, it is easier to which compressing, compressing titanium additives will not be because of particle diameter
It is meticulous and scattered, it is readily transported;Simultaneously in compacting, without by the excessively consolidation of titanium additives pressure, being added under smaller density
Agent is also plastic.After additive is added into aluminum melt, density is smaller rapidly to be melted.
Prioritization scheme 5, the further optimization to prioritization scheme 4, described binding agent are polyanion cellulose.Inventor
Found through experiment, during using polyanion cellulose as binding agent, adding the additive of aluminum melt can gradually melt from outside to inside
Solution, be not in the phenomenon of titanium valve scaling loss.
It is another object of the present invention to provide base case one:A kind of preparation side for being used to produce the titanium agent of aluminium alloy
Method, including (1) crushing, (2) weighing, (3) mix, (4) compacting, (5) are dried and (6) packaging, are in inert gas in step 1
Protection is lower to crush, and the particle size range that titanium valve is chosen after crushing is 10-700 mesh, and the size distribution of aluminium powder is 40-500 mesh, fluxing agent
Powder size is distributed as 40-500 mesh;Between step 2 and 3, set up and have the following steps:Quality according to obtained by step 2 weighing is total
Number, weighs surfactant, and prepare surfactant solution according to 0.5%-2% mass percent;The mistake that step 3 mixes
Journey is carried out in the environment of air is completely cut off, and the above-mentioned surfactant solution prepared is spilled into.
The advantages of above-mentioned preparation method, is:
1. the present invention is protected when making metal dust using inert gas, metal powder surface shape can be effectively prevented
Into oxide-film.In addition, the process that step 3 mixes is carried out in the environment of air is completely cut off, titanium valve, aluminium so can be effectively prevented
Powder is oxidized.
2. surfactant formulatory forming surfactants solution is sprayed at compound by the preparation method of the present invention
In, the content of surfactant is less, by way of sprinkling surface additive can be made to be sufficiently mixed with titanium valve, aluminium powder.
Prioritization scheme 7, the further optimization to base case one, between step 2 and 3, also set up and have the following steps:According to
Quality sum obtained by step 2 weighing, weighs binding agent, and be configured to bond according to 0.5%-2% mass percent
Agent solution;During step 3 mixes, also the above-mentioned binder solution prepared is spilled into.It can be made by way of being spilled into
Binding agent is sufficiently mixed with titanium valve, aluminium powder.
Embodiment
Surfactant of the present invention is commercially available prod, and classifying type not can be used.Can be stearic acid, dodecane
Base benzene sulfonic acid sodium salt, fatty glyceride, polysorbate etc..Surfactant in following embodiment uses detergent alkylate sulphur
Sour sodium.
The fluxing agent of the present invention can be hexafluoro sodium aluminate, sodium chloride, potassium chloride, sodium fluoride, potassium fluoride, sodium sulphate, carbon
Sour sodium etc., the fluxing agent in following embodiment select hexafluoro sodium aluminate.
The shape of product of the present invention can be pie, American football shape, spherical etc., and variously-shaped using effect is identical, with
Product in lower embodiment is American football shape, and the raw material proportioning of the product of each embodiment, product index are as shown in the table:
It will be illustrated below by taking embodiment 1 as an example:
Embodiment 1
The present embodiment is used for the titanium agent for producing aluminium alloy, Φ 16mm*11mm*4mm American football shape is made, by quality hundred
Point than meter, titanium valve 85%, aluminium powder 10%, hexafluoro sodium aluminate 3%, neopelex 2%, it is compressing after density be
2.6g/cm3。
Above-mentioned additive is made according to following methods:
(1) crush:Protected using inert gas, titanium, aluminum metal and hexafluoro sodium aluminate are protected in inert gas
Crushed respectively under shield, the wherein particle size range of titanium valve is 10-700 mesh, and the particle size range of aluminium powder is 40-500 mesh, hexafluoro aluminium
The powder size scope of sour sodium is 40-500 mesh;
Wherein the size distribution of titanium valve accounts for the 35-40% of titanium valve total content, the mesh of 100 mesh -325 for the titanium valve of 325-700 mesh
Titanium valve account for the 35%-45% of titanium valve total content, the titanium valve of 60-100 mesh accounts for the 10%-15% of titanium valve total content, 10-60 purposes
Titanium valve accounts for the 0-5% of titanium valve total content;The size distribution of aluminium powder is 50-500 mesh;The powder size of hexafluoro sodium aluminate is distributed as
50-500 mesh.Protected simultaneously using inert gas, to prevent titanium valve, aluminium powder and hexafluoro sodium aluminate powder from being combined generation with oxygen
Metal oxide film, so as to ensure the quality of titanium additives.
(2) weighing:By the titanium valve obtained by step 1, aluminium powder, hexafluoro sodium aluminate powder according to following weight than carrying out weighing:
Titanium valve is 85%, aluminium powder 10%, hexafluoro sodium aluminate powder for 3%.
(3) neopelex solution is prepared:Quality sum according to obtained by step 2 weighing, according to 2% quality
Percentage prepares neopelex solution, and the concentration of described neopelex solution is 30%.
(4) titanium valve, aluminium powder and the hexafluoro aluminic acid sodium powder obtained by step 2 are moved in batch mixer, opens batch mixer according to 20-
30 revs/min of rotating speed, batch mixing 2 minutes obtain preliminary blended stock, and mixing process is also carried out under inert gas shielding.
