CN109988931A - A kind of aluminium alloy refiner material and its preparation method and application - Google Patents
A kind of aluminium alloy refiner material and its preparation method and application Download PDFInfo
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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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
Technical field
The present invention relates to aluminum alloy modifier field, in particular to a kind of aluminium alloy refiner material and preparation method thereof.
Background technique
The silicon tissue of aluminium alloy is made of the starlike primary silicon of five coarse valves and long acicular Eutectic Silicon in Al-Si Cast Alloys, these forms
Silicon mutually isolates Al matrix for serious, causes stress to be concentrated at the tip of Si phase and edges and corners, and alloy is easy along the boundary of crystal grain
Place or plate Si itself crack and form crackle, and alloy is made to become fragile, and mechanical performance especially elongation percentage significantly reduces, cutting
Machining function is also bad.In order to change the existence of silicon, the mechanical property of alloy is improved, it is thin generally to add alterant to alloy
Change primary silicon and Eutectic Silicon in Al-Si Cast Alloys.
More to the research of aluminum alloy modifier both at home and abroad, common Modification Manners are individually added into a kind of element, also have
Multiple element and compound, both methods, which is added, all has good refining effect to primary silicon and Eutectic Silicon in Al-Si Cast Alloys.Main change
Prime element includes phosphorus, sodium, barium, rare earth and calcium, these elements can be used as single alterant, can also form composite modifier, such as sulphur
Phosphorus composite modifier, rare earth phosphorus composite modifier, barium phosphorus composite modifier, sodium phosphorus composite modifier, carbon phosphorus composite modifier and
Barium phosphorus composite modifier etc..Although these single or composite modifiers have preferable primary silicon refining effect, when going bad
Remain obvious disadvantage.
When using red phosphorus as alterant, burning point is relatively low, and transport and preservation are difficult, and during fine degenerate, combustion
It burns acutely, causes the reduction of phosphorus absorptivity, generate poison gas, seriously pollute environment, secondly during melting, be easy to produce a large amount of
Reaction slag and compound, corrode furnace lining, increase the loss of aluminium.And when rotten with A1-P intermediate alloy, although overcoming
State defect, but A1-P intermediate alloy is due to toxic, and the more complex price of production technology is higher, therefore is unfavorable for industrial metaplasia
It produces.When sodium alterant is to ZLD101A Aluminum alloy modification, there is the disadvantages of absorption poisoning effect, deteriorating time is short.Barium mainly influences
Primary silicon pattern in ZLD101A aluminium alloy is not apparent on the influence of the size of primary silicon.And it is rotten using barium, due to
Barium is reacted with chlorine, cannot refine degasification with chlorine or double salt containing chlorine.Barium is rotten, and there is also easily cause air-breathing, expensive etc. to lack
Point, therefore cannot be widely applied in industrial production.Air-breathing is easily caused in calcium metamorphic process, it is tight due to requiring calcium content
Lattice, therefore technique is difficult to grasp, and modification effect is not so good as phosphorus and sodium.Thinning effect is unobvious when rare earth is as single alterant,
It must combine and assist sodium and the agent of phosphorus iso-metamorphism can just play metamorphism.There is also alterant elements to press down mutually for other composite modifiers
System, production slag production gas is excessive, accurate to match the problems such as difficulty.
The basic principle of spray forming technology is that by the atomization of metal liquid stream, to be broken into great Dong tiny using high-pressure inert gas
Drop, not yet completely before solidification, be deposited into and receive on matrix, base shape and controlled by rationally setting to beg for receive at it
Its motion mode is made, billet, pipe, slab, disk etc. with rapid solidification structure feature can be directly produced from liquid metal
Deposition blank of different shapes.Molten metal is flowed out through diversion pipe, and the high-speed flow for being atomized jet expansion is broken, and mist column is thin
The molten drop jet stream of small disperse；Atomized droplet jet stream accelerates under high-speed flow momentum, and carries out strong heat with modern stream
Exchange；Before reaching deposition surface, the molten drop less than a certain critical dimension is frozen into aptamer particle, and larger size remains as liquid
State, and the molten drop of intermediate sizes is then containing half solidified particle of certain proportion liquid phase, these big and small coagulation grades are different
Molten drop high-speed impact deposition surface, and adhere on heavy private surface, sprawls, accumulates, fuse it is fast after one thin semi liquid state layer of formation
Fast solidification and crystallization, gradually stone product is grown to serve as a bulk deposition base.The size of these molten drop particles is total to VELOCITY DISTRIBUTION with atomization
The design of device, the variation of the flow velocity of atomizing medium and flow and change, and variation range is very wide.Particle can collide
When, in addition to a part continues to be retained with metastable energy storage by particle, rest part is changed into the heat release of heating once again of particle, deformation stream
Broken and heat dissipation is deformed therewith in the dynamic or incoming deposited particles reached in advance.Final granule is deposited device or previous heavy
The cooling cohesion of lamination.In flight course, melting droplet is fully cured and melts droplet group to be existed particle in liquid form completely
Two kinds of extreme cases.The first situation can not achieve close metallic bond and combine, and can not obtain lithosomic body；Second situation is not
It is able to achieve high cooling rate, it is similar to traditional founding mode, ideal microstructure can not be obtained.In general, particle ruler
It is very little less than 5 μm, particle is fully cured in flight course；Particle size is greater than 500 μm, and particle is in complete liquid.Injection is molten
Drop group particle size distribution should be controlled, form molten drop by solid-state, semisolid and liquid three parts, by adjusting, control
Technological parameter processed obtains ideal lithosomic body.
Chinese invention CN201210245793.4 discloses a kind of long-acting alterant of used in aluminium alloy casting, contains following matter
Measure the substance of concentration: Ba 5-30%, B 5-20%, P 5-20%, aluminium is surplus.Compared with prior art, mentioned component
Alterant, the characteristics of combining the elements such as Ba, B, P in Aluminum alloy modification.Wherein Ba is to primary silicon in alusil alloy and eutectic
Silicon have good modification effect, have the advantages that lasting modification effects, without air-breathing be inclined to and price it is lower.B, P refines crystal grain and makees
With very by force, obvious thinning effect can be played to the Al crystal grain in alusil alloy metallographic structure, equally there is rotten long-lasting nature.The change
Matter agent is not only obvious to aluminum alloy organization's refinement α phase (aluminium) and rotten eutectic Si effect, and cost is lower compared with aluminium barium alterant.
