CN109988931A - A kind of aluminum alloy refinement material and its preparation method and application - Google Patents

Abstract

The present invention discloses a kind of aluminium alloy refiner material and its preparation method and application, is related to aluminum alloy modifier field.Aluminium alloy refiner material is made of the raw material of following weight ratio: potassium fluoroaluminate 5~8%, cryolite 7~11%, disodium hydrogen phosphate hydrate 3-5%, potassium chloride 5-7%, sodium chloride 4-8%, barium acetate 0.4-0.8%, barium nitrate 3-6%, samaric fluoride 0.2-0.9%, aluminum acetate 0.2-0.9%, aluminium chloride 6-8%, lepidolite compound powder 15-20%, surplus are fine aluminium；Four kinds of barium, sodium, lithium, samarium alterants are combined according to its characteristic, using jet deposition and the loose sintered body of one step preparation structure of calcining is squeezed, rotten activity has been effectively retained, has had deterioration latency stage short, effective deteriorating time is long, the stable feature of modification effect.Lepidolite powder can be used as rotten agent carrier degasification slagging-off, wherein the high rigidity substance being rich in can be obviously improved alloy rigidity.

Description

A kind of aluminum alloy refinement material and its preparation method and application

technical field

The invention relates to the field of aluminum alloy modifiers, in particular to an aluminum alloy refining material and a preparation method thereof.

Background technique

The silicon structure of the aluminum alloy is composed of coarse five-lobed star-shaped primary silicon and long needle-shaped eutectic silicon. These forms of silicon phase will severely split the Al matrix and cause stress concentration at the tips and corners of the Si phase. The alloy is easy to form cracks along the grain boundaries, or the plate Si itself cracks, which makes the alloy brittle, the mechanical properties, especially the elongation, are significantly reduced, and the cutting function is not good. In order to change the existing state of silicon and improve the mechanical properties of the alloy, a modifier is generally added to the alloy to refine primary silicon and eutectic silicon.

There are many researches on aluminum alloy modifiers at home and abroad. The common modification methods include adding an element alone, or adding a variety of elements and compounds. Both of these methods have a good refining effect on primary silicon and eutectic silicon. . The main metamorphic elements include phosphorus, sodium, barium, rare earth and calcium. These elements can be used as single modifiers or as composite modifiers, such as sulfur-phosphorus composite modifiers, rare earth phosphorus composite modifiers, barium-phosphorus composite modifiers, sodium Phosphorus composite modifier, carbon-phosphorus composite modifier, barium-phosphorus composite modifier, etc. Although these single or composite modifiers have good primary silicon refinement, they still have obvious shortcomings when they are metamorphosed.

When red phosphorus is used as a modifier, the ignition point is relatively low, transportation and storage are difficult, and in the process of refining and metamorphism, the combustion is violent, resulting in a decrease in phosphorus absorption rate, toxic gas generation, and serious environmental pollution. Secondly, in the process of smelting, it is easy to A large amount of reaction slag and compounds are produced, which corrode the furnace lining and increase the loss of aluminum. When the A1-P master alloy is used for modification, although the above-mentioned defects are overcome, the A1-P master alloy is not conducive to industrial production due to its toxicity, complex production process and high price. When the sodium modifying agent is used to modify the ZLD101A aluminum alloy, there are disadvantages such as adsorption poisoning and short modification time. Barium mainly affects the morphology of primary crystal silicon in ZLD101A aluminum alloy, and has little effect on the size of primary crystal silicon. Moreover, barium is used for deterioration. Due to the reaction of barium and chlorine, it cannot be refined and degassed with chlorine gas or chlorine-containing double salt. Barium metamorphism also has disadvantages such as easy to cause inhalation and high price, so it cannot be widely used in industrial production. It is easy to cause inhalation in the process of calcium deterioration. Due to the strict requirements on calcium content, the process is difficult to master, and the deterioration effect is not as good as that of phosphorus and sodium. When rare earth is used as a single modifier, the refining effect is not obvious, and it must be combined and assisted by modifiers such as sodium and phosphorus to play a metamorphic effect. Other composite modifiers also have many problems such as mutual inhibition of metamorphic elements, excessive slag and gas production, and difficulty in precise proportioning.

The basic principle of spray forming technology is to use high-pressure inert gas to atomize and break the metal liquid flow into large and small droplets, and deposit them on the receiving substrate before it is completely solidified. Its movement mode can directly produce different shapes of deposition blanks with rapid solidification structure characteristics such as round ingots, tube blanks, slabs, discs, etc. from liquid metal. The molten metal flows out through the guide tube and is broken by the high-speed airflow at the outlet of the atomizing nozzle, and the mist column is a small dispersed droplet jet; Exchange; before reaching the deposition surface, the droplets smaller than a certain critical size solidify into aptamer particles, the larger size remains liquid, while the intermediate size droplets contain a certain proportion of liquid phase semi-solidified particles. The molten droplets with different degrees of solidification hit the deposition surface at high speed, and adhere, spread, accumulate and fuse on the deposition surface to form a thin semi-liquid layer and then rapidly solidify and crystallize, and gradually grow into a large sedimentary blank. The size and co-velocity distribution of these droplet particles varies with the design of the atomizer, the flow rate and flow rate of the atomizing medium, and the variation range is very wide. When the total energy of the particles collides, except for a part that continues to be retained by the particles as metastable energy storage, the rest is transformed into the particles' reheating and exothermic, deformation flow or introduction into the pre-arrived deposited particles, followed by deformation and fragmentation and heat consumption. scattered. Finally the particles are cooled and agglomerated by the precipitator or the previous deposition layer. During the flight of the particles, the molten droplets are completely solidified and the molten droplets are completely in liquid form. In the first case, a tight metal bond cannot be achieved, and a deposition body cannot be obtained; in the second case, a high cooling rate cannot be achieved, and an ideal microstructure cannot be obtained, similar to the traditional casting method. In general, particles with a particle size smaller than 5 μm are fully solidified during flight; particles larger than 500 μm are in a completely liquid state. The particle size distribution of the sprayed droplet group should be controlled so that the droplet consists of three parts: solid, semi-solid and liquid. An ideal deposit can be obtained by adjusting and controlling process parameters.

Chinese invention CN201210245793.4 discloses a long-acting modifier for aluminum alloy casting, which contains the following substances by mass concentration: Ba is 5-30%, B is 5-20%, P is 5-20%, and aluminum is the excess quantity. Compared with the prior art, the modifier of the above-mentioned composition combines the characteristics of Ba, B, P and other elements in the modification of the aluminum alloy. Among them, Ba has a good metamorphic effect on primary silicon and eutectic silicon in Al-Si alloy, and has the advantages of long-term metamorphism, no tendency to getter and low price. B and P have a strong effect on grain refinement, which can significantly refine Al grains in the metallographic structure of Al-Si alloy, and also have the characteristics of metamorphism and long-term effect. The modifying agent not only has obvious effect on the microstructure refinement of α-phase (aluminum) and modified eutectic Si of the aluminum alloy, but also has a lower cost than the aluminum-barium modifying agent.

