CN109943742A - A kind of alloy improved materials and preparation method thereof - Google Patents
A kind of alloy improved materials and preparation method thereof Download PDFInfo
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- CN109943742A CN109943742A CN201910286137.0A CN201910286137A CN109943742A CN 109943742 A CN109943742 A CN 109943742A CN 201910286137 A CN201910286137 A CN 201910286137A CN 109943742 A CN109943742 A CN 109943742A
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Abstract
The present invention discloses a kind of alloy improved materials and preparation method thereof, is related to aluminum alloy modifier field.Alloy improved materials are made of jet deposition powder, sodium salt degeneration agent and adhesive, jet deposition powder: sodium salt degeneration agent: 5~10:1 of weight ratio~3:1 of adhesive；Three kinds of strontium, sodium, rare earth neodymium alterants are combined according to its characteristic, have been effectively retained rotten activity, have deterioration latency stage short, effective deteriorating time is long, the stable feature of modification effect.Kaolinite clay powder can be used as rotten agent carrier degasification slagging-off in raw material, smelting efficiency be promoted, wherein the aluminium oxide and silica that are rich in can be obviously improved alloy rigidity.The luminescent properties of neodymium element may make aluminium alloy to carry the characteristics of luminescence, without coating luminescent material.Tiny intermediate alloy powder is prepared using one step founding of spray deposition in preparation method, then bonds extrusion forming with sodium alterant, makes the rapidly dissolvable dispersion of alterant, shortens incubation period, it is quickly and effectively rotten.
Description
Technical field
The present invention relates to alloy inoculant field, in particular to a kind of alloy improved materials 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, strontium, 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, strontium 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 A356 Aluminum alloy modification, there is the disadvantages of absorption poisoning effect, deteriorating time is short.Strontium mainly influences
Primary silicon pattern in A356 aluminium alloy is not apparent on the influence of the size of primary silicon.And it is rotten using strontium, due to strontium with
Chlorine reaction cannot refine degasification with chlorine or double salt containing chlorine.Strontium it is rotten there is also easily cause air-breathing, it is expensive the disadvantages of,
Therefore it cannot be widely applied in industrial production.Air-breathing is easily caused in calcium metamorphic process, it is stringent due to requiring calcium content,
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, must knot
It closes and assists sodium and the agent of phosphorus iso-metamorphism that can just play metamorphism.There is also alterant elements to inhibit mutually for other composite modifiers,
It is excessive to produce slag production gas, it is 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 patent CN201711456432.3 be related to a kind of alterant, using its refining aluminium alloy preparation method and
The aluminium alloy arrived.The ingredient of alterant is Te:1-5% according to weight percent, and Sb ingredient is according to weight percent are as follows: 1-
10%, surplus Al.Ternary alterant is added in the Al-Si alloy that temperature is 680-750 DEG C, makes the Te content being added
0.05-0.2wt%, it is i.e. pourable after uniform stirring degasification.Its modification process is easy to use, Te, Sb composite inoculating effect are good, becomes
Matter reduces Eutectic Silicon in Al-Si Cast Alloys alongst with width direction size.
Foregoing invention uses aluminium strontium and aluminium tellurium ternary alloy three-partalloy as alterant, only by the modification effect letter of Te, Sb element
Single superposition, the fusing point for not accounting for intermediate alloy is higher, and dispersing and dissolving is more difficult, and the fusing point of two kinds of alterant elements is also each
Not identical, composite inoculating works slowly, and incubation period is long, can not quickly and effectively go bad to hypoeutectic aluminium alloy, although finally
The size of Eutectic Silicon in Al-Si Cast Alloys can be reduced, but prolonged melting also be easy to cause the scaling loss of aluminium, change aluminium alloy composition, reduce mechanics
Performance, and refining deaeration step can not be saved in fusion process, reduce the efficiency of alusil alloy production, it is therefore desirable to develop one
Kind not only can efficient modifying-refining, but also the Multifunctional aluminium alloy that can be removed the gred with degasification goes bad material.