Foregoing invention uses barium, boron, P elements in aluminium formation intermediate alloy as alterant, although modification effect is obvious,
Deteriorating time is long, but the defect that Al-P alloy can not be overcome toxic, and intermediate alloy is comparatively dense, disperses slower, action of going bad
Relatively slow, incubation period is long, can not quickly and effectively go bad to hypoeutectic aluminium alloy, although the ruler of Eutectic Silicon in Al-Si Cast Alloys may finally be reduced
It is very little, but prolonged melting also be easy to cause the scaling loss of aluminium, changes aluminium alloy composition, reduces mechanical property, and in fusion process
Refining deaeration step can not be saved, the efficiency of alusil alloy production is reduced, it is therefore desirable to which developing a kind of both can efficiently go bad
Refinement, and the rotten material of Multifunctional aluminium alloy that can be removed the gred with degasification.
Summary of the invention
The technical problems to be solved by the invention: can not go bad simultaneously in the process for current ZLD101A aluminium alloy smelting
Processing and slagging-off degasification and the problem of common alterant is ineffective and easy scaling loss, the present invention provide a kind of aluminium alloy and refine material
Material, solves the above problems, while slow casting intermediate alloy alterant melting, incubation period length, preparation process being overcome to be difficult to control
Defect.
In order to solve the above technical problems, the present invention provides technical solution below:
A kind of aluminium alloy refiner material, is made of the following raw material: 5~8wt% of potassium fluoroaluminate, 7~11wt% of cryolite,
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%, lepidolite 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% carbonic acid
Potassium, surplus are 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.
Preferably, the potassium fluoroaluminate, cryolite, disodium hydrogen phosphate hydrate, potassium chloride, sodium chloride, barium acetate, nitre
Sour barium, samaric fluoride, aluminum acetate, aluminium chloride, aphanitic graphite, potassium carbonate, phosphotungstic acid, samaric nitrate, fine aluminium purity be all larger than
99.9wt%, partial size are 100~150 mesh；The samaric nitrate is six nitric hydrate samariums；Contain 4.56 in the aluminium alloy refiner material
~7.65wt% rare earth samarium phosphotungstate.
A kind of preparation method of above-mentioned aluminium alloy refiner material includes following specific steps:
(1) compound containing samarium is prepared as follows: being dissolved in 1000 parts by weight respectively after samaric nitrate and phosphotungstic acid are weighed
Dehydrated alcohol, samaric nitrate ethanol solution is added dropwise to while stirring in phosphotungstic acid ethanol solution, after being thoroughly mixed be added lithium cloud
Female powder stirs 30-40h in 30 DEG C of constant temperature, ethyl alcohol volatilizees completely in 60-80 DEG C of vacuum oven, baking oven is dried to over dry, crushes
Samarium compound must be contained by crossing 50 meshes afterwards；
(2) preparation of lepidolite compound powder: according to weight ratio by aphanitic graphite, compound containing samarium, potassium carbonate, lithium cloud
Female powder carries out ingredient, and 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
Mixed powder is crossed into 150~250 meshes after vaporized alcohol is complete 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 Yu Shimo
740-770 DEG C is heated in crucible, by barium acetate, barium nitrate, samaric fluoride, acetic acid after fine aluminium ingot is completely melt as aluminium solution
Aluminium, aluminium chloride are added, and 1500~2000rpm stirs 10min, stand the slag of removal aluminium melt surface generation after 5min；It rises
High alumina melt temperature is kept the temperature after stirring 1~3min to 800-820 DEG C, using in the preparation of multi-layer spray deposition plate preparation facilities
Between alloy powder, jet deposition powder parameter are as follows: atomization gas be industrial high-pressure inert gas, atomization pressure 3~
5MPa, vertical spray distance are 245-330mm, and drain bore is 3~5mm, and spray angle is 35 °~45 °, and pouring temperature is
730-750 DEG C, graphite crucible temperature is 750-780 DEG C, and sediment pan is horizontal positioned, sediment pan horizontal movement velocity is 1.1~
2.2mm/s, vertically moving down speed is 0.67~1.14mm/s, and sediment pan makees horizontal round-trip fortune every 35s~55s with identical speed
Dynamic, until sedimentary powder thickness stops deposition when reaching 15~25cm, cooled to room temperature scrapes off 1~3cm of surface layer thickness
Powder takes the powder of 12~20cm among sedimentary to obtain intermediate alloy powder；
(4) ball milling in ball mill, ball milling powder after cooling is all added in lepidolite compound powder and intermediate alloy powder
It is spare after 200~250 meshes excessively of end；The good powder of ball milling is placed in the metallic cylinder mold of 50~70mm of diameter, 10~
After 30MPa precompressed, be forced into 150~250KN, 3~8min of pressure maintaining under 150~250KN pressure, commutation at the same pressure into
The two-sided compacting of row, 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.
Preferably, lepidolite meal component are as follows: Al2O3For 23.98~28.34wt%, H2O is 1.22~2.09wt%, FeO
It is 0.02~0.09wt% for 0.34~1.08wt%, MgO, CaO is 0.32~1.22wt%, TiO2≤ 0.03wt%, K2O is
10.10~12.45wt%, Na2O is 0.05~0.25wt%, Li2O be 3.55~4.07wt%, MnO be 0.29~
0.89wt%, F are 3.20~4.90wt%, Rb2O is 0.29~0.42wt%, Cs2O is 0.22~0.63wt%, and surplus is
SiO2, the partial size of the lepidolite powder is 80~100 mesh.
Preferably, the parameter of ball milling is that ratio of grinding media to material is added by the ratio of 10:1 in the step (4), revolving speed for 50~
100r/min, Ball-milling Time 2~4h primary every 15~30min commutation.
