It is a kind of to be used to produce fine powder chalybeate 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 aluminum alloy-iron 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 combination power are in molten aluminum
In diffusion velocity control.The common 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 be added, it is necessary to be added by way of intermediate alloy
Enter.This is 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 molten aluminum 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 not meet the requirements, 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 component 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 the number containing impurity or impurity content, 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, production cost height, 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 cannot 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, in recent years it is thought that helping alloying element in low temperature using cosolvent
I.e. 710 DEG C or so molten alloy metallic elements, people are referred to as metallic addition.According to different performance requirements, usually in aluminium
The alloying element of heterogeneity and content is added, melted in liquid, to obtain the aluminium alloy of different model and classification.At present, alloy
Element usually has copper, silicon, magnesium, zinc, manganese, iron, chromium etc..During implementation, the temperature of aluminum alloy melt casting is usually 710 DEG C or so, for
Low melting point or the big alloying element of melting degree are added in molten aluminum directly in the form of elemental metals powder and can melted, but for
The high-melting-points such as manganese, iron, chromium or the small alloying element of melting degree, elemental metals powder is just difficult to be melted in molten aluminum, if by aluminium
The temperature of liquid smelting furnace is increased to manganese, iron, the temperature of chromium metal, then the molten aluminum in smelting furnace will gasify, therefore solution is
At a temperature of aluminium will not gasify, quickly the metals such as manganese, iron, chromium are melted, in order to reach this purpose, people have contemplated that by
Manganese, iron, chromium powder are broken, and add fluxing agent in the powder, and solid shape is made, i.e. our usually said manganese agent, chalybeate, chromium
Agent, puts into molten aluminum smelting furnace when by manganese agent, chalybeate, chromium agent, and explosion type reaction occurs rapidly in molten aluminum for fluxing agent, generation
Heat can reach the temperature for melting the metals such as manganese, iron, chromium within a period of time.But such a mode needs largely to help
Flux could be realized, therefore in every piece of additive product, manganese, iron, the content of chromium only up to reach 85% or so, if will add
The manganese in agent product, iron, the content of chromium is added to bring up to more than 90%, then the amount of corresponding fluxing agent is then reduced, and is added by product
After into molten aluminum, manganese, iron, chromium in additive cannot melt completely;In addition, for the powder such as manganese, iron, chromium in manufacturing process
Granularity, content proportioning etc. have special requirement.By taking iron as an example, iron-holder is in the particle diameter distribution of the iron powder of 85% chalybeate:Greatly
In the requirement of 60 mesh below 5%, 60-80 mesh is 30%-35%, and 80-100 mesh is 15%-20%, and 100-325 mesh is 35%-
45%, less than the requirement of 325 mesh below 10%;Above-mentioned granularity is mainly between 60-325 mesh, it is seen that and size distribution is very narrow,
Usually in disintegrating process, size distribution is narrower, and the technological requirement of crushing is higher, so the iron powder of above-mentioned size distribution is to powder
With regard to very high, the cost of processing is also very high for the requirement of broken technique, such as in shredding stage, we just need more than 85% iron
The granularity of powder is not greater than 60 mesh, while cannot be less than 325 mesh, but the grain that existing disintegrating process often cannot be so stringent
Distribution is spent, therefore the chalybeate qualification rate produced is usually less than 60%.Furthermore since existing iron line aluminium alloy adds
The particle mean size of iron powder entirety in agent is larger, after adding molten aluminum, since the specific surface area of the larger iron powder of granularity is small, and surface energy
Also it is small, so as to melt relatively slowly, and require casting melting temperatur higher, be usually 710 DEG C or so.In addition, in order to avoid additive produces
Product are loose in transportational process, additive product usually are pressed into density higher pie or spherical, density is typically larger than
5.0g/cm3, but for the higher additive product of density, after adding molten aluminum, on the one hand, melt slower, melt the time
Usually 15-20min, melts time length;On the other hand, the additive for adding aluminum melt is easily sunk to the bottom, once sinking to the bottom, can be caused
Iron powder fusing speed slows down, and it is uneven that iron powder can be caused to disperse after dissolving;Another further aspect, more closely knit additive product exist
Surface can form the protective film of densification in fusion processes, so as to cause inside can not continue to melt, can thus make the rate of recovery compared with
Low, highest is only capable of reaching 90% or so.