Summary of the invention
The technical problems to be solved by the invention: for can not Metamorphism treatment simultaneously during current A356 aluminium alloy smelting
With the problem of slagging-off degasification and common alterant be ineffective and easy scaling loss, the present invention provides a kind of alloy improved materials, solution
The above problem, while casting intermediate alloy alterant being overcome to melt the defect that slow, incubation period is long, preparation process is difficult to control.
In order to solve the above technical problems, the present invention provides technical solution below:
A kind of alloy improved materials are made of, jet deposition powder jet deposition powder, sodium salt degeneration agent and adhesive:
Sodium salt degeneration agent: 5~10:1 of weight ratio~3:1 of adhesive；
The jet deposition powder is by oxalic acid aluminium 4.3-7.7wt%, manganese acetate 1.5-2.8wt%, strontium nitrate 21-
26wt%, composite ceramic 22-37wt%, surplus are made of fine aluminium, and the sodium salt degeneration agent is by hexafluoro sodium aluminate 26-
38wt%, potassium fluoroaluminate 28-34wt%, potassium chloride 15-21wt%, surplus are sodium chloride composition；
The composite ceramic by 15-18wt% graphite, 20-28wt% silica, 5-8wt% molybdic acid RE composite,
5-8wt% boron oxide, 5-8wt% pitch, surplus are the preparation of kaolinite clay powder；The molybdic acid RE composite by neodymium nitrate/
Sodium molybdate calcined material and kaolinite clay powder composition.
Preferably, the oxalic acid aluminium, manganese acetate, strontium nitrate, hexafluoro sodium aluminate, potassium fluoroaluminate, potassium chloride, sodium chloride, stone
Ink, silica, boron oxide, sodium molybdate, neodymium nitrate, fine aluminium purity be all larger than 99.9wt%, partial size is 100~150 mesh, described
The molybdic acid sodium salt containing 44.89~65.32wt% rare earth neodymium in neodymium nitrate/sodium molybdate calcined material, the particle of the jet deposition powder
Partial size is 5~30 μm；Described adhesive is one of adhesive for polyurethane, epoxy resin, acrylate adhesive, the drip
Blueness is one of bitumen, coal tar pitch, asphalt.
A kind of preparation method of above-mentioned alloy improved materials includes following specific steps:
(1) molybdic acid RE composite is prepared as follows: 10-17g sodium molybdate being added in 1000mL dehydrated alcohol, sets
In the ethanol solution 1000mL on magnetic stirring apparatus, instilling the 15-23g containing neodymium nitrate dropwise, 36-48h is stirred in 30 DEG C of constant temperature, it is molten
10-12h to dry, 500~650 DEG C of 0.5~3h of calcining is dried after agent volatilization in 60-80 DEG C of baking oven, obtains sodium molybdate/neodymium nitrate calcining
Object is added 1L dehydrated alcohol and 105-120g kaolinite clay powder, filters after homogenate after being cooled to room temperature, precipitating drying is taken to make
Obtain molybdic acid RE composite；
(2) preparation of composite ceramic: according to 15-18wt% graphite, 20-28wt% silica, 5-8wt% molybdic acid rare earth
Compound, 5-8wt% boron oxide, 5-8wt% pitch, surplus are that kaolinite clay powder carries out ingredient, and whole raw materials are placed in row
The mixing of celestial body grinding jar grinding at room temperature, obtains troubled liquor with the steel ball in alcohol rinse ball grinder and tank, which is placed in very
In empty drying box, mixed powder is put into briquet in mold after vaporized alcohol is complete, compression moulding pressure is 15~