A kind of Aluminum alloy modification method carries out Metamorphism treatment to ZLD101A aluminium alloy with above-mentioned aluminium alloy refiner material, tool
Steps are as follows for body:
(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 refinement material, additional amount are 1.5~2.0wt% of ZLD101A aluminium alloy, and aluminium alloy refiner material are completely forced into molten
Body fluid face is hereinafter, being subsequently agitated for 40~70s, stopping stirring and standing heat preservation 4-14min；Ultrasound is carried out to solution when standing heat preservation
Processing, 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 50~70h of timeliness,
Air-cooled aluminium alloy to obtain the final product.
Preferably, the ZLD101A al alloy component is Si 6.0~7.0% by weight percentage, Fe 0.02~
0.06%, Ti0.01~0.02%, Mg 0.2~0.4%, Cu≤0.06%, Mn≤0.08%, Zn≤0.08%, Ca≤
0.02%, total impurities≤0.5%, surplus Al.
It is that the present invention obtains the utility model has the advantages that
(1) the lepidolite powder in compound containing samarium and rare earth samarium element can change other raw materials and ZLD101A aluminium alloy
The form and size for the harmful phase that middle calcium, zinc, copper, lead and other elements are formed, prevent impurity phase segregation, while saving slug removing step；
Rare earth samarium element can also assist improving sodium, barium, lithium alterant to the fine degenerate effect of Eutectic Silicon in Al-Si Cast Alloys, change tissue morphology, improve
Change the Metamorphism treatment efficiency of alloy phase material；
(2) lepidolite powder effectively can help degasification to remove the gred, ultrasonication solution also can effectively degasification, prevent hypereutectic
The material for generating stomata in aluminium alloy castings, therefore being prepared in the present invention while Metamorphism treatment can also degasification slagging-off, save
Remove the gred deaeration step, promotes smelting efficiency, silica and aluminium oxide and lithia rich in lepidolite powder, titanium dioxide
Silicon can react generation aluminum oxide and elementary silicon, being mingled with for aluminum oxide in melting with Al can further promote alloy
Hardness, and the content of Eutectic Silicon in Al-Si Cast Alloys in alloy can be improved in elementary silicon, changes the composition ratio of alloy, further increases ZLD101A aluminium
The mechanical property of alloy.The addition of Li element can supplement the type and content of alterant again, cooperate sodium, and barium alterant quickly has
Effect is rotten.
(3) present invention is disposably sintered after being squeezed lepidolite compound powder, master alloyed powder, is had in sintering process
A variety of combination reactions, if samaric fluoride and samaric nitrate and phosphotungstic acid form rare earth samarium phosphotungstate, graphite and element silicon, which are formed, to be carbonized
Silicon, silica and Al form aluminium oxide etc., under vacuum condition, can eliminate the possibility of element oxide, extrusion process is then further
The distance between tiny raw material powder raw material is reduced, keeps each element diffusion-sintering more uniformly thorough, combination reaction energy consumption reduces, dilute
The yields such as native samarium phosphotungstate are higher.The preparatory melting of intermediate alloy is dusted, and rare earth samarium phosphotungstate and sodium iso-metamorphism can be reduced
Scaling loss of the agent under calcining and high melt repeatedly finally adds the sintering of lepidolite composite powder crushing failure at high speed, can not only protect
The activity of sodium, barium, Li alterant is stayed, production efficiency can also be improved, the primary uniform chemical combination for completing multiple element or combination.
(4) after powder squeezes sintering, there are a large amount of loose and porous structures, but concluding is a solid-state entirety, is conducive to claim
Cutting when amount and using when fater disintegration be scattered in melt, other objects such as drift and be adhered to furnace wall when powder being avoided to be added
On body.
(5) silicon carbide, silica, aluminium oxide etc. are then present in aluminium alloy refiner material as dispersed phase, and when use mentions
The hardness of high ZLD101A aluminium alloy；Alterant fast onset modification effect under the catalysis of rare earth samarium, incubation period is short, with sodium
The scaling loss of alterant, barium, Li and rare earth samarium alterant play long-acting metamorphism, reach Metamorphism treatment effect stability, processing has
The effect time is long and without preclinical effect, and the mechanical property of the alloy after processing, which has, more to be significantly improved.
(6) sodium alterant itself has excellent modification effect, rapid-action, but that there are deteriorating times is short, and easy scaling loss lacks
Point, rare earth samarium modification effect itself is unobvious, but sodium and barium, Li alterant can be assisted to improve modification effect, and barium, Li alterant become
The matter time is long, and modification effect is good, but incubation period is long, can be complementary with sodium alterant, can effectively refine after triplicity coarse
Primary silicon and α-Al phase, overcome number of drawbacks existing for single alterant, and rapid-action with going bad, the incubation time is short, effectively become
Matter time range is big, the stable feature of modification effect, and crystalline silicon phase and α-Al are mutually bright in the ZLD101A aluminium alloy after processing
Aobvious refinement, crystal phase partial size can be down to 20 μm or so, so that the mechanical property of alloy is significantly improved.
Specific embodiment
Below by the description to embodiment, specific embodiments of the present invention will be described in further detail, with side
Those skilled in the art is helped to have more complete, accurate and deep understanding to inventive concept of the invention, technical solution.
Embodiment 1: it is prepared as follows aluminium alloy refiner material:
One, the preparation of raw material:
Lepidolite meal component are as follows: Al2O3For 23.98wt%, H2O is 1.22wt%, and FeO 0.34wt%, MgO are
0.02wt%, CaO 0.32wt%, TiO2≤ 0.03wt%, K2O is 10.10wt%, Na2O is 0.05wt%, Li2O is
3.55wt%, MnO 0.29wt%, F 3.20wt%, Rb2O is 0.29wt%, Cs2O is 0.22wt%, surplus SiO2, lithium
The partial size of mica powder is 80 mesh.