The above invention uses barium, boron, and phosphorus elements to form an intermediate alloy in aluminum as a modifier. Although the modification effect is obvious and the modification time is long, the poisonous defect of the Al-P alloy cannot be overcome, and the intermediate alloy is relatively dense, and the dispersion is relatively slow. The effect is slow, the incubation period is long, and the hypoeutectic aluminum alloy cannot be rapidly and effectively metamorphosed. Although the size of the eutectic silicon can eventually be reduced, the long-term smelting can also easily cause the burning loss of the aluminum, change the composition of the aluminum alloy, and reduce the mechanical properties. In addition, the refining and degassing step cannot be omitted in the smelting process, which reduces the efficiency of aluminum-silicon alloy production. Therefore, it is necessary to develop a multi-functional aluminum alloy metamorphic material that can not only efficiently metamorphose and refine, but also degas and remove slag.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention: in view of the problems that metamorphism treatment and slag removal and degassing cannot be carried out at the same time in the current ZLD101A aluminum alloy smelting process, and the commonly used modifiers are ineffective and easy to burn out, the present invention provides an aluminum alloy refining material. , to solve the above problems, and at the same time overcome the defects of slow melting, long incubation period and difficult control of the preparation process of the casting master alloy modifier.

In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:

An aluminum alloy refining material is made from the following raw materials: potassium fluoroaluminate 5-8wt%, sodium fluoroaluminate 7-11wt%, disodium hydrogen phosphate hydrate 3-5wt%, potassium chloride 5-7wt% , sodium chloride 4-8wt%, barium acetate 0.4-0.8wt%, barium nitrate 3-6wt%, samarium fluoride 0.2-0.9wt%, aluminum acetate 0.2-0.9wt%, aluminum chloride 6-8wt%, lithium Mica composite powder 15-20wt%, the balance is pure aluminum;

The lepidolite compound powder contains 14-19% cryptocrystalline graphite, 36-39% samarium-containing compound, 0.5-0.9% potassium carbonate, and the balance is lepidolite powder; the samarium-containing compound is composed of 250-280 It is prepared from lepidolite powder in parts by weight, 31-35 parts by weight of phosphotungstic acid, 31-37 parts by weight of samarium nitrate and 2000 parts by weight of absolute ethanol.

Preferably, the potassium fluoroaluminate, sodium fluoroaluminate, disodium hydrogen phosphate hydrate, potassium chloride, sodium chloride, barium acetate, barium nitrate, samarium fluoride, aluminum acetate, aluminum chloride, cryptocrystalline The purity of graphite, potassium carbonate, phosphotungstic acid, samarium nitrate and pure aluminum are all greater than 99.9wt%, and the particle size is 100-150 mesh; the samarium nitrate is hexahydrate samarium nitrate; the aluminum alloy refining material contains 4.56 g ~7.65 wt% rare earth samarium phosphotungstate.

A preparation method of the above-mentioned aluminum alloy refining material, comprising the following specific steps:

(1) the samarium-containing compound is prepared as follows: after the samarium nitrate and phosphotungstic acid are weighed, they are respectively dissolved in the absolute ethanol of 1000 parts by weight, and the samarium nitrate ethanol solution is added dropwise to the phosphotungstic acid ethanol solution while stirring, After complete mixing, add lepidolite powder, stir at a constant temperature of 30°C for 30-40h, completely volatilize the ethanol in a vacuum drying oven at 60-80°C, dry in an oven to dryness, crush and pass through a 50-mesh sieve to obtain a samarium-containing compound;

(2) Preparation of lepidolite compound powder: the cryptocrystalline graphite, samarium-containing compound, potassium carbonate, and lepidolite powder are batched according to the weight ratio, and all the raw materials are placed in a planetary ball mill to grind and mix at room temperature, and the rotating speed is 150～300rpm. , the grinding time is 30-45min, rinse the ball mill jar and the steel balls in the jar with alcohol to obtain a turbid liquid, place the liquid in a vacuum drying oven, and after the alcohol is completely evaporated, pass the mixed powder through a 150-250 mesh sieve to obtain lepidolite Compound powder;

(3) take by weight barium acetate, barium nitrate, samarium fluoride, aluminium acetate, aluminium chloride, pure aluminium, pure aluminium ingot is heated to 740-770 ℃ in graphite crucible, treat pure aluminium ingot completely melted into After the aluminum melt, barium acetate, barium nitrate, samarium fluoride, aluminum acetate, and aluminum chloride are added, and stirred at 1500-2000 rpm for 10 minutes. After standing for 5 minutes, the slag generated on the surface of the aluminum melt is removed; the temperature of the aluminum melt is increased to 800-820℃, stir for 1-3min and then keep warm, use the multi-layer spray deposition plate preparation device to prepare the master alloy powder. The spray deposition powder milling parameters are: the atomizing gas is an industrial high-pressure inert gas, the atomizing gas pressure is 3-5MPa, The vertical spray distance is 245-330mm, the inner diameter of the catheter is 3-5mm, the spray angle is 35°-45°, the pouring temperature is 730-750°C, the graphite crucible temperature is 750-780°C, the deposition tray is placed horizontally, and the deposition tray is placed horizontally. The horizontal moving speed is 1.1～2.2mm/s, the vertical moving speed is 0.67～1.14mm/s, the deposition plate makes horizontal reciprocating motion at the same speed every 35s～55s, and stops the deposition when the powder thickness of the deposit layer reaches 15～25cm , cooled to room temperature naturally, scraped off the powder with a thickness of 1-3 cm on the surface layer, and took the powder with a thickness of 12-20 cm in the middle of the deposition layer to obtain the master alloy powder;

(4) All the lepidolite composite powder and master alloy powder are added to the ball mill for ball milling, and the cooled ball milled powder is passed through a 200-250 mesh sieve for later use; the ball-milled powder is placed in a metal cylinder mold with a diameter of 50-70 mm , After 10-30MPa pre-pressing, pressurize to 150-250KN, hold pressure under 150-250KN pressure for 3-8min, reverse the direction and carry out double-sided pressing under the same pressure, place the compact in a vacuum sintering furnace, vacuumize The temperature is 1～9×10 ^-4 Pa, the temperature is raised to 450～560°C at 50～80℃/min, the temperature is kept for 30～60min, and then the aluminum alloy refined material is obtained by cooling to room temperature with the furnace under vacuum.

Preferably, the composition of the lepidolite powder is: Al ₂ O ₃ is 23.98-28.34 wt %, H ₂ O is 1.22-2.09 wt %, FeO is 0.34-1.08 wt %, MgO is 0.02-0.09 wt %, and CaO is 0.32-2. _{F _ _ _} It is 3.20-4.90wt%, Rb2O is 0.29-0.42wt%, _Cs2O is _0.22-0.63wt %, the balance is _SiO2 , and the particle size of the lepidolite powder is 80-100 mesh.

Preferably, the parameters of ball milling in the step (4) are that the ratio of ball to material is added at a ratio of 10:1, the rotation speed is 50-100 r/min, the direction is reversed every 15-30 min, and the ball-milling time is 2-4 h.