55MPa is put into roaster after being embedded with graphite powder, at 890-950 DEG C after heat preservation 1-2 hours, cooled to room temperature, and removal
Ground on grinder after graphite powder, until particle size at 15~30 microns to get composite ceramic；
(3) oxalic acid aluminium 4.3-7.7wt%, manganese acetate 1.5-2.8wt%, strontium nitrate 21-26wt%, composite ceramic are pressed
22-37wt%, surplus are that fine aluminium weighs raw material, and fine aluminium ingot is heated to 700-750 DEG C in heat preservation crucible, complete to fine aluminium ingot
Oxalic acid aluminium, manganese acetate, strontium nitrate are added after being molten into aluminium solution, and 1000~3000rpm stirs 5min, goes after standing 5min
The slag generated except aluminium melt surface；Aluminum melt temperature is increased to 850-900 DEG C, while composite ceramics are added to aluminum melt again
Powder, 500~1000rpm stand 10min after stirring 3~8min；
(4) jet deposition powder, spray deposition processing parameter are as follows: mist are prepared using multi-layer spray deposition plate preparation facilities
Change gas is industrial high-pressure inert gas, and 3.5~6.5MPa of atomization pressure, vertical spray distance is 300-400mm, is led
Liquid pipe internal diameter is 2~3.5mm, and spray angle is 45 °~60 °, and pouring temperature is 795-840 DEG C, and heat preservation crucible temperature is 805-
855 DEG C, sediment pan is horizontal positioned, and sediment pan horizontal movement velocity is 0.7~2.5mm/s, vertically move down speed be 0.55~
0.88mm/s, sediment pan make horizontal back and forth movement every 30s~120s with identical speed, until sedimentary powder thickness reaches 10
Stop deposition when~15cm；
(5) jet deposition powder is cooled to room temperature after the completion of depositing, sodium salt degeneration agent is proportionally added into, after being sufficiently mixed
Adhesive is added, 15~25MPa extrusion molding, 24~36h of standing demould up to alloy improved materials in mold after stirring.
Preferably, kaolinite clay meal component are as follows: Al2O3For 32.69~35.75wt%, H2O is 9.3~13.8wt%,
Fe2O3It is 0.18~0.46wt% for 1.12~1.99wt%, MgO, CaO is 0.32~1.22wt%, Ti2O be 0.15~
0.34wt%, K2O+Na2O is 0.44~1.49wt%, surplus SiO2, the partial size of the kaolinite clay powder is 80~100
Mesh；The inert gas is one of carbon dioxide, argon gas, nitrogen, radon gas.
A kind of aluminium alloy preparation method carries out Metamorphism treatment to A356 aluminium alloy using above-mentioned alloy improved materials, specifically
Steps are as follows:
(1) melting in induction furnace by A356 aluminium alloy adjusts 750-760 DEG C of smelting temperature, smelting time 35min；
(2) after A356 aluminium alloy is completely melt, under 400~800rpm stirring condition, change in 740-760 DEG C of investment alloy
Good timber material, additional amount are 2.5~4.3wt% of A356 aluminium alloy, and alloy improved materials are completely forced into solution liquid level hereinafter,
It is subsequently agitated for 20~50s, stops stirring and standing heat preservation 5-20min；Solution is ultrasonically treated when standing heat preservation, frequency is
15~40kHz, processing time are 5~20min, are cast in casting mold after melt is cooled to 730-740 DEG C；
(3) it is demoulded after casting natural cooling, 415~445 DEG C of solid solution 55min, water cooling, 130~150 DEG C of 50~70h of timeliness,
Air-cooled aluminium alloy to obtain the final product.