Potassium fluoroaluminate, cryolite, disodium hydrogen phosphate hydrate, potassium chloride, sodium chloride, barium acetate, barium nitrate, fluorination
Samarium, aluminum acetate, aluminium chloride, aphanitic graphite, potassium carbonate, phosphotungstic acid, samaric nitrate, fine aluminium purity be all larger than 99.9wt%, grain
Diameter is 100 mesh；The samaric nitrate is six nitric hydrate samariums；
ZLD101A al alloy component is Si 6.0%, Fe 0.02%, Ti 0.01%, Mg 0.2% by weight percentage,
Cu≤0.06%, Mn≤0.08%, Zn≤0.08%, Ca≤0.02%, total impurities≤0.5%, surplus Al.
Two, the preparation of aluminium alloy refiner material
(1) compound containing samarium is prepared as follows: being divided after 31 parts by weight samaric nitrates and 31 parts by weight phosphotungstic acids are weighed
It is not dissolved in the dehydrated alcohol of 1000 parts by weight, samaric nitrate ethanol solution is added dropwise to while stirring in phosphotungstic acid ethanol solution, it is complete
250 parts by weight lepidolite powder are added after full mixing, stirs 30h in 30 DEG C of constant temperature, waves ethyl alcohol completely in 60 DEG C of vacuum ovens
Hair, baking oven are dried to over dry, and samarium compound must be contained by smashing it through 50 meshes；
(2) preparation of lepidolite compound powder: according to 14wt% aphanitic graphite, 36wt% compound containing samarium, 0.5wt%
Potassium carbonate, surplus are that lepidolite powder carries out ingredient, and whole raw materials are placed in planetary ball mill tank grinding at room temperature and are mixed, revolving speed
150rpm, milling time 30min obtain troubled liquor with the steel ball in alcohol rinse ball grinder and tank, which are placed in very
In empty drying box, mixed powder is crossed into 150 meshes after vaporized alcohol is complete and obtains lepidolite compound powder；
(3) potassium fluoroaluminate 5wt%, cryolite 7wt%, disodium hydrogen phosphate hydrate 3wt%, chlorination are weighed by weight
Potassium 5wt%, sodium chloride 4wt%, barium acetate 0.4wt%, barium nitrate 3wt%, samaric fluoride 0.2wt%, aluminum acetate 0.2wt%, chlorine
Change aluminium 6wt%, surplus is fine aluminium；Fine aluminium is heated to 740 DEG C in graphite crucible, after fine aluminium ingot is completely melt as aluminium solution
Barium acetate, barium nitrate, samaric fluoride, aluminum acetate, aluminium chloride are added, and 1500rpm stirs 10min, remove aluminium after standing 5min
The slag that bath surface generates；Aluminum melt temperature is increased to 800 DEG C, is kept the temperature after stirring 1min, using multi-layer spray deposition plate
Preparation facilities prepares intermediate alloy powder, jet deposition powder parameter are as follows: atomization gas is industrial high-pressure inert gas, atomization
Gas pressure 3MPa, vertical spray distance are 245mm, and drain bore is 3mm, and spray angle is 35 °, pouring temperature 730
DEG C, graphite crucible temperature is 750 DEG C, and sediment pan is horizontal positioned, and sediment pan horizontal movement velocity is 1.1mm/s, vertically moves down speed
Degree is 0.67mm/s, and sediment pan makees horizontal back and forth movement every 35s with identical speed, until sedimentary powder thickness reaches 15cm
When stop deposition, cooled to room temperature scrapes off the powder of surface layer 1cm thickness, and the powder of sedimentary centre 12cm is taken to obtain intermediate conjunction
Bronze end；
(4) ball milling in ball mill is all added in lepidolite compound powder and intermediate alloy powder, ratio of grinding media to material is by 10:1's
Ratio adds powder, and revolving speed 50r/min is primary every 15min commutation, Ball-milling Time 2h.Ball-milled powder after cooling crosses 200
It is spare after mesh；The good powder of ball milling is placed in the metallic cylinder mold of diameter 50mm, after 10MPa precompressed, is forced into
150KN, the pressure maintaining 3min under 150KN pressure, commutation carry out two-sided compacting at the same pressure, briquetting are placed in vacuum sintering furnace
In, suction is 1 × 10-4Pa, 50 DEG C/min are warming up to 450 DEG C, keep the temperature 30min, then cool to room with the furnace under vacuum
Temperature is up to aluminium alloy refiner material.The phosphotungstate of rare earth samarium containing 4.56wt% in aluminium alloy refiner material is carbonized containing 8.45wt%
Silicon, aluminium oxide 38.67wt%.
Metamorphism treatment is carried out to ZLD101A aluminium alloy with above-mentioned aluminium alloy refiner material, the specific steps are as follows:
(1) melting in induction furnace by ZLD101A aluminium alloy adjusts 730 DEG C of smelting temperature, smelting time 35min；
(2) after ZLD101A aluminium alloy is completely melt, under 400rpm stirring condition, material is refined in 740 DEG C of investment aluminium alloys
Material, additional amount are the 1.5wt% of ZLD101A aluminium alloy, and aluminium alloy refiner material is completely forced into solution liquid level hereinafter, then
40s is stirred, stops stirring and standing heat preservation 4min；Solution is ultrasonically treated when standing heat preservation, frequency is 22~kHz, place
The reason time is 4min, is cast in casting mold after melt is cooled to 720 DEG C；
(3) it is demoulded after casting natural cooling, 330 DEG C of solid solution 55min, water cooling, 100 DEG C of timeliness 50h, air-cooled aluminium to obtain the final product closes
Gold.
Embodiment 2: it is prepared as follows aluminium alloy refiner material:
One, the preparation of raw material:
Lepidolite meal component are as follows: Al2O3For 28.34wt%, H2O is 2.09wt%, and FeO 1.08wt%, MgO are
0.09wt%, CaO 1.22wt%, TiO2≤ 0.03wt%, K2O is 12.45wt%, Na2O is 0.25wt%, Li2O is
4.07wt%, MnO 0.89wt%, F 4.90wt%, Rb2O is 0.42wt%, Cs2O is 0.63wt%, surplus SiO2, lithium
The partial size of mica powder is 100 mesh.