An aluminum alloy modification method, wherein the above-mentioned aluminum alloy refining material is used to modify the ZLD101A aluminum alloy, and the specific steps are as follows:

(1) Smelting the ZLD101A aluminum alloy in an induction furnace, adjusting the smelting temperature to 730-750°C and the smelting time to 35min;

(2) After the ZLD101A aluminum alloy is completely melted, under the stirring condition of 400-800 rpm, put in the aluminum alloy refining material at 740-760 ℃, and the addition amount is 1.5-2.0wt% of the ZLD101A aluminum alloy, and the aluminum alloy refining material is added. Completely press into the solution below the liquid level, then stir for 40-70 s, stop stirring and let stand for 4-14 min; ultrasonically treat the solution while standing and keep warm, the frequency is 22-38 kHz, and the treatment time is 4-14 min. After cooling to 720-735℃, it is poured into the mold;

(3) The casting is demolded after natural cooling, solid solution at 330～370℃ for 55min, water cooling, aging at 100～110℃ for 50～70h, and air cooling to obtain aluminum alloy.

Preferably, the composition of the ZLD101A aluminum alloy is Si 6.0-7.0%, Fe 0.02-0.06%, Ti 0.01-0.02%, Mg 0.2-0.4%, Cu≤0.06%, Mn≤0.08%, Zn≤0.08% by weight 0.08%, Ca≤0.02%, total impurities≤0.5%, and the balance is Al.

The beneficial effects obtained by the present invention:

(1) The lepidolite powder and rare earth samarium element in the samarium-containing composite can change the shape and size of the harmful phases formed by other raw materials and elements such as calcium, zinc, copper, and lead in the ZLD101A aluminum alloy, prevent the segregation of impurity phases, and save energy at the same time. The step of removing slag; rare earth samarium element can also assist in improving the refining and modification effect of sodium, barium and lithium modifiers on eutectic silicon, changing the microstructure and improving the modification treatment efficiency of changing alloy phase materials;

(2) The lepidolite powder can effectively assist in degassing and slag removal, and ultrasonic treatment of the solution can also effectively degas and prevent pores from being generated in the hypereutectic aluminum alloy castings. Therefore, the material prepared in the present invention can also be degassed during the metamorphic treatment. Gas and slag removal, saves the step of removing slag and degassing, and improves the smelting efficiency. The lepidolite powder is rich in silica, alumina and lithium oxide. Silica can react with Al during smelting to form aluminum oxide and silicon. , the inclusion of Al2O3 can further improve the hardness of the alloy, and the simple substance of silicon can increase the content of eutectic silicon in the alloy, change the composition ratio of the alloy, and further improve the mechanical properties of ZLD101A aluminum alloy. The addition of Li element can supplement the type and content of the modifier, and the sodium and barium modifier can be quickly and effectively modified.

(3) In the present invention, the lepidolite composite powder and the master alloy powder are extruded and then sintered at one time. There are various compound reactions in the sintering process, such as samarium fluoride and samarium nitrate and phosphotungstic acid to form rare earth samarium phosphotungstic acid salt , graphite and silicon elements form silicon carbide, silicon dioxide and Al form alumina, etc. Under vacuum conditions, the possibility of element oxidation can be eliminated, and the extrusion process can further reduce the distance between the fine raw material powder and raw materials, so that the diffusion and sintering of each element is more efficient. In order to be uniform and thorough, the energy consumption of the compound reaction is reduced, and the yield of rare earth samarium phosphotungstate is higher. The pre-melting powder spraying of the master alloy can reduce the burning loss of the modifiers such as rare earth samarium phosphotungstate and sodium under repeated calcination and high-temperature smelting, and finally add lepidolite composite powder for rapid extrusion and sintering, which can not only retain sodium and barium , The activity of Li modifier can also improve production efficiency, and complete the uniform compounding or combination of various elements at one time.

(4) After the powder is extruded and sintered, there are a large number of loose and porous structures, but they are linked into a solid whole, which is conducive to cutting during weighing and rapid disintegration and dispersing in the melt during use, avoiding powder dispersion and adhesion when adding. on the furnace wall and other objects.

(5) Silicon carbide, silicon oxide, aluminum oxide, etc. exist as dispersed phases in the aluminum alloy refining material, which improves the hardness of ZLD101A aluminum alloy when used; the modifier quickly exerts the metamorphic effect under the catalysis of rare earth samarium, and the incubation period is short. With the burning loss of the sodium modifier, the barium, Li and rare earth samarium modifiers play a long-term metamorphic effect, achieving a stable metamorphic treatment effect, a long effective treatment time and no incubation period. The mechanical properties of the treated alloy are more obvious. improve.

(6) The sodium modifier itself has excellent metamorphic effect and has a fast onset, but it has the shortcomings of short metamorphic time and easy burning. The metamorphic effect of rare earth samarium itself is not obvious, but it can assist sodium, barium and Li modifiers to improve the metamorphic effect , Barium and Li modifiers have a long metamorphic time and good metamorphic effect, but have a long incubation period and can be complementary to sodium modifiers. The combination of the three can effectively refine the coarse primary silicon and α-Al phases, and overcome the existence of a single modifier. A variety of defects, with the characteristics of fast onset of metamorphism, short incubation time, large effective metamorphic time range, and stable metamorphic effect. After treatment, the crystalline silicon phase and α-Al phase in the ZLD101A aluminum alloy are obviously refined, and the grain size of the crystal phase is It can be reduced to about 20 μm, which makes the mechanical properties of the alloy significantly improved.

Detailed ways

The specific embodiments of the present invention will be described in further detail below through the description of the embodiments, so as to help those skilled in the art to have a more complete, accurate and in-depth understanding of the inventive concept and technical solutions of the present invention.

Embodiment 1: prepare aluminum alloy refinement material as follows:

1. Preparation of raw materials:

The composition of lepidolite powder is: Al ₂ O ₃ is 23.98wt%, H ₂ O is 1.22wt%, FeO is 0.34wt%, MgO is 0.02wt%, CaO is 0.32wt%, TiO ₂ ≤0.03wt%, K ₂ O is 10.10wt%, Na2O is 0.05wt%, _Li2O is _3.55wt %, _MnO is 0.29wt%, F is 3.20wt%, Rb2O is 0.29wt%, _Cs2O is 0.22wt%, The remainder is SiO ₂ , and the particle size of the lepidolite powder is 80 meshes.

Potassium fluoroaluminate, sodium fluoroaluminate, disodium hydrogen phosphate hydrate, potassium chloride, sodium chloride, barium acetate, barium nitrate, samarium fluoride, aluminum acetate, aluminum chloride, cryptocrystalline graphite, potassium carbonate, The purity of phosphotungstic acid, samarium nitrate and pure aluminum are all greater than 99.9wt%, and the particle size is 100 mesh; the samarium nitrate is hexahydrate samarium nitrate;

The composition of ZLD101A aluminum alloy by weight is Si 6.0%, Fe 0.02%, Ti 0.01%, Mg 0.2%, Cu≤0.06%, Mn≤0.08%, Zn≤0.08%, Ca≤0.02%, total impurities≤0.5% , the remainder is Al.