The content of the invention
Melt that the time is short, iron recovery is high is used to produce aluminium alloy the technical problem to be solved in the present invention is to provide a kind of
Fine powder chalybeate.
It is an object of the invention to provide following base case:It is a kind of to be used to produce the fine powder chalybeate of aluminium alloy, mainly by
The pie or American football shape that iron powder, aluminium powder, fluxing agent compacting form, the iron powder, aluminium powder are broken under inert gas shielding respectively
It is broken, surfactant is further included, the mass percent of each component is respectively:It is iron powder 90%-98%, aluminium powder 0-9.48%, fluxing
Agent 0.01%-5%, surfactant 0.5%-2%, wherein,
a:The particle size distribution of iron powder is 10-700 mesh, its particle mean size is 100--400 mesh;
b:The particle size distribution of the inorganic salts of aluminium powder and aluminium is 40-500 mesh, its particle mean size is 80--350 mesh.
Technical solution of the present invention has the following advantages:
1st, iron particle size is distributed as 10-700 mesh in the present invention, and the iron powder of 325-700 mesh accounts for the 35%- of iron powder total content
The iron powder of 40%, 100-325 mesh accounts for the 40%-45% of iron powder total content, and the distribution of iron particle size is very big, compressing
Afterwards, the ferrous powder granules surface of larger granularity is wrapped up by the iron powder of smaller particle size completely, after product is added in molten aluminum, due to smaller
The specific surface area bigger of granularity iron powder, surface energy is big, so heating is very fast, smaller particle size iron powder is while melting, also by heat
Amount passes to the ferrous powder granules of larger granularity, and the iron powder that just can so greatly speed up larger granularity melts, so as to shorten addition aluminium
The melting time of the additive of liquid.
2nd, since the particle size distribution of the iron powder 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 of the present invention product, aluminum melt temperature can be with as low as 670 DEG C, so as to reduce
Fuel when casting is molten uses, and saves the energy;
3rd, the content of iron powder is high in the chalybeate of this programme, and up to 90-98%, when aluminium alloy casting is molten, its in additive is led
What is acted on is iron powder, 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 molten aluminum after be a kind of impurity, so fluxing agent is fewer, cast the aluminium alloy melted out
Quality is better.
3rd, preparation method of the invention has used surfactant, on the one hand, surfactant is acted on suspending, is used
After surfactant so that even the product that additive density of the invention is larger, suspension can be also in aluminum melt
State, will not sink to the bottom, and 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 molten aluminum, and additive product can fluctuate, so can make
Disperse evenly after iron powder 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 ferrous metal 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 iron
Density after powder and aluminium powder shaping can be done smaller, can quickly 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.
Drawn by melting experiment, the iron powder rate of recovery of the invention can just reach 100% in 10min or so, and iron powder returns
Yield is very high.
Prioritization scheme 1, the further optimization to base case, the particle size distribution of the iron powder is 10-700 mesh, its
The iron powder of middle 325-700 mesh accounts for the 35%-40% of iron powder total content, and the iron powder of 100-325 mesh accounts for the 40%- of iron powder total content
The iron powder of 45%, 60-100 mesh accounts for the 5%-15% of iron powder total content, and the iron powder of 10-60 mesh accounts for the 0-5% of iron powder total content.Hair
A person of good sense has found through experiment, more excellent using additive product melting time, iron recovery made from above-mentioned size distribution.
Prioritization scheme 2, the further optimization to base case, the iron powder 93%, aluminium powder 3%, fluxing agent 3%, surface
Activating agent 1%, the density after above-mentioned composition is compressing are 3.7g/cm3.Inventor is through experiment discovery, said ratio and density
Additive product to melt time, iron recovery more excellent.