Potassium fluoroaluminate, cryolite, disodium hydrogen phosphate hydrate, potassium chloride, sodium chloride, barium acetate, barium nitrate, fluorination
Samarium, aluminum acetate, aluminium chloride, aphanitic graphite, potassium carbonate, phosphotungstic acid, samaric nitrate, fine aluminium purity be all larger than 99.9wt%, grain
Diameter is 150 mesh；The samaric nitrate is six nitric hydrate samariums；
ZLD101A al alloy component is Si 7.0%, Fe 0.06%, Ti 0.02%, Mg 0.4% by weight percentage,
Cu≤0.06%, Mn≤0.08%, Zn≤0.08%, Ca≤0.02%, total impurities≤0.5%, surplus Al.
Two, the preparation of aluminium alloy refiner material
(1) compound containing samarium is prepared as follows: being divided after 37 parts by weight samaric nitrates and 35 parts by weight phosphotungstic acids are weighed
It is not dissolved in the dehydrated alcohol of 1000 parts by weight, samaric nitrate ethanol solution is added dropwise to while stirring in phosphotungstic acid ethanol solution, it is complete
280 parts by weight lepidolite powder are added after full mixing, stirs 40h in 30 DEG C of constant temperature, waves ethyl alcohol completely in 80 DEG C of vacuum ovens
Hair, baking oven are dried to over dry, and samarium compound must be contained by smashing it through 50 meshes；
(2) preparation of lepidolite compound powder: according to 19wt% aphanitic graphite, 39wt% compound containing samarium, 0.9wt%
Potassium carbonate, surplus are that lepidolite powder carries out ingredient, and whole raw materials are placed in planetary ball mill tank grinding at room temperature and are mixed, revolving speed
300rpm, milling time 45min obtain troubled liquor with the steel ball in alcohol rinse ball grinder and tank, which are placed in very
In empty drying box, mixed powder is crossed into 250 meshes after vaporized alcohol is complete and obtains lepidolite compound powder；
(3) potassium fluoroaluminate 8wt%, cryolite 11wt%, disodium hydrogen phosphate hydrate 5wt%, chlorine are weighed by weight
Change potassium 7wt%, sodium chloride 8wt%, barium acetate 0.8wt%, barium nitrate 6wt%, samaric fluoride 0.9wt%, aluminum acetate 0.9wt%,
Aluminium chloride 8wt%, surplus are fine aluminium；Fine aluminium is heated to 770 DEG C in graphite crucible, is completely melt to fine aluminium ingot as aluminium solution
Barium acetate, barium nitrate, samaric fluoride, aluminum acetate, aluminium chloride are added afterwards, and 2000rpm stirs 10min, are removed after standing 5min
The slag that aluminium melt surface generates；Aluminum melt temperature is increased to 820 DEG C, is kept the temperature after stirring 3min, using multi-layer spray deposition plate
Material preparation facilities prepares intermediate alloy powder, jet deposition powder parameter are as follows: atomization gas is industrial high-pressure inert gas, mist
Change gas pressure 5MPa, vertical spray distance is 330mm, and drain bore is 5mm, and spray angle is 45 °, and pouring temperature is
750 DEG C, graphite crucible temperature is 780 DEG C, and sediment pan is horizontal positioned, and sediment pan horizontal movement velocity is 2.2mm/s, is vertically moved down
Speed is 1.14mm/s, and sediment pan makees horizontal back and forth movement every 55s with identical speed, until sedimentary powder thickness reaches
Stop deposition when 25cm, cooled to room temperature scrapes off the powder of surface layer 3cm thickness, takes during the powder of sedimentary centre 20cm obtains
Between alloy powder；
(4) ball milling in ball mill is all added in lepidolite compound powder and intermediate alloy powder, ratio of grinding media to material is by 10:1's
Ratio adds powder, and revolving speed 100r/min is primary every 30min commutation, Ball-milling Time 4h.Ball-milled powder mistake after cooling
It is spare after 250 meshes；The good powder of ball milling is placed in the metallic cylinder mold of diameter 70mm, after 30MPa precompressed, is forced into
250KN, the pressure maintaining 8min under 250KN pressure, commutation carry out two-sided compacting at the same pressure, briquetting are placed in vacuum sintering furnace
In, suction is 9 × 10-4Pa, 80 DEG C/min are warming up to 560 DEG C, keep the temperature 60min, then cool to room with the furnace under vacuum
Temperature is up to aluminium alloy refiner material.The phosphotungstate of rare earth samarium containing 7.65wt% in aluminium alloy refiner material is carbonized containing 10.41wt%
Silicon, aluminium oxide 40.22wt%.
Metamorphism treatment is carried out to ZLD101A aluminium alloy with above-mentioned aluminium alloy refiner material, the specific steps are as follows:
(1) melting in induction furnace by ZLD101A aluminium alloy adjusts 750 DEG C of smelting temperature, smelting time 35min；
(2) after ZLD101A aluminium alloy is completely melt, under 800rpm stirring condition, material is refined in 760 DEG C of investment aluminium alloys
Material, additional amount are the 2.0wt% of ZLD101A aluminium alloy, and aluminium alloy refiner material is completely forced into solution liquid level hereinafter, then
70s is stirred, stops stirring and standing heat preservation 14min；Solution is ultrasonically treated when standing heat preservation, frequency 38kHz, processing
Time is 14min, is cast in casting mold after melt is cooled to 735 DEG C；
(3) it is demoulded after casting natural cooling, 370 DEG C of solid solution 55min, water cooling, 110 DEG C of timeliness 70h, air-cooled aluminium to obtain the final product closes
Gold.
Embodiment 3: it is prepared as follows aluminium alloy refiner material:
One, the preparation of raw material:
Lepidolite meal component are as follows: Al2O3For 26.12wt%, H2O is 1.69wt%, and FeO 0.75wt%, MgO are
0.05wt%, CaO 0.81wt%, TiO2≤ 0.03wt%, K2O is 11.33wt%, Na2O is 0.14wt%, Li2O is
3.84wt%, MnO 0.57wt%, F 4.11wt%, Rb2O is 0.35wt%, Cs2O is 0.41wt%, surplus SiO2, lithium
The partial size of mica powder is 90 mesh.