2. Preparation of aluminum alloy refining materials

(1) The samarium-containing compound is prepared as follows: 31 parts by weight of samarium nitrate and 31 parts by weight of phosphotungstic acid are respectively dissolved in 1,000 parts by weight of absolute ethanol, and the samarium nitrate ethanol solution is added dropwise to phosphorus while stirring. In the tungstic acid ethanol solution, add 250 parts by weight of lepidolite powder after complete mixing, stir at a constant temperature of 30 °C for 30 hours, completely volatilize the ethanol in a vacuum drying oven at 60 °C, dry it in an oven to dryness, and pass through a 50-mesh sieve after crushing to obtain samarium-containing Complex;

(2) Preparation of lepidolite composite powder: according to 14wt% cryptocrystalline graphite, 36wt% samarium-containing composite, 0.5wt% potassium carbonate, and the balance is lepidolite powder for batching, and all raw materials are placed in a planetary ball mill at room temperature Grinding and mixing, rotating speed 150rpm, grinding time 30min, rinsing the ball mill jar and the steel balls in the jar with alcohol to obtain a turbid liquid, placing the liquid in a vacuum drying box, after the alcohol has evaporated completely, pass the mixed powder through a 150-mesh sieve to obtain lithium Mica complex powder;

(3) Weigh out potassium fluoroaluminate 5wt%, sodium fluoroaluminate 7wt%, disodium hydrogen phosphate hydrate 3wt%, potassium chloride 5wt%, sodium chloride 4wt%, barium acetate 0.4wt%, nitric acid by weight ratio barium 3wt%, samarium fluoride 0.2wt%, aluminum acetate 0.2wt%, aluminum chloride 6wt%, the balance is pure aluminum; pure aluminum is heated to 740 ℃ in a graphite crucible, and the pure aluminum ingot is completely melted into an aluminum solution Then, barium acetate, barium nitrate, samarium fluoride, aluminum acetate, and aluminum chloride were added, and stirred at 1500 rpm for 10 minutes. After standing for 5 minutes, the slag formed on the surface of the aluminum melt was removed; the temperature of the aluminum melt was raised to 800 ° C, and the stirring was carried out. After 1 min of heat preservation, a multi-layer spray deposition plate preparation device was used to prepare the master alloy powder. The spray deposition powder milling parameters were: the atomizing gas was an industrial high-pressure inert gas, the atomizing gas pressure was 3 MPa, the vertical spray distance was 245 mm, and the inner diameter of the catheter was is 3mm, the injection angle is 35°, the pouring temperature is 730°C, the temperature of the graphite crucible is 750°C, the deposition plate is placed horizontally, the horizontal movement speed of the deposition plate is 1.1mm/s, and the vertical moving speed is 0.67mm/s. Make horizontal reciprocating motion at the same speed every 35s, stop the deposition when the powder thickness of the deposited layer reaches 15cm, cool to room temperature naturally, scrape off the powder with a thickness of 1cm on the surface layer, and take the powder of 12cm in the middle of the deposition layer to obtain the master alloy powder;

(4) All the lepidolite composite powder and master alloy powder are added to the ball mill for ball milling, and the powder is added at a ratio of 10:1 to the ball-to-material ratio. The cooled ball-milled powder is passed through a 200-mesh sieve and used for later use; the ball-milled powder is placed in a metal cylinder mold with a diameter of 50mm, pre-pressed at 10MPa, then pressurized to 150KN, and maintained at a pressure of 150KN for 3 minutes. Double-sided pressing is carried out under pressure, the compact is placed in a vacuum sintering furnace, the vacuum degree is 1×10 ^-4 Pa, the temperature is raised to 450 °C at 50 °C/min, and the temperature is kept for 30 minutes, and then cooled to room temperature with the furnace under vacuum. Obtain aluminum alloy refinement material. The aluminum alloy refining material contains 4.56wt% of rare earth samarium phosphotungstate, 8.45wt% of silicon carbide and 38.67wt% of alumina.

The ZLD101A aluminum alloy is subjected to modification treatment with the above-mentioned aluminum alloy refining materials, and the specific steps are as follows:

(1) Smelting the ZLD101A aluminum alloy in an induction furnace, adjusting the smelting temperature to 730°C and the smelting time to 35min;

(2) After the ZLD101A aluminum alloy is completely melted, under the stirring condition of 400 rpm, the aluminum alloy refining material is added at 740 ° C, and the addition amount is 1.5wt% of the ZLD101A aluminum alloy, and the aluminum alloy refining material is completely pressed into the liquid level of the solution Next, stir for 40 s, stop stirring and keep for 4 minutes; when the solution is kept at rest, ultrasonically treat the melt with a frequency of 22-kHz and a treatment time of 4 minutes, and then cool the melt to 720 °C and cast it into the mold;

(3) The casting is demolded after natural cooling, solid solution at 330°C for 55min, water cooling, aging at 100°C for 50h, and air cooling to obtain aluminum alloy.

Embodiment 2: prepare aluminum alloy refinement material as follows:

1. Preparation of raw materials:

The composition of lepidolite powder is: Al ₂ O ₃ is 28.34wt%, H ₂ O is 2.09wt%, FeO is 1.08wt%, MgO is 0.09wt%, CaO is 1.22wt%, TiO ₂ ≤0.03wt%, K ₂ O is 12.45wt%, Na2O is _0.25wt %, _Li2O is _4.07wt %, MnO is 0.89wt%, F is 4.90wt%, Rb2O is 0.42wt%, _Cs2O is 0.63wt%, The balance is SiO ₂ , and the particle size of the lepidolite powder is 100 meshes.

Potassium fluoroaluminate, sodium fluoroaluminate, disodium hydrogen phosphate hydrate, potassium chloride, sodium chloride, barium acetate, barium nitrate, samarium fluoride, aluminum acetate, aluminum chloride, cryptocrystalline graphite, potassium carbonate, The purity of phosphotungstic acid, samarium nitrate and pure aluminum are all greater than 99.9wt%, and the particle size is 150 mesh; the samarium nitrate is hexahydrate samarium nitrate;

ZLD101A aluminum alloy composition by weight percentage is Si 7.0%, Fe 0.06%, Ti 0.02%, Mg 0.4%, Cu≤0.06%, Mn≤0.08%, Zn≤0.08%, Ca≤0.02%, total impurities≤0.5% , the remainder is Al.

2. Preparation of aluminum alloy refining materials

(1) The samarium-containing compound is prepared as follows: 37 parts by weight of samarium nitrate and 35 parts by weight of phosphotungstic acid are respectively dissolved in 1000 parts by weight of dehydrated ethanol, and the samarium nitrate ethanol solution is added dropwise to phosphorus while stirring. In the tungstic acid ethanol solution, after complete mixing, add 280 parts by weight of lepidolite powder, stir at a constant temperature of 30 °C for 40 hours, completely volatilize the ethanol in a vacuum drying oven at 80 °C, dry it in an oven to dryness, and pass through a 50-mesh sieve after crushing to obtain samarium-containing Complex;

(2) Preparation of lepidolite composite powder: according to 19wt% cryptocrystalline graphite, 39wt% samarium-containing composite, 0.9wt% potassium carbonate, and the balance is lepidolite powder for batching, and all raw materials are placed in a planetary ball mill at room temperature Grinding and mixing, rotating speed 300rpm, grinding time 45min, rinse the ball mill jar and the steel balls in the jar with alcohol to obtain a turbid liquid, put the liquid in a vacuum drying box, and after the alcohol evaporates completely, pass the mixed powder through a 250-mesh sieve to obtain lithium Mica complex powder;