Preferably, the A356 al alloy component is Si 4.1~7.2%, Fe 0.02~0.06% by weight percentage,
Ti 0.13~0.19%, Mg≤0.22%, Cu≤0.13%, Mn≤0.12%, Zn≤0.03%, Ca≤0.02%, surplus are
Al。
It is that the present invention obtains the utility model has the advantages that
(1) the kaolinite clay powder in molybdic acid RE composite and rare earth neodymium element can change other raw materials and A356 aluminium
The form and size for the harmful phase that calcium, zinc, copper, lead and other elements are formed in alloy, prevent impurity phase segregation, while saving slagging-off step
Suddenly；Rare earth neodymium element can also assist improving sodium, strontium 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) neodymia can be resolved under neodymium nitrate hydrate heat-flash, and neodymia is mixed valence steady oxide, is improved
Sodium, strontium alterant modification effect catalytic activity reduce, the present invention in neodymium nitrate, sodium molybdate are reacted to generation in ethanol system
Rare earth molybdenum acid sodium-salt, and using kaolinite clay powder as the carrier of rare earth molybdenum acid sodium-salt, rear earth element nd under high temperature can be eliminated and urged
Change the defect that activity reduces, improves Aluminum alloy modification treated mechanical property indirectly.Meanwhile the neodymium in rare earth neodymium molybdic acid sodium salt
Element has relatively strong blue red fluorescence characteristic, therefore aluminium alloy product can be made to carry luminescent properties, sends out without coating again
Luminescent material can be used for indoor or automobile decoration under dark condition.
(3) kaolinite clay powder effectively can help degasification to remove the gred, ultrasonication solution also can effectively degasification, prevented
The material for generating stomata in eutectic Al-base alloy casting, therefore being prepared in the present invention while Metamorphism treatment can also degasification slagging-off,
Slagging-off deaeration step is saved, smelting efficiency is promoted, contains a large amount of silica and aluminium oxide, titanium dioxide in kaolinite clay powder
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 A356 aluminium alloy
Mechanical property.
(4) present invention prepares sodium, strontium, RE multiple modification using raw material melting once, and raw material adds in two times when melting
Enter, is firstly added oxalic acid aluminium, manganese acetate, strontium nitrate and fine aluminium and forms aluminium-strontium master alloy as strontium alterant, without additional system
Standby aluminium-strontium master alloy adds composite ceramic, rare earth neodymium sodium molybdate salt is dispersed into aluminium ladder intermediate alloy as raw material
Solution, then jet deposition powder is prepared using spray deposition technology, increase inert gas pressure on technological parameter, improves shearing
Power reduces nozzle diameter, increases spray distance etc. and makes deposited particles tiny, and will not bond, become powdered, due to injection
Deposition process condensation is fast, is not susceptible to aoxidize, and retains the activity of aluminium ladder intermediate alloy, and founding to greatest extent, once complete at powder
At raising preparation efficiency；Since sodium alterant is intolerant to scaling loss, extrusion molding is bonded after directly mixing with pulverized powder, most
Limits remain the activity of sodium alterant, at the same be conducive to weigh when cut and using when fater disintegration be scattered in melt
In.
(5) aluminium oxide, boron oxide, titanium oxide, silica etc. are then present in alloy improved materials as dispersed phase, use
The hardness of Shi Tigao A356 aluminium alloy；Sodium, strontium alterant the fast onset modification effect under the catalysis of rare earth neodymium, incubation period is short,
With the scaling loss of sodium alterant, strontium and rare earth neodymium alterant play long-acting metamorphism, reach Metamorphism treatment effect stability, handle
Effective 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 an excellent modification effect, but there are deteriorating time is short and poisoning effect, rare earth neodymium sheet
Body modification effect is unobvious, but sodium and strontium alterant can be assisted to improve modification effect, and strontium alterant itself has air-breathing, price high
Expensive disadvantage, but deteriorating time is long, modification effect is good, and kaolinite clay as carrier can degasification, overcome strontium alterant
Defect can effectively refine coarse primary silicon and α-Al phase, overcome number of drawbacks existing for single alterant after triplicity,
Rapid-action with going bad, the incubation time is short, and effective deteriorating time range is big, dissolves rapidly, and modification effect stablizes excellent feature,
Mutually obvious refinement, crystal phase partial size can be down to 20 μm or so to crystalline silicon phase with α-Al in A356 aluminium alloy after processing, 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: alloy improved materials are prepared as follows:
One, the preparation of raw material:
Oxalic acid aluminium, manganese acetate, strontium nitrate, hexafluoro sodium aluminate, potassium fluoroaluminate, potassium chloride, sodium chloride, graphite, silica, oxygen
Change boron, sodium molybdate, neodymium nitrate, fine aluminium purity be all larger than 99.9wt%, partial size is 100 mesh；
Kaolinite clay meal component are as follows: Al2O3For 32.69wt%, H2O is 9.3wt%, Fe2O3It is for 1.12wt%, MgO
0.18wt%, CaO 0.32wt%, Ti2O is 0.15wt%, K2O+Na2O is 0.44wt%, surplus SiO2, the kaolinite
The partial size of clay powder is 80 mesh；
The inert gas is carbon dioxide or nitrogen.