Prioritization scheme 3, the further optimization to base case, the density range of the fine powder aluminum alloy-iron additive
For 2.8-5.0g/cm3.In above-mentioned density range, adding the additive of additive-aluminium melt can float in aluminum melt, melt
During, additive can fluctuate in aluminum melt, accelerate fusing speed.
Prioritization scheme 4, the further optimization to any one of base case, prioritization scheme 1,2,3, further includes binding agent, presses
Mass percentage, binding agent account for 0-3%.Binding agent effectively can condense together iron metal powder, therefore for grain
The meticulous powder in footpath is readily formed agglomerating effect, it is easier to which compressing, compressing iron additive will not be because of particle diameter
It is meticulous and scattered, it is readily transported;At the same time in compacting, without by the excessively consolidation of iron additive pressure, being added under smaller density
Agent is also plastic.After additive is added aluminum melt, density is smaller rapidly to be melted.
Prioritization scheme 5, the further optimization to prioritization scheme 4, the binding agent is 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, is not in the phenomenon of iron powder scaling loss.
It is another object of the present invention to provide base case one:A kind of system for the fine powder chalybeate for being used to produce aluminium alloy
Preparation Method, including (1) crushing, (2) weighing, (3) mix, (4) compacting, (5) are dry and (6) packaging, are in inertia in step 1
Crushed under gas shield, the particle size range that iron powder is chosen after crushing is 10-700 mesh, and the size distribution of aluminium powder is 40-500 mesh, is helped
Flux powder size distribution is 40-500 mesh;Between step 2 and 3, add and have the following steps:According to the matter obtained by step 2 weighing
Amount sum, weighs surfactant, and prepare surfactant solution according to the mass percent of 0.5%-2%;Step 3 mixes
Process be to be carried out in the environment of air is completely cut off, and above-mentioned prepared surfactant solution is spilled into.
The advantages of above-mentioned preparation method, is:
1st, the present invention is protected when making metal dust using inert gas, can effectively prevent metal powder surface shape
Into oxide-film.In addition, the process that step 3 mixes is carried out in the environment of air is completely cut off, iron powder, aluminium so can be effectively prevented
Powder is aoxidized.
2nd, preparation method of the invention is by surfactant formulatory forming surfactants solution, and is sprayed at mixture
In, the content of surfactant is less, by way of sprinkling surface additive can be made to be sufficiently mixed with iron powder, aluminium powder.
Prioritization scheme 7, the further optimization to base case one, between step 2 and 3, also adds and has the following steps:According to
Quality sum obtained by step 2 weighing, weighs binding agent, and be configured to bond according to the mass percent of 0.5%-2%
Agent solution;During step 3 mixes, also above-mentioned prepared binder solution is spilled into.It can be made by way of being spilled into
Binding agent is sufficiently mixed with iron powder, aluminium powder.
Embodiment
Surfactant of the present invention is commercial product, 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 fine powder chalybeate for producing aluminium alloy, the American football shape of Φ 16mm*11mm*4mm is made, by matter
Measure percentages, iron powder 90%, aluminium powder 6%, hexafluoro sodium aluminate 3%, neopelex 1%, it is compressing after it is close
Spend for 2.8g/cm3。
Above-mentioned additive is made according to following methods:
(1) crush:Protected using inert gas, ferrous metal, aluminum metal and hexafluoro sodium aluminate are protected in inert gas
Crushed respectively under shield, the wherein particle size range of iron powder 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 iron powder accounts for the 35-40% of iron powder total content, -325 mesh of 100 mesh for the iron powder of 325-700 mesh
Iron powder account for the 35%-45% of iron powder total content, the iron powder of 60-100 mesh accounts for the 10%-15% of iron powder total content, 10-60 purposes
Iron powder accounts for the 0-5% of iron powder 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 at the same time using inert gas, to prevent iron powder, aluminium powder and hexafluoro sodium aluminate powder from being combined generation with oxygen
Metal oxide film, so as to ensure the quality of iron additive.