(3) Weigh potassium fluoroaluminate 8wt%, sodium fluoroaluminate 11wt%, disodium hydrogen phosphate hydrate 5wt%, potassium chloride 7wt%, sodium chloride 8wt%, barium acetate 0.8wt%, nitric acid by weight ratio barium 6wt%, samarium fluoride 0.9wt%, aluminum acetate 0.9wt%, aluminum chloride 8wt%, the balance is pure aluminum; pure aluminum is heated to 770 ℃ in a graphite crucible, and the pure aluminum ingot is completely melted into an aluminum solution Then, barium acetate, barium nitrate, samarium fluoride, aluminum acetate, and aluminum chloride were added, and stirred at 2000 rpm for 10 minutes. After standing for 5 minutes, the slag generated on the surface of the aluminum melt was removed; the temperature of the aluminum melt was raised to 820 ° C, and the stirring was carried out. After 3 minutes of heat preservation, a multi-layer spray deposition plate preparation device was used to prepare the master alloy powder. The spray deposition powder milling parameters were: the atomizing gas was an industrial high-pressure inert gas, the atomizing gas pressure was 5 MPa, the vertical spray distance was 330 mm, and the inner diameter of the catheter was is 5mm, the spray angle is 45°, the pouring temperature is 750°C, the temperature of the graphite crucible is 780°C, the deposition plate is placed horizontally, the horizontal movement speed of the deposition plate is 2.2mm/s, and the vertical downward movement speed is 1.14mm/s. Make horizontal reciprocating motion at the same speed every 55s, stop the deposition when the powder thickness of the deposited layer reaches 25cm, cool to room temperature naturally, scrape off the powder with a thickness of 3cm on the surface layer, and take the powder of 20cm in the middle of the deposition layer to obtain the master alloy powder;

(4) All the lepidolite composite powder and the master alloy powder are added to the ball mill for ball milling, and the ball-to-material ratio is added at a ratio of 10:1. The cooled ball-milled powder is passed through a 250-mesh sieve and used for later use; the ball-milled powder is placed in a metal cylinder mold with a diameter of 70mm, pre-pressed at 30MPa, then pressurized to 250KN, and maintained at a pressure of 250KN for 8 minutes. Double-sided pressing is carried out under pressure, the compact is placed in a vacuum sintering furnace, the vacuum degree is 9 × 10 ^-4 Pa, the temperature is raised to 560 °C at 80 °C/min, the temperature is kept for 60 minutes, and then cooled to room temperature with the furnace under vacuum. Obtain aluminum alloy refinement material. The aluminum alloy refining material contains 7.65wt% of rare earth samarium phosphotungstate, 10.41wt% of silicon carbide and 40.22wt% of alumina.

The ZLD101A aluminum alloy is subjected to modification treatment with the above-mentioned aluminum alloy refining materials, and the specific steps are as follows:

(1) Smelting the ZLD101A aluminum alloy in an induction furnace, adjusting the smelting temperature to 750°C and the smelting time to 35min;

(2) After the ZLD101A aluminum alloy is completely melted, under the stirring condition of 800 rpm, put in the aluminum alloy refining material at 760°C, and the addition amount is 2.0wt% of the ZLD101A aluminum alloy, and completely press the aluminum alloy refining material into the liquid level of the solution Then, stir for 70 s, stop stirring and keep for 14 minutes; when keeping for 14 minutes, ultrasonically treat the melt with a frequency of 38 kHz and a treatment time of 14 minutes, and cool the melt to 735 ° C and cast it into the mold;

(3) The castings are demolded after natural cooling, solid solution at 370 °C for 55 minutes, water cooling, aging at 110 °C for 70 hours, and air cooling to obtain aluminum alloys.

Embodiment 3: prepare aluminum alloy refinement material as follows:

1. Preparation of raw materials:

The composition of lepidolite powder is: Al ₂ O ₃ is 26.12wt%, H ₂ O is 1.69wt%, FeO is 0.75wt%, MgO is 0.05wt%, CaO is 0.81wt%, TiO ₂ ≤0.03wt%, K ₂ O is 11.33wt%, Na2O is _0.14wt %, _Li2O is _3.84wt %, MnO is 0.57wt%, F is 4.11wt%, Rb2O is 0.35wt%, _Cs2O is 0.41wt%, The remainder is SiO ₂ , and the particle size of the lepidolite powder is 90 meshes.

Potassium fluoroaluminate, sodium fluoroaluminate, disodium hydrogen phosphate hydrate, potassium chloride, sodium chloride, barium acetate, barium nitrate, samarium fluoride, aluminum acetate, aluminum chloride, cryptocrystalline graphite, potassium carbonate, The purity of phosphotungstic acid, samarium nitrate and pure aluminum are all greater than 99.9wt%, and the particle size is 130 mesh; the samarium nitrate is hexahydrate samarium nitrate;

ZLD101A aluminum alloy composition by weight percentage is Si 6.5%, Fe 0.04%, Ti 0.015%, Mg 0.3%, Cu≤0.06%, Mn≤0.08%, Zn≤0.08%, Ca≤0.02%, total impurities≤0.5 %, the remainder is Al.

2. Preparation of aluminum alloy refining materials

(1) The samarium-containing compound is prepared as follows: 35 parts by weight of samarium nitrate and 33 parts by weight of phosphotungstic acid are respectively dissolved in 1000 parts by weight of absolute ethanol, and the samarium nitrate ethanol solution is added dropwise to phosphorus while stirring. In the tungstic acid ethanol solution, after complete mixing, add 265 parts by weight of lepidolite powder, stir at a constant temperature of 30 °C for 35 hours, completely volatilize the ethanol in a vacuum drying oven at 70 °C, dry it in an oven to dryness, and pass through a 50-mesh sieve after crushing to obtain samarium-containing Complex;

(2) Preparation of lepidolite compound powder: according to 16.5wt% cryptocrystalline graphite, 37.5wt% samarium-containing compound, 0.7wt% potassium carbonate, and the balance is lepidolite powder for batching, and all raw materials are placed in a planetary ball mill The jar was ground and mixed at room temperature, the rotation speed was 225 rpm, and the grinding time was 38 min. The ball mill jar and the steel balls in the jar were rinsed with alcohol to obtain a turbid liquid. The liquid was placed in a vacuum drying box. After the alcohol evaporated completely, the mixed powder was passed through a 200-mesh sieve. Obtain lepidolite compound powder;

(3) Weigh potassium fluoroaluminate 6.5wt%, sodium fluoroaluminate 9wt%, disodium hydrogen phosphate hydrate 4wt%, potassium chloride 6wt%, sodium chloride 6wt%, barium acetate 0.6wt%, barium nitrate 4.5wt%, samarium fluoride 0.55wt%, aluminum acetate 0.55wt%, aluminum chloride 7wt%, the balance is pure aluminum; pure aluminum is heated in a graphite crucible to 755 ℃, and the pure aluminum ingot is completely melted into After the aluminum melt, barium acetate, barium nitrate, samarium fluoride, aluminum acetate, and aluminum chloride were added, and stirred at 1750 rpm for 10 minutes. After standing for 5 minutes, the slag generated on the surface of the aluminum melt was removed; the temperature of the aluminum melt was increased to 810 ° C After stirring for 2min, keep the temperature, and use the multi-layer spray deposition plate preparation device to prepare the master alloy powder. The spray deposition powder milling parameters are: the atomizing gas is an industrial high-pressure inert gas, the atomizing gas pressure is 4MPa, the vertical spraying distance is 285mm, and the liquid conducting The inner diameter of the tube is 4mm, the spray angle is 40°, the pouring temperature is 740°C, the temperature of the graphite crucible is 765°C, the deposition plate is placed horizontally, the horizontal movement speed of the deposition plate is 1.65mm/s, and the vertical downward movement speed is 0.9mm/s. The deposition plate moves horizontally back and forth at the same speed every 45s until the deposition layer powder thickness reaches 20cm and stops the deposition, naturally cools to room temperature, scrapes off the 2cm-thick powder on the surface layer, and takes 16cm of powder in the middle of the deposition layer to obtain the intermediate alloy powder;