A356 al alloy component is Si 4.1% by weight percentage, Fe 0.02%, Ti 0.13%, Mg≤0.22%,
Cu≤0.13%, Mn≤0.12%, Zn≤0.03%, Ca≤0.02%, surplus Al；
Sodium salt degeneration agent is sodium chloride by hexafluoro sodium aluminate 26wt%, potassium fluoroaluminate 28wt%, potassium chloride 15wt%, surplus
It is sufficiently mixed preparation；
Two, the preparation of alloy improved materials
(1) molybdic acid RE composite is prepared as follows: 10g sodium molybdate being added in 1000mL dehydrated alcohol, is placed in
On magnetic stirring apparatus, the ethanol solution 1000mL of the 15g containing neodymium nitrate is instilled dropwise, stirs 36-h, solvent volatilization in 30 DEG C of constant temperature
10h to dry, 500 DEG C of calcining 0.5h is dried in 60 DEG C of baking ovens afterwards, obtains sodium molybdate/neodymium nitrate calcined material, neodymium nitrate/sodium molybdate calcining
1L dehydrated alcohol and 105g kaolinite clay powder is added in the molybdic acid of rare earth neodymium containing 44.89wt% sodium salt in object after being cooled to room temperature, even
It is filtered after slurry, precipitating drying is taken to obtain molybdic acid RE composite；
(2) preparation of composite ceramic: according to 15wt% graphite, 20wt% silica, 5wt% molybdic acid RE composite,
5wt% boron oxide, 5wt% bitumen, surplus are that kaolinite clay powder carries out ingredient, and whole raw materials are placed in planetary ball mill tank
Grinding at room temperature mixing, obtains troubled liquor with the steel ball in alcohol rinse ball grinder and tank, which is placed in vacuum oven
In, mixed powder is put into briquet in mold after vaporized alcohol is complete, compression moulding pressure is 15MPa, with graphite powder packet
It is put into roaster after burying, after 890 DEG C keep the temperature 1 hour, cooled to room temperature is ground on grinder after removing graphite powder
Mill, until particle size at 15 microns to get composite ceramic；
(3) oxalic acid aluminium 4.3wt%, manganese acetate 1.5wt%, strontium nitrate 21wt%, composite ceramic 22wt% are pressed, surplus is
Fine aluminium weighs raw material, fine aluminium ingot is heated to 700 DEG C in heat preservation crucible, by oxalic acid after fine aluminium ingot is completely melt as aluminium solution
Aluminium, manganese acetate, strontium nitrate are added, and 1000rpm stirs 5min, stand the slag of removal aluminium melt surface generation after 5min；It rises
Composite ceramic is added to aluminum melt to 850 DEG C, while again in high alumina melt temperature, stands 10min after 500rpm stirring 3min；
(4) jet deposition powder, spray deposition processing parameter are as follows: mist are prepared using multi-layer spray deposition plate preparation facilities
Change gas is industrial high-pressure inert gas, and atomization pressure 3.5MPa, vertical spray distance is 300mm, drain bore
For 2mm, spray angle is 45 °, and pouring temperature is 795 DEG C, and heat preservation crucible temperature is 805 DEG C, and sediment pan is horizontal positioned, sediment pan
Horizontal movement velocity is 0.7mm/s, and vertically moving down speed is 0.55mm/s, and sediment pan is horizontal past with identical speed work every 30s
Movement is returned, until sedimentary powder thickness stops deposition when reaching 10cm, the grain diameter of jet deposition powder is controlled 5~10
μm；
(5) jet deposition powder is cooled to room temperature after the completion of depositing, by jet deposition powder: sodium salt degeneration agent: poly- ammonia
The weight ratio of ester adhesive is that sodium salt degeneration agent is added in 5:1:1, adhesive for polyurethane is added after being sufficiently mixed, in mold after stirring
Middle 15MPa extrusion molding is stood for 24 hours, is demoulded up to alloy improved materials.