(2) weighing:Iron powder obtained by step 1, aluminium powder, hexafluoro sodium aluminate powder are subjected to weighing according to following weight ratio:
Iron powder is 90%, aluminium powder 6%, hexafluoro sodium aluminate powder for 3%.
(3) neopelex solution is prepared:Quality sum according to obtained by step 2 weighing, according to 1% quality
Percentage prepares neopelex solution, and the concentration of the neopelex solution is 30%.
(4) iron powder, 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 also carries out under inert gas shielding.
(5) the neopelex spray solution obtained by step 3 is opened in the preliminary mixture 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 uniformly 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 uniformly mixed, you can enters 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 megapascal
Pressure be pressed;Compressing product density is 2.8g/cm3。
(7) product for obtaining step 6 is put into drying oven dry so that its moisture is less than 0.2%.
(8) it is finished product with In Aluminium Foil Packing by the high content iron additive 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:Iron powder obtained by step 1, aluminium powder, hexafluoro sodium aluminate powder are subjected to weighing according to following weight ratio:
Iron powder 98%, hexafluoro sodium aluminate powder 0.01%;
(3) neopelex solution is prepared:Quality sum according to obtained by step 2 weighing, according to 1.99%
Mass percent prepares neopelex solution;
(6) compressing product density is 4.8g/cm3。
Embodiment 5
The present embodiment difference from Example 1 is:
(2) weighing:Iron powder obtained by step 1, aluminium powder, hexafluoro sodium aluminate powder are claimed according to following mass percent
Material:Iron powder 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 the binder solution is 20%.
(6) the neopelex solution obtained by step 3 and step 4 and polyanion cellulose spray solution are existed
In preliminary mixture obtained by step 5, batch mixer is opened, sets its stirring frequency as 20-30 revs/min, mixing time 20
Minute, you can obtain uniformly mixed compound powder.
(7) compound powder for obtaining step 6 moves into press-forming machine, uses pressure to be carried out for the pressure of 10-30 megapascal
Compacting, it is 2.8g/cm that density is obtained after shaping3Be used for produce the fine powder chalybeate 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 less than 0.4% for oxygen content.
Moisture of the present invention is measured by common aqueous content test method.
The method of the present invention due to employing polyanion cellulose and neopelex at the same time, 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:
The chalybeate XF-Fe75 for choosing 3 aluminum alloy-iron additives and in the market purchase from embodiment 1-5 respectively is carried out
Melt test, be respectively put into 3 be used for test graphite crucible molten aluminum calciner in, in the different periods to each
Solution in molten aluminum melting furnace is sampled, and after it is cooled to solid, is dissolved with acid, and acid used is concentrated nitric acid and dense
The mixed in hydrochloric acid for 50% is spent, both volume ratios are 1:1, the content of iron in solution is then measured with ICP detectors, so that
To the average recovery rate of iron, wherein, it is total that the rate of recovery of iron refers to that iron powder is dissolved in iron powder in the quality in aluminum melt and additive
The ratio of quality.The rate of recovery of iron is higher, illustrates that the amount that iron powder melts in the additive of unit mass is more.Table 1, table 2, table 3 divide
It is not the melting result of the test of the rate of recovery of iron at 710 DEG C, 690 DEG C, 670 DEG C, 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 iron of the additive of embodiment 1-5 is substantially than in the market purchase
The rate of recovery of chalybeate XF-Fe75 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, iron recovery during 10-15min, that is, reachable
To 95-100%, reach compared with prior art during more than 20min for highest iron recovery, iron recovery higher, melt the time
Short
3. the minimum melting temperature of additive of the present invention can as low as 670 DEG C, 710 DEG C compared with the prior art reduce 40
DEG C, greatly save smelting furnace energy consumption.Therefore, chalybeate of the present invention is melted in efficient in molten aluminum, less energy consumption, and cost is low.