(4) All the lepidolite composite powder and master alloy powder are added to the ball mill for ball milling, and the ball-to-material ratio is added in a ratio of 10:1. The rotation speed is 75r/min, and the direction is reversed every 25min. The cooled ball-milled powder is passed through a 230-mesh sieve and used for later use; the ball-milled powder is placed in a metal cylinder mold with a diameter of 60mm, pre-pressed at 20MPa, and then pressurized to 200KN, maintained at a pressure of 200KN for 5.5min, and reversed at Double-sided pressing was carried out under the same pressure, and the compact was placed in a vacuum sintering furnace with a vacuum degree of 5 × 10 ^-4 Pa, 65 °C/min heated to 505 °C, kept for 45 minutes, and then cooled to room temperature with the furnace under vacuum That is, the aluminum alloy refined material is obtained. The aluminum alloy refining material contains 6.23wt% of rare earth samarium phosphotungstate, 9.87wt% of silicon carbide and 36.88wt% of alumina.

The ZLD101A aluminum alloy is subjected to modification treatment with the above-mentioned aluminum alloy refining materials, and the specific steps are as follows:

(1) Smelting the ZLD101A aluminum alloy in an induction furnace, adjusting the smelting temperature to 740°C and the smelting time to 35min;

(2) After the ZLD101A aluminum alloy is completely melted, under the stirring condition of 600rpm, put in the aluminum alloy refining material at 750°C, and the addition amount is 1.75wt% of the ZLD101A aluminum alloy, and completely press the aluminum alloy refining material into the liquid level of the solution Next, stir for 55 s, stop stirring and keep for 9 minutes; when keeping for 9 minutes, ultrasonically treat the melt with a frequency of 30 kHz and a treatment time of 9 minutes, and cool the melt to 727 ° C and cast it into the mold;

(3) The casting is demolded after natural cooling, solid solution at 350℃ for 55min, water cooling, aging at 105℃ for 60h, and air cooling to obtain aluminum alloy.

Comparative Example 1: The ZLD101A aluminum alloy was subjected to modification treatment using the modifying agent and modification method disclosed in Chinese Patent CN201210245793.4, and the obtained aluminum alloy was used for subsequent mechanical property test comparison.

Comparative Example 2: Others are the same as Example 3, except that elemental aluminum powder is used to replace the lepidolite powder.

Comparative Example 3: Others are the same as in Example 3, except that the lepidolite composite powder is added to the aluminum melt together with other raw materials in step (3) for smelting during the preparation process.

In order to test the modification effect of the present invention and the influence on the mechanical properties of aluminum alloys, the following experiments were carried out on the aluminum alloys prepared in Comparative Examples 1-3 and Examples 1-3:

1. Mechanical properties test

The ZLD101A aluminum alloy castings prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to mechanical property testing and SEM observation of crystal phase size.

The obtained sample was machined into a standard 8mm short tensile test bar according to GB6397-86, and the tensile test was carried out on a microelectronic control universal testing machine to measure its tensile strength, hardness and elongation. The final result was 6 average value of the samples. The results are shown in Table 1.

Table 1 Testing results of mechanical properties of ZLD101A aluminum alloy castings

2. Metallographic determination

The sample was taken from the center of the alloy test bar, and after grinding and polishing, its microstructure was observed under an optical microscope. Four different fields of view were taken to observe and measure the crystal size of the α-Al phase and the eutectic silicon phase in each field of view. The statistical results are shown in Table 2.

Table 2 α-Al phase and eutectic silicon phase crystal size test results

group α-Al phase size (μm) Eutectic silicon phase size (μm) Example 1 24.6±1.9 19.2±1.0 Example 2 21.1±1.5 19.4±1.1 Example 3 23.3±1.8 20.8±1.2 Comparative Example 1 30.5±2.0 28.9±1.6 Comparative Example 2 46.2±1.7 49.1±1.3 Comparative Example 3 48.7±2.5 38.5±2.1 ZLD101A 68.8±1.2 58.9±2.3

The results of Table 1 combined with Table 2 show that although the crystal size of Comparative Example 1 is effectively reduced due to the use of phosphorus, barium and boron modifiers, the effect and final mechanical properties of the aluminum alloy are significantly lower than those of Example 3. One is that the lack of The strengthening effect of rare earth modifier makes the size of α-Al phase and eutectic silicon larger, resulting in lower mechanical properties. Second, due to the lack of high-hardness dispersed phases such as silicon carbide and alumina, the hardness and mechanical properties of aluminum alloys are higher Low.

Comparative Example 2 did not use lepidolite powder, resulting in the lack of lithium modifier contained in the alloy refining material, as well as the lack of high-hardness dispersed phases such as alumina, silicon oxide and silicon carbide generated by subsequent sintering, resulting in the final modification effect. Compared to Example 3, the final hardness and mechanical properties of the aluminum alloy are also lower than those of Example 3.

In Comparative Example 3, a high-temperature smelting method was used to prepare the alloy refiner, and the smelting and calcination were repeated during the preparation process, and the temperature was higher and the duration was longer, resulting in partial burning of the modifier, making the final metamorphic effect significantly worse than that. Example 3.

3. Hole observation

After the samples were scanned by SEM, 10 different fields of view were taken for each sample to observe whether there were holes in a single field of view and the average number of holes in each field of view. The results are shown in Table 3.

Table 3 Observation results of sample holes

Table 1 combined with the data in Table 3 shows that no slag and degassing operation was performed in Examples 1 to 3, but since the modifier contained lepidolite powder, the degassing operation was completed at the same time as the metamorphic treatment, and the degassing effect was better, so that the final There are no holes in the alloy castings. In Comparative Example 2, no lepidolite powder was used, and no slag and degassing steps were carried out, resulting in a large number of holes in the alloy casting, and the existence of impurities such as zinc, calcium, copper, etc. Segregation phenomenon, the formation of holes and segregation makes the alloy mechanical Performance is significantly reduced. Comparative Example 1 can only reduce the inhalation tendency due to the longer deterioration time, but cannot completely avoid the generation of pores. There are still a small number of pores in the aluminum alloy casting, which is not conducive to subsequent forging and mechanical properties improvement.