Metamorphism treatment is carried out to A356 aluminium alloy using above-mentioned alloy improved materials, the specific steps are as follows:
(1) melting in induction furnace by A356 aluminium alloy adjusts 750 DEG C of smelting temperature, smelting time 35min；
(2) after A356 aluminium alloy is completely melt, under 400rpm stirring condition, in 740 DEG C of investment alloy improved materials, add
Enter amount and be the 2.5wt% of A356 aluminium alloy, and alloy improved materials are completely forced into solution liquid level hereinafter, being subsequently agitated for 20s, stops
It only stirs and stands heat preservation 5min；Solution being ultrasonically treated when standing heat preservation, frequency 15kHz, the processing time is 5min,
It is cast in casting mold after melt is cooled to 730 DEG C；
(3) it is demoulded after casting natural cooling, 415 DEG C of solid solution 55min, water cooling, 130 DEG C of timeliness 50h, air-cooled aluminium to obtain the final product closes
Gold.
Embodiment 2: alloy improved materials are prepared as follows:
One, the preparation of raw material:
Oxalic acid aluminium, manganese acetate, strontium nitrate, hexafluoro sodium aluminate, potassium fluoroaluminate, potassium chloride, sodium chloride, graphite, silica, oxygen
Change boron, sodium molybdate, neodymium nitrate, fine aluminium purity be all larger than 99.9wt%, partial size is 150 mesh；
Kaolinite clay meal component are as follows: Al2O3For 35.75wt%, H2O is 13.8wt%, Fe2O3It is for 1.99wt%, MgO
0.46wt%, CaO 1.22wt%, Ti2O is 0.34wt%, K2O+Na2O is 1.49wt%, surplus SiO2, the kaolinite
The partial size of clay powder is 100 mesh；
The inert gas is argon gas；
A356 al alloy component is Si 7.2% by weight percentage, Fe 0.06%, Ti 0.19%, Mg≤0.22%,
Cu≤0.13%, Mn≤0.12%, Zn≤0.03%, Ca≤0.02%, surplus Al
Sodium salt degeneration agent is sodium chloride by hexafluoro sodium aluminate 38wt%, potassium fluoroaluminate 34wt%, potassium chloride 21wt%, surplus
It is sufficiently mixed preparation；
Two, the preparation of alloy improved materials
(1) molybdic acid RE composite is prepared as follows: 17g sodium molybdate being added in 1000mL dehydrated alcohol, is placed in
On magnetic stirring apparatus, the ethanol solution 1000mL of the 23g containing neodymium nitrate is instilled dropwise, 48h is stirred in 30 DEG C of constant temperature, after solvent volatilization
12h to dry, 650 DEG C of calcining 3h is dried in 80 DEG C of baking ovens, obtains sodium molybdate/neodymium nitrate calcined material, in neodymium nitrate/sodium molybdate calcined material
1L dehydrated alcohol and 120g kaolinite clay powder is added, after homogenate in the molybdic acid sodium salt of rare earth neodymium containing 65.32wt% after being cooled to room temperature
It filters, precipitating drying is taken to obtain molybdic acid RE composite；
(2) preparation of composite ceramic: according to 18wt% graphite, 28wt% silica, 8wt% molybdic acid RE composite,
8wt% boron oxide, 8wt% coal tar pitch, surplus are that kaolinite clay powder carries out ingredient, and whole raw materials are placed in planetary ball mill tank
Grinding at room temperature mixing, obtains troubled liquor with the steel ball in alcohol rinse ball grinder and tank, which is placed in vacuum oven