Potassium fluoroaluminate, cryolite, disodium hydrogen phosphate hydrate, potassium chloride, sodium chloride, barium acetate, barium nitrate, fluorination
Samarium, aluminum acetate, aluminium chloride, aphanitic graphite, potassium carbonate, phosphotungstic acid, samaric nitrate, fine aluminium purity be all larger than 99.9wt%, grain
Diameter is 130 mesh；The samaric nitrate is six nitric hydrate samariums；
ZLD101A al alloy component is Si 6.5%, Fe 0.04%, Ti 0.015%, Mg by weight percentage
0.3%, Cu≤0.06%, Mn≤0.08%, Zn≤0.08%, Ca≤0.02%, total impurities≤0.5%, surplus Al.
Two, the preparation of aluminium alloy refiner material
(1) compound containing samarium is prepared as follows: being divided after 35 parts by weight samaric nitrates and 33 parts by weight phosphotungstic acids are weighed
It is not dissolved in the dehydrated alcohol of 1000 parts by weight, samaric nitrate ethanol solution is added dropwise to while stirring in phosphotungstic acid ethanol solution, it is complete
265 parts by weight lepidolite powder are added after full mixing, stirs 35h in 30 DEG C of constant temperature, waves ethyl alcohol completely in 70 DEG C of vacuum ovens
Hair, baking oven are dried to over dry, and samarium compound must be contained by smashing it through 50 meshes；
(2) preparation of lepidolite compound powder: according to 16.5wt% aphanitic graphite, 37.5wt% compound containing samarium,
0.7wt% potassium carbonate, surplus are that lepidolite powder carries out ingredient, and whole raw materials are placed in planetary ball mill tank grinding at room temperature and are mixed, are turned
Fast 225rpm, milling time 38min obtain troubled liquor with the steel ball in alcohol rinse ball grinder and tank, which are placed in
In vacuum oven, mixed powder is crossed into 200 meshes after vaporized alcohol is complete and obtains lepidolite compound powder；
(3) potassium fluoroaluminate 6.5wt%, cryolite 9wt%, disodium hydrogen phosphate hydrate 4wt%, chlorine are weighed by weight
Change potassium 6wt%, sodium chloride 6wt%, barium acetate 0.6wt%, barium nitrate 4.5wt%, samaric fluoride 0.55wt%, aluminum acetate
0.55wt%, aluminium chloride 7wt%, surplus are fine aluminium；Fine aluminium is heated to 755 DEG C in graphite crucible, it is completely molten to fine aluminium ingot
Barium acetate, barium nitrate, samaric fluoride, aluminum acetate, aluminium chloride are added after turning to aluminium solution, and 1750rpm stirs 10min, stands
The slag that aluminium melt surface generates is removed after 5min；Aluminum melt temperature is increased to 810 DEG C, is kept the temperature after stirring 2min, using multilayer
Jet deposition plate preparation facilities prepares intermediate alloy powder, jet deposition powder parameter are as follows: atomization gas is industrial high pressure
Inert gas, atomization pressure 4MPa, vertical spray distance are 285mm, and drain bore is 4mm, and spray angle is 40 °,
Pouring temperature is 740 DEG C, and graphite crucible temperature is 765 DEG C, and sediment pan is horizontal positioned, and sediment pan horizontal movement velocity is
1.65mm/s, vertically moving down speed is 0.9mm/s, and sediment pan makees horizontal back and forth movement every 45s with identical speed, until deposition
Layer powder thickness stops deposition when reaching 20cm, and cooled to room temperature scrapes off the powder of surface layer 2cm thickness, takes among sedimentary
The powder of 16cm obtains intermediate alloy powder；
(4) ball milling in ball mill is all added in lepidolite compound powder and intermediate alloy powder, ratio of grinding media to material is by 10:1's
Ratio adds powder, and revolving speed 75r/min is primary every 25min commutation, Ball-milling Time 3h.Ball-milled powder after cooling crosses 230
It is spare after mesh；The good powder of ball milling is placed in the metallic cylinder mold of diameter 60mm, after 20MPa precompressed, is forced into
200KN, the pressure maintaining 5.5min under 200KN pressure, commutation carry out two-sided compacting at the same pressure, briquetting are placed in vacuum-sintering
In furnace, suction is 5 × 10-4Pa, 65 DEG C/min are warming up to 505 DEG C, keep the temperature 45min, then cool to the furnace under vacuum
Room temperature is up to aluminium alloy refiner material.The phosphotungstate of rare earth samarium containing 6.23wt%, carbon containing 9.87wt% in aluminium alloy refiner material
SiClx, aluminium oxide 36.88wt%.
Metamorphism treatment is carried out to ZLD101A aluminium alloy with above-mentioned aluminium alloy refiner material, the specific steps are as follows:
(1) melting in induction furnace by ZLD101A aluminium alloy adjusts 740 DEG C of smelting temperature, smelting time 35min；
(2) after ZLD101A aluminium alloy is completely melt, under 600rpm stirring condition, material is refined in 750 DEG C of investment aluminium alloys
Material, additional amount are the 1.75wt% of ZLD101A aluminium alloy, and aluminium alloy refiner material is completely forced into solution liquid level hereinafter, with
After stir 55s, stop stirring and simultaneously stand heat preservation 9min；Solution is ultrasonically treated when standing heat preservation, frequency 30kHz, place
The reason time is 9min, is cast in casting mold after melt is cooled to 727 DEG C；
(3) it is demoulded after casting natural cooling, 350 DEG C of solid solution 55min, water cooling, 105 DEG C of timeliness 60h, air-cooled aluminium to obtain the final product closes
Gold.
Comparative examples 1: using alterant and Modification Manners pair disclosed in Chinese patent CN201210245793.4
ZLD101A aluminium alloy carries out Metamorphism treatment, and gained aluminium alloy is compareed for subsequent mechanical property test.