4. Determination and comparison of deterioration time range

The modifier materials prepared in Comparative Examples 1 and 3 and Example 3 were treated with ZLD101A aluminum alloy according to the alloy preparation method in Example 3, and the modification time range was measured. The method is as follows:

After the ZLD101A aluminum alloy was melted, different modifier materials were added respectively, the stirring time was 60s, and the holding time for static modification was 1min, 5min, 10min, 15min, 20min, 40min, 80min, 160min, 240min, 360min, and different metamorphisms were measured respectively. The crystal size of the eutectic silicon in the alloy prepared under the time, the results are shown in Table 4:

Table 4 Variation of eutectic silicon crystal size in alloys with time

Deterioration time (min) Comparative Example 1 Comparative Example 3 Example 3 1 88.8μm 81.3μm 35.5μm 5 85.3μm 74.6μm 24.5μm 10 82.7μm 61.2μm 21.2μm 15 72.3μm 50.2μm 19.3μm 20 58.2μm 38.2μm 19.7μm 40 33.7μm 37.9μm 20.1μm 80 31.1μm 38.0μm 20.8μm 160 33.3μm 37.2μm 22.7μm 240 37.2μm 39.9μm 23.9μm 360 38.4μm 41.7μm 31.6μm

From the results in Table 4, it can be seen that the aluminum alloy refined material prepared in Example 3 can quickly produce a metamorphic effect after a short incubation period. This is due to the loose structure of the refined material, which can be quickly dissolved and dispersed in the metal liquid after adding, and the sodium The rapid metamorphism of the modifier makes the metamorphic incubation period short, and the best metamorphic effect can be achieved in 1 to 5 minutes, while the cooperation of other long-acting modifiers such as barium, Li, and rare earth samarium elements in the refining material makes the aluminum alloy refining material After 5 minutes, the stable metamorphic period is reached, and the stable metamorphic effect can last for more than 6 hours. The effective metamorphic time span is large, which can meet the effective metamorphic time requirement of most aluminum alloy smelting, and make up for the short metamorphic time of sodium modifier.

However, the metamorphic material prepared in Comparative Example 1 started to produce obvious metamorphic effect in about 40 minutes, and the effect was slow, which easily led to the burning loss of aluminum and the inhalation of the melt. This was because the intermediate alloy was relatively dense, and it took time to melt and disperse. , and in order to maximize the metamorphic effect, phosphorus, barium, and boron are required, so the onset is slow. Although the subsequent metamorphic effect is relatively stable and lasts longer, the aluminum alloy metamorphic treatment effect is not as good as Example 3.

In Comparative Example 3, all raw materials were directly added for melting and casting, and the burning loss of the sodium modifier was serious in the preparation process, so the onset of its metamorphic effect was relatively slow, and the metamorphic effect was worse than that of Example 3, and the metamorphic effect after 20min tended to be It is stable and lasts as long as 6 hours. This is because its metamorphic effect mainly comes from barium, Li modifier and rare earth samarium, but because the total amount of modifier in the aluminum alloy refined material decreases after the sodium modifier is burned, the metamorphic effect changes. Difference.

To sum up, the lepidolite powder and rare earth samarium element in the samarium-containing composite can change the shape and size of the harmful phases formed by other raw materials and elements such as calcium, zinc, copper, and lead in the ZLD101A aluminum alloy, and prevent the segregation of impurity phases. At the same time, the slag removal step is omitted; the rare earth samarium element can also assist in improving the refining and metamorphic effect of sodium, barium and lithium modifiers on eutectic silicon, changing the microstructure and improving the modification efficiency of alloy phase materials; lepidolite powder can effectively help Degassing and slag removal, ultrasonic treatment of the solution can also effectively degas and prevent pores from being generated in the hypereutectic aluminum alloy castings. Therefore, the material prepared in the present invention can also be degassed and slag removed during the metamorphic treatment, saving slag and degassing Step, improve the smelting efficiency, the lepidolite powder is rich in silica, alumina and lithium oxide, silica can react with Al during smelting to form aluminum oxide and silicon, and the inclusion of aluminum oxide can further Improve the hardness of the alloy, and the simple substance of silicon can increase the content of eutectic silicon in the alloy, change the composition ratio of the alloy, and further improve the mechanical properties of ZLD101A aluminum alloy. The addition of Li element can supplement the type and content of the modifier, and the sodium and barium modifier can be quickly and effectively modified. In the invention, the lepidolite composite powder and the intermediate alloy powder are extruded and then sintered at one time. There are various compound reactions in the sintering process, such as samarium fluoride and samarium nitrate and phosphotungstic acid to form rare earth samarium phosphotungstate, graphite and tungsten. Silicon element forms silicon carbide, silicon dioxide and Al form alumina, etc. Under vacuum conditions, the possibility of element oxidation can be eliminated, and the extrusion process can further reduce the distance between the fine raw material powder and raw materials, so that the diffusion and sintering of each element is more uniform and thorough. , the energy consumption of the compound reaction is reduced, and the yield of rare earth samarium phosphotungstate is higher. The pre-melting powder spraying of the master alloy can reduce the burning loss of the modifiers such as rare earth samarium phosphotungstate and sodium under repeated calcination and high-temperature smelting, and finally add lepidolite composite powder for rapid extrusion and sintering, which can not only retain sodium and barium , The activity of Li modifier can also improve production efficiency, and complete the uniform compounding or combination of various elements at one time. After the powder is extruded and sintered, there are a lot of loose and porous structures, but they are combined into a solid whole, which is conducive to cutting during weighing and rapid disintegration and dispersing in the melt during use, preventing powder from scattering and adhering to the furnace wall when added. on other objects. Silicon carbide, silicon oxide, aluminum oxide, etc. exist as dispersed phases in the aluminum alloy refining material, which increases the hardness of ZLD101A aluminum alloy when used; the modifier quickly exerts the metamorphic effect under the catalysis of rare earth samarium, and the incubation period is short. For the burning loss of the modifier, the barium, Li and rare earth samarium modifiers play a long-term metamorphic effect, achieving a stable metamorphic treatment effect, a long effective treatment time and no incubation period, and the mechanical properties of the treated alloy are significantly improved. The sodium modifier itself has an excellent metamorphic effect and has a fast onset of effect, but it has the shortcomings of short metamorphic time and easy burning. Li modifier has a long metamorphic time and good metamorphic effect, but has a long incubation period and can be complementary to sodium modifier. The combination of the three can effectively refine the coarse primary silicon and α-Al phases, and overcome many defects of a single modifier. , has the characteristics of fast onset of metamorphism, short incubation time, large effective metamorphic time range, and stable metamorphic effect. After treatment, the crystalline silicon phase and α-Al phase in ZLD101A aluminum alloy are obviously refined, and the grain size of the crystal phase can be reduced to About 20 μm, the mechanical properties of the alloy are significantly improved.

The above embodiments are only to illustrate the technical idea of the present invention, and cannot limit the protection scope of the present invention. Any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the present invention. The technology not involved in the present invention can be realized by the existing technology.