In, mixed powder is put into briquet in mold after vaporized alcohol is complete, compression moulding pressure is 55MPa, with graphite powder packet
It is put into roaster after burying, after 950 DEG C keep the temperature 2 hours, cooled to room temperature is ground on grinder after removing graphite powder
Mill, until particle size at 30 microns to get composite ceramic；
(3) oxalic acid aluminium 7.7wt%, manganese acetate 2.8wt%, strontium nitrate 26wt%, composite ceramic 37wt% are pressed, surplus is
Fine aluminium weighs raw material, fine aluminium ingot is heated to 750 DEG C in heat preservation crucible, by oxalic acid after fine aluminium ingot is completely melt as aluminium solution
Aluminium, manganese acetate, strontium nitrate are added, and 3000rpm stirs 5min, stand the slag of removal aluminium melt surface generation after 5min；It rises
Composite ceramic is added to aluminum melt to 900 DEG C, while again in high alumina melt temperature, stands 10min after 1000rpm stirring 8min；
(4) jet deposition powder, spray deposition processing parameter are as follows: mist are prepared using multi-layer spray deposition plate preparation facilities
Change gas is industrial high-pressure inert gas, and atomization pressure 6.5MPa, vertical spray distance is 400mm, drain bore
For 3.5mm, spray angle is 60 °, and pouring temperature is 840 DEG C, and heat preservation crucible temperature is 855 DEG C, and sediment pan is horizontal positioned, deposition
Disk horizontal movement velocity is 2.5mm/s, and vertically moving down speed is 0.88mm/s, and sediment pan makees level every 120s with identical speed
Back and forth movement, until sedimentary powder thickness stops deposition when reaching 15cm, the grain diameter of jet deposition powder is controlled 10
~20 μm；
(5) jet deposition powder is cooled to room temperature after the completion of depositing, by jet deposition powder: sodium salt degeneration agent: epoxy
The weight ratio of resin be 10:3:1 be added sodium salt degeneration agent, epoxy resin is added after being sufficiently mixed, after stirring in mold 25MPa
Extrusion molding stands 36h, demoulds up to alloy improved materials.
Metamorphism treatment is carried out to A356 aluminium alloy using above-mentioned alloy improved materials, the specific steps are as follows:
(1) melting in induction furnace by A356 aluminium alloy adjusts 760 DEG C of smelting temperature, smelting time 35min；
(2) after A356 aluminium alloy is completely melt, under 800rpm stirring condition, in 760 DEG C of investment alloy improved materials, add
Enter amount and be the 4.3wt% of A356 aluminium alloy, and alloy improved materials are completely forced into solution liquid level hereinafter, being subsequently agitated for 50s, stops
It only stirs and stands heat preservation 20min；Solution being ultrasonically treated when standing heat preservation, frequency 40kHz, the processing time is 20min,
It is cast in casting mold after melt is cooled to 740 DEG C；
(3) it is demoulded after casting natural cooling, 445 DEG C of solid solution 55min, water cooling, 150 DEG C of timeliness 70h, air-cooled aluminium to obtain the final product closes
Gold.