Comparative examples 2: other are same as Example 3, the difference is that replacing lepidolite powder using simple substance aluminium powder.
Comparative examples 3: other are same as Example 3, the difference is that by lepidolite compound in preparation process
Melting in aluminum melt is added in step (3) in powder together with other raw materials.
In order to test modification effect of the invention and to the influence of Mechanical Properties of Aluminum Alloys, by comparative examples 1~3 and in fact
The aluminium alloy prepared in example 1~3 is applied to be tested as follows:
1, Mechanics Performance Testing
The ZLD101A aluminium alloy castings prepared in Examples 1 to 3 and comparative examples 1~4 are subjected to mechanics properties testing
And SEM observes crystal phase size.
By obtained sample by GB6397-86, it is machined to the short tensile test bar of 8mm of standard, it is omnipotent in Controlled by micro computer
Tension test is carried out on testing machine, surveys its tensile strength, hardness and elongation, and final result takes the average value of 6 samples.As a result
It is shown in Table 1.
1 ZLD101A Mechanical Property in Aluminum Alloy Castings testing result of table
2, metallographic measures
Sample is taken at the centre of alloy coupon sample, and by polishing, polishing, it is microcosmic to observe its under an optical microscope
Tissue takes 4 different visuals field, and α-Al phase and eutectic silicon crystal size, statistical result are shown in Table 2 in each visual field of Observe and measure.
2 α-Al phase of table and eutectic silicon crystal size testing result
| Group | α-Al phase size (μm) | Eutectic silicon size (μm) |
| Embodiment 1 | 24.6±1.9 | 19.2±1.0 |
| Embodiment 2 | 21.1±1.5 | 19.4±1.1 |
| Embodiment 3 | 23.3±1.8 | 20.8±1.2 |
| Comparative examples 1 | 30.5±2.0 | 28.9±1.6 |
| Comparative examples 2 | 46.2±1.7 | 49.1±1.3 |
| Comparative examples 3 | 48.7±2.5 | 38.5±2.1 |
| ZLD101A | 68.8±1.2 | 58.9±2.3 |
Table 1 combine table 2 the result shows that, comparative examples 1 due to use phosphorus, barium, boron alterant, although effectively reducing crystalline substance
Body size, but effect and final Mechanical Properties of Aluminum Alloys are substantially less than embodiment 3, one is due to lacking rare earth alterative
Invigoration effect makes the size of α-Al phase and Eutectic Silicon in Al-Si Cast Alloys larger, and mechanical property is caused to reduce, the second is due to lacking silicon carbide, oxygen
Change the high rigidity dispersed phases such as aluminium, so that the hardness and mechanical property of aluminium alloy are lower.
Comparative examples 2 do not use lepidolite powder, cause alloy refinement material to lack the lithium alterant contained by it, together
When also lack the high rigidity dispersed phases such as aluminium oxide, the silicon carbide that silica and follow-up sintering generate so that final modification effect
It is worse than embodiment 3, the final hardness and mechanical property of aluminium alloy are also below embodiment 3.
Alloy refinement agent is prepared using high melt method in comparative examples 3, melting is repeated during the preparation process and forges
It burns, and temperature is higher, the duration is longer, causes alterant to have part scaling loss, so that final modification effect is significantly worse than reality
Apply example 3.
3, hole is observed
After sample SEM scanning, each sample takes 10 different visuals field, observes in the single visual field with the presence or absence of hole and each
Average cell number in the visual field, the results are shown in Table 3.
3 sample hole of table observes result
Table 1 combine table 3 statistics indicate that, slagging-off degasification operation is not carried out in Examples 1 to 3, but due to containing in alterant
There is lepidolite powder, degasification operation is completed while Metamorphism treatment, degassing effect is preferable, so that in final alloy-steel casting not
There are holes.Without using lepidolite powder in comparative examples 2, slagging-off deaeration step is not also carried out, is caused in alloy-steel casting
Hole number is more, and there are the impurity segregations phenomenon such as zinc, calcium, copper, hole and segregations to be formed such that the mechanical property of alloy is aobvious
Writing reduces.Comparative examples 1 only can be reduced air-breathing tendency since deteriorating time is longer, can not avoid the generation of stomata, aluminium completely
Still there is a small amount of stomata in alloy-steel casting, be unfavorable for subsequent forging molding and mechanical property is promoted.
4, the measurement and comparison of deteriorating time range
By the rotten agent material prepared in comparative examples 1 and 3 and embodiment 3 according to the alloy preparation side in embodiment 3
Method handles ZLD101A aluminium alloy, carries out the measurement of deteriorating time range, the method is as follows:
After ZLD101A aluminum alloy melting, it is separately added into different rotten agent materials, mixing time 60s is stood rotten
Soaking time is 1min, 5min, 10min, 15min, and 20min, 40min, 80min, 160min, 240min, 360min are surveyed respectively
The crystal size of Eutectic Silicon in Al-Si Cast Alloys in the alloy prepared under fixed different deteriorating times, the results are shown in Table 4:
In 4 alloy of table Eutectic Silicon in Al-Si Cast Alloys crystal size with time-histories variation
| Deteriorating time (min) | Comparative examples 1 | Comparative examples 3 | Embodiment 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 |
As seen from the results in Table 4, the aluminium alloy refiner material prepared in embodiment 3 can be generated quickly after of short duration incubation period
Modification effect, this is because refiner material is loosely organized, it is rapidly dissolvable after addition to be scattered in metal liquid, and sodium alterant
Rapid deterioration so that deterioration latency stage is short, 1~5min can reach best modification effect, and other length in refiner material
The mutual cooperation of alterant such as barium, Li, rare earth samarium element is imitated so that aluminium alloy refiner material reaches rotten stationary phase after 5min,
The sustainable 6h or more of stable modification effect, effective deteriorating time range spans are big, can meet having for most of aluminium alloy smeltings
Rotten duration demand is imitated, the short disadvantage of sodium alterant deteriorating time is compensated for.