Claims (7)

1. a kind of aluminium alloy refiner material, which is characterized in that be made of the following raw material: 5~8wt% of potassium fluoroaluminate, cryolite 7 ~11wt%, disodium hydrogen phosphate hydrate 3-5wt%, potassium chloride 5-7wt%, sodium chloride 4-8wt%, barium acetate 0.4- 0.8wt%, barium nitrate 3-6wt%, samaric fluoride 0.2-0.9wt%, aluminum acetate 0.2-0.9wt%, aluminium chloride 6-8wt%, lithium cloud Female compound powder 15-20wt%, surplus are fine aluminium；

The lepidolite compound powder aphanitic graphite containing 14-19%, 36-39% compound containing samarium, 0.5-0.9% potassium carbonate, Surplus is lepidolite powder；The compound containing samarium by 250~280 parts by weight lepidolite powder, 31~35 parts by weight phosphotungstic acids, 31~ 37 parts by weight samaric nitrates and 2000 parts by weight dehydrated alcohols are made.

2. a kind of aluminium alloy refiner material according to claim 1, it is characterised in that: the potassium fluoroaluminate, fluoaluminic acid Sodium, disodium hydrogen phosphate hydrate, potassium chloride, sodium chloride, barium acetate, barium nitrate, samaric fluoride, aluminum acetate, aluminium chloride, cryptocrystalline stone Ink, potassium carbonate, phosphotungstic acid, samaric nitrate, fine aluminium purity be all larger than 99.9wt%, partial size is 100~150 mesh；The samaric nitrate For six nitric hydrate samariums；The phosphotungstate containing 4.56~7.65wt% rare earth samarium in the aluminium alloy refiner material.

3. a kind of preparation method of aluminium alloy refiner material as claimed in claim 1 or 2, which is characterized in that comprising following specific Step:

(1) compound containing samarium is prepared as follows: being dissolved in the nothing of 1000 parts by weight after samaric nitrate and phosphotungstic acid are weighed respectively Samaric nitrate ethanol solution is added dropwise in phosphotungstic acid ethanol solution by water-ethanol while stirring, and lepidolite powder is added after being thoroughly mixed, 30-40h is stirred in 30 DEG C of constant temperature, ethyl alcohol is volatilized completely in 60-80 DEG C of vacuum oven, baking oven is dried to over dry, smashes it through 50 meshes must contain samarium compound；

(2) preparation of lepidolite compound powder: according to weight ratio by aphanitic graphite, compound containing samarium, potassium carbonate, lepidolite powder Ingredient is carried out, whole raw materials are placed in planetary ball mill tank grinding at room temperature and are mixed, 150~300rpm of revolving speed, milling time 30~ 45min obtains troubled liquor with the steel ball in alcohol rinse ball grinder and tank, which is placed in a vacuum drying oven, to wine Mixed powder is crossed into 150~250 meshes after essence evaporation completely and obtains lepidolite compound powder；

(3) barium acetate, barium nitrate, samaric fluoride, aluminum acetate, aluminium chloride, fine aluminium are weighed by weight, by fine aluminium ingot in graphite crucible In be heated to 740-770 DEG C, by barium acetate, barium nitrate, samaric fluoride, aluminum acetate, chlorine after fine aluminium ingot is completely melt as aluminium solution Change aluminium to be added, and 1500~2000rpm stirs 10min, removes the slag that aluminium melt surface generates after standing 5min；It is molten to increase aluminium Temperature keeps the temperature after stirring 1~3min to 800-820 DEG C, prepares intermediate alloy using multi-layer spray deposition plate preparation facilities Powder, jet deposition powder parameter are as follows: atomization gas be industrial high-pressure inert gas, 3~5MPa of atomization pressure, vertically Spray distance is 245-330mm, and drain bore is 3~5mm, and spray angle is 35 °~45 °, pouring temperature 730-750 DEG C, graphite crucible temperature is 750-780 DEG C, and sediment pan is horizontal positioned, and sediment pan horizontal movement velocity is 1.1~2.2mm/s, is hung down Directly moving down speed is 0.67~1.14mm/s, and sediment pan makees horizontal back and forth movement every 35s~55s with identical speed, until heavy Lamination powder thickness stops deposition when reaching 15~25cm, and cooled to room temperature scrapes off the powder of 1~3cm of surface layer thickness, and it is heavy to take The powder of 12~20cm obtains intermediate alloy powder among lamination；

(4) ball milling in ball mill, ball-milled powder mistake after cooling is all added in lepidolite compound powder and intermediate alloy powder It is spare after 200~250 meshes；The good powder of ball milling is placed in the metallic cylinder mold of 50~70mm of diameter, 10~30MPa is pre- After pressure, it is forced into 150~250KN, 3~8min of pressure maintaining under 150~250KN pressure, commutation carries out two-sided at the same pressure Compacting, briquetting is placed in vacuum sintering furnace, and suction is 1~9 × 10^-4Pa, 50~80 DEG C/min are warming up to 450~560 DEG C, 30~60min is kept the temperature, cools to room temperature with the furnace under vacuum then up to aluminium alloy refiner material.

4. a kind of preparation method of aluminium alloy refiner material according to claim 3, it is characterised in that: lepidolite powder at It is divided into: Al₂O₃For 23.98~28.34wt%, H₂O is 1.22~2.09wt%, and FeO is 0.34~1.08wt%, MgO 0.02 ~0.09wt%, CaO are 0.32~1.22wt%, TiO₂≤ 0.03wt%, K₂O is 10.10~12.45wt%, Na₂O is 0.05 ~0.25wt%, Li₂O is 3.55~4.07wt%, and MnO is 0.29~0.89wt%, and F is 3.20~4.90wt%, Rb₂O is 0.29~0.42wt%, Cs₂O is 0.22~0.63wt%, surplus SiO₂, the partial size of the lepidolite powder is 80~100 mesh.

5. a kind of preparation method of aluminium alloy refiner material according to claim 3, it is characterised in that: the step (4) parameter of ball milling is that ratio of grinding media to material is added in the ratio of 10:1 in, and revolving speed is 50~100r/min, is commutated every 15~30min Once, 2~4h of Ball-milling Time.

6. a kind of Aluminum alloy modification method, which is characterized in that using aluminium alloy refiner material pair described in claims 1 or 2 ZLD101A aluminium alloy carries out Metamorphism treatment, the specific steps are as follows:

(1) melting in induction furnace by ZLD101A aluminium alloy adjusts 730-750 DEG C of smelting temperature, smelting time 35min；

(2) after ZLD101A aluminium alloy is completely melt, under 400~800rpm stirring condition, in 740-760 DEG C of investment aluminium alloy Refiner material, additional amount are 1.5~2.0wt% of ZLD101A aluminium alloy, and aluminium alloy refiner material is completely forced into solution liquid Face is hereinafter, being subsequently agitated for 40~70s, stopping stirring and standing heat preservation 4-14min；Solution is carried out at ultrasound when standing heat preservation Reason, frequency are 22~38kHz, and the processing time is 4~14min, are cast in casting mold after melt is cooled to 720-735 DEG C；

(3) it is demoulded after casting natural cooling, 330~370 DEG C of solid solution 55min, water cooling, 100~110 DEG C of timeliness 50~70h are air-cooled Up to aluminium alloy.

7. a kind of aluminium alloy preparation method according to claim 6, it is characterised in that: the ZLD101A al alloy component It is by weight percentage Si 6.0~7.0%, Fe 0.02~0.06%, Ti 0.01~0.02%, Mg 0.2~0.4%, Cu ≤ 0.06%, Mn≤0.08%, Zn≤0.08%, Ca≤0.02%, total impurities≤0.5%, surplus Al.