(5) the neopelex spray solution obtained by step 3 is opened in the preliminary compound obtained by step 4
Batch mixer is opened, sets its stirring frequency as 20-30 revs/min, mixing time is 20 minutes, you can obtains well mixed mixing
Feed powder;After this step, ingredient analysis can be carried out by extracting the sample that is mixed with of 5 different parts, if 5 testing results are inclined
Difference is in 0.001%, then explanation is well mixed, you can into step 6, otherwise continues on batch mixer, carries out 20 minutes again
Batch mixing.
(6) compound powder for obtaining step 5 moves into the spherical press-forming machine of metal dust, uses line pressure as 10 MPas
Pressure be pressed;Compressing product density is 2.6g/cm3。
(7) product for obtaining step 6 is put into drying oven and dried so that its moisture is less than 0.2%.
(8) it is finished product with In Aluminium Foil Packing by the high content titanium additives obtained by step 7.
Oxygen content test will be carried out, the result of measure is using nitrogen hydrogen-oxygen analyzer by finished product made from the above method
Oxygen content is less than 0.5%.
Embodiment 2
The present embodiment difference from preparation of Example 1 is:
(2) weighing:By the titanium valve obtained by step 1, aluminium powder, hexafluoro sodium aluminate powder according to following weight than carrying out weighing:
Titanium valve 90%, aluminium powder 5%, hexafluoro sodium aluminate powder 3%;
(3) neopelex solution is prepared:Quality sum according to obtained by step 2 weighing, according to 2% quality
Percentage prepares neopelex solution;
(6) compressing product density is 3.0g/cm3。
Embodiment 5
The present embodiment difference from Example 1 is:
(2) weighing:Titanium valve obtained by step 1, aluminium powder, hexafluoro sodium aluminate powder are claimed according to following mass percent
Material:Titanium valve 90%, aluminium powder 4%, hexafluoro sodium aluminate powder 4%.
(3) neopelex solution is prepared:Quality sum according to obtained by step 2 weighing, according to 1% quality
Percentage prepares neopelex solution.
(4) binder solution is prepared:Quality sum according to obtained by step 2 weighing, is prepared according to 1% mass percent
Polyanion cellulose solution, the concentration of described binder solution is 20%.
(6) the neopelex solution obtained by step 3 and step 4 and polyanion cellulose spray solution are existed
In preliminary compound obtained by step 5, batch mixer is opened, sets its stirring frequency as 20-30 revs/min, mixing time 20
Minute, you can obtain well mixed compound powder.
(7) compound powder for obtaining step 6 moves into press-forming machine, uses pressure to be carried out for 10-30 MPas of pressure
Compacting, it is 3.4g/cm that density is obtained after shaping3Be used for produce the titanium agent of aluminium alloy.
Oxygen content test will be carried out using conventional method using nitrogen hydrogen-oxygen analyzer by finished product made from the above method,
The result of measure is that oxygen content is less than 0.4%.
Moisture of the present invention is measured by common aqueous content test method.
The inventive method due to employing polyanion cellulose and neopelex simultaneously, therefore for particle diameter
Very thin powder is easier polymerization forming, while can reduce the bonding machine meeting of metal dust and oxygen, so that product is oxygen-containing
Amount reduces, and more further improves the quality of product of the present invention.
Experiment:
3 aluminium alloy titanium additives and the red sharp metal material in Wuyi of in the market purchase are chosen from embodiment 1-5 respectively
The titanium agent (75Ti) of material Co., Ltd carries out melting test, be respectively put into 3 be used for test the aluminium liquid of graphite crucible melt
Solve in stove, the solution in each aluminium liquid melting furnace is sampled in the different periods, will with acid after it is cooled to solid
It dissolves, the mixed in hydrochloric acid that acid used is concentrated nitric acid and concentration is 50%, and both volume ratios are 1:1, then detected with ICP
The content of titanium in instrument measurement solution, so as to obtain the average recovery rate of titanium, wherein, the rate of recovery of titanium refers to that titanium valve is dissolved in aluminium and melted
The ratio of titanium valve gross mass in internal quality and additive.The rate of recovery of titanium is higher, illustrates titanium valve in the additive of unit mass
The amount of melting is more.Table 1, table 2, table 3 are the melting result of the test of the rate of recovery of titanium at 710 DEG C, 690 DEG C, 670 DEG C respectively,
Concrete outcome is as follows:
Table 1
Table 2
Table 3
Conclusion:
1. in temperature under the same conditions, the rate of recovery of the titanium of embodiment 1-5 additive is substantially than in the market purchase
The rate of recovery of titanium agent (75Ti) is high, and it is short to melt the time.
2. the additive in 1-5 of the embodiment of the present invention is at a temperature of 670 DEG C, titanium recovery rate during 10-15min is reachable
To 95-100%, reach compared with prior art during more than 20min for highest titanium recovery rate, titanium recovery rate is higher, melts the time
Short
3. the minimum melting temperature of additive of the present invention can as little as 670 DEG C, 710 DEG C compared to prior art reduce 40
DEG C, greatly save smelting furnace energy consumption.Therefore, titanium agent of the present invention is melted in the efficiency high in aluminium liquid, less energy consumption, and cost is low.