And the rotten material prepared in comparative examples 1 just starts to generate apparent modification effect in 40min or so, works
Slowly, it is easy to cause the scaling loss and melt air-breathing of aluminium, this is because intermediate alloy is comparatively dense, dispersion is melted and needs the time, and
To maximize the cooperation for playing modification effect and needing phosphorus, barium, boron again, so it is slower to work, although subsequent modification effect is more
Stablize, the duration is also longer, but Aluminum alloy modification treatment effect is not so good as embodiment 3.
It is directly added into whole raw materials in comparative examples 3 and carries out founding, the scaling loss of sodium alterant is serious in preparation process, because
The action of this its modification effect is more slow, and modification effect is worse compared with embodiment 3, and modification effect tends towards stability after 20 min,
And the duration is up to 6h, this is because its modification effect is mainly from barium, Li alterant and rare earth samarium, but due to sodium alterant
Aluminium alloy refiner material mesometamorphism agent total amount is reduced after scaling loss, therefore modification effect is deteriorated.
In conclusion the lepidolite powder and rare earth samarium element in compound containing samarium can change other raw materials and ZLD101A
The form and size for the harmful phase that calcium, zinc, copper, lead and other elements are formed in aluminium alloy, prevent impurity phase segregation, while saving slagging-off
Step；Rare earth samarium element can also assist improving sodium, barium, lithium alterant to the fine degenerate effect of Eutectic Silicon in Al-Si Cast Alloys, change tissue morphology,
Improve the Metamorphism treatment efficiency for changing alloy phase material；Lepidolite powder effectively can help degasification to remove the gred, ultrasonication solution
Can effectively degasification, prevent from generating stomata in hypereutectic aluminium alloy castings, therefore the material prepared in the present invention is in Metamorphism treatment
While can also degasification slagging-off, save slagging-off deaeration step, promote smelting efficiency, silica rich in lepidolite powder
With aluminium oxide and lithia, silica can be reacted in melting with Al generates aluminum oxide and elementary silicon, aluminum oxide
Be mingled with the hardness that can further promote alloy, and the content of Eutectic Silicon in Al-Si Cast Alloys in alloy can be improved in elementary silicon, changes the composition of alloy
Ratio further increases the mechanical property of ZLD101A aluminium alloy.The addition of Li element can supplement the type of alterant and contain again
Amount, cooperates sodium, and barium alterant quickly and effectively goes bad.Lepidolite compound powder, master alloyed powder squeeze latter by the present invention
Secondary property is sintered, and there are many combination reaction in sintering process, such as samaric fluoride and samaric nitrate and phosphotungstic acid form rare earth samarium phosphotungstate,
Graphite and element silicon form silicon carbide, and silica and Al form aluminium oxide etc., and under vacuum condition, can eliminate element oxide can
Can, extrusion process then further reduces the distance between tiny raw material powder raw material, keeps each element diffusion-sintering more uniformly thorough,
Combination reaction energy consumption reduces, and the yields such as rare earth samarium phosphotungstate are higher.The preparatory melting of intermediate alloy is dusted, and rare earth samarium can be reduced
The scaling loss of phosphotungstate and the agent of sodium iso-metamorphism under calcining and high melt repeatedly, finally adds lepidolite composite powder and quickly squeezes
Pressure sintering, can not only retain the activity of sodium, barium, Li alterant, can also improve production efficiency, primary completion multiple element
Uniform chemical combination or combination.After powder squeezes sintering, there are a large amount of loose and porous structures, but concluding is a solid-state entirety, favorably
Cutting when weighing and using when fater disintegration be scattered in melt, drift and be adhered to furnace wall etc. it when powder being avoided to be added
On his object.Silicon carbide, silica, aluminium oxide etc. are then present in aluminium alloy refiner material as dispersed phase, and when use improves
The hardness of ZLD101A aluminium alloy；Alterant fast onset modification effect under the catalysis of rare earth samarium, incubation period is short, as sodium becomes
The scaling loss of matter agent, barium, Li and rare earth samarium alterant play long-acting metamorphism, reach Metamorphism treatment effect stability, and processing is effective
Time is long and without preclinical effect, and the mechanical property of the alloy after processing, which has, more to be significantly improved.Sodium alterant itself
Rapid-action with excellent modification effect, but that there are deteriorating times is short, the shortcomings that easy scaling loss, rare earth samarium modification effect itself is not
Obviously, but sodium and barium, Li alterant can be assisted to improve modification effect, barium, Li alterant deteriorating time are long, and modification effect is good, but
Incubation period is long, can be complementary with sodium alterant, and coarse primary silicon and α-Al phase can be effectively refined after triplicity, is overcome single
Number of drawbacks existing for alterant, rapid-action with going bad, the incubation time is short, and effective deteriorating time range is big, and modification effect is steady
Fixed feature, crystalline silicon phase and α-Al are mutually obviously refined in the ZLD101A aluminium alloy after processing, and crystal phase partial size can be down to 20
μm or so, so that the mechanical property of alloy is significantly improved.
The above examples only illustrate the technical idea of the present invention, and this does not limit the scope of protection of the present invention, all
According to the technical idea provided by the invention, any changes made on the basis of the technical scheme each falls within the scope of the present invention
Within；The technology that the present invention is not directed to can be realized by the prior art.
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.
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| CN114378281A (en) * | 2021-12-30 | 2022-04-22 | 江苏华能节能科技有限公司 | Preparation process of high-strength high-silicon aluminum alloy material |
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| CN111996409A (en) * | 2020-09-02 | 2020-11-27 | 湘潭大学 | Grain refining method for preventing silicon poisoning of aluminum-silicon alloy |
| CN111996409B (en) * | 2020-09-02 | 2021-07-02 | 湘潭大学 | Grain refining method for preventing silicon poisoning of aluminum-silicon alloy |
| CN114378281A (en) * | 2021-12-30 | 2022-04-22 | 江苏华能节能科技有限公司 | Preparation process of high-strength high-silicon aluminum alloy material |
| CN114378281B (en) * | 2021-12-30 | 2023-11-03 | 江苏华能节能科技有限公司 | Preparation process of high-strength high-silicon aluminum alloy material |
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