Embodiment 3: alloy improved materials are prepared as follows:
One, the preparation of raw material:
Oxalic acid aluminium, manganese acetate, strontium nitrate, hexafluoro sodium aluminate, potassium fluoroaluminate, potassium chloride, sodium chloride, graphite, silica, oxygen
Change boron, sodium molybdate, neodymium nitrate, fine aluminium purity be all larger than 99.9wt%, partial size is 125 mesh；
Kaolinite clay meal component are as follows: Al2O3For 34.09wt%, H2O is 11.34wt%, Fe2O3For 1.59wt%, MgO
For 0.32wt%, CaO 0.80wt%, Ti2O is 0.25wt%, K2O+Na2O is 0.91wt%, surplus SiO2, the kaolinite
The partial size of stone clay powder is 90 mesh；
The inert gas is radon gas.
A356 al alloy component is Si 5.7% by weight percentage, Fe 0.04%, Ti 0.16%, Mg≤0.22%,
Cu≤0.13%, Mn≤0.12%, Zn≤0.03%, Ca≤0.02%, surplus Al；
Sodium salt degeneration agent is sodium chloride by hexafluoro sodium aluminate 32wt%, potassium fluoroaluminate 31wt%, potassium chloride 18wt%, surplus
It is sufficiently mixed preparation；
Two, the preparation of alloy improved materials
(1) molybdic acid RE composite is prepared as follows: 13.5g sodium molybdate being added in 1000mL dehydrated alcohol, sets
In the ethanol solution 1000mL on magnetic stirring apparatus, instilling the 19g containing neodymium nitrate dropwise, 42h, solvent volatilization are stirred in 30 DEG C of constant temperature
11h is dried in 70 DEG C of baking ovens afterwards to doing, 575 DEG C of calcining 1.75h obtain sodium molybdate/neodymium nitrate calcined material, neodymium nitrate/sodium molybdate is forged
The molybdic acid sodium salt of rare earth neodymium containing 55.54wt% in object is burnt, 1L dehydrated alcohol and 113g kaolinite clay powder are added after being cooled to room temperature,
It is filtered after homogenate, precipitating drying is taken to obtain molybdic acid RE composite；
(2) preparation of composite ceramic: compound according to 16.5wt% graphite, 24wt% silica, 6.5wt% molybdic acid rare earth
Object, 6.5wt% boron oxide, 6.5wt% asphalt, surplus are that kaolinite clay powder carries out ingredient, and whole raw materials are placed in row
The mixing of celestial body grinding jar grinding at room temperature, obtains troubled liquor with the steel ball in alcohol rinse ball grinder and tank, which is placed in very
In empty drying box, mixed powder is put into briquet in mold after vaporized alcohol is complete, compression moulding pressure is 35MPa, is used
It is put into roaster after graphite powder embedding, after 920 DEG C keep the temperature 1.5 hours, cooled to room temperature is being ground after removing graphite powder
Ground on grinding machine, until particle size at 22 microns to get composite ceramic；
(3) remaining by oxalic acid aluminium 6.0wt%, manganese acetate 2.11wt%, strontium nitrate 23.5wt%, composite ceramic 30wt%
Amount is that fine aluminium weighs raw material, and fine aluminium ingot is heated to 725 DEG C in heat preservation crucible, will after fine aluminium ingot is completely melt as aluminium solution
Oxalic acid aluminium, manganese acetate, strontium nitrate are added, and 2000rpm stirs 5min, remove the molten of aluminium melt surface generation after standing 5min
Slag；Aluminum melt temperature is increased to 875 DEG C, while composite ceramic is added to aluminum melt again, is stood after 750rpm stirring 5.5min
10min；
(4) jet deposition powder, spray deposition processing parameter are as follows: mist are prepared using multi-layer spray deposition plate preparation facilities
Change gas is industrial high-pressure inert gas, and atomization pressure 5MPa, vertical spray distance is 350mm, and drain bore is
2.75mm, spray angle are 52 °, and pouring temperature is 815 DEG C, and heat preservation crucible temperature is 830 DEG C, and sediment pan is horizontal positioned, deposition
Disk horizontal movement velocity is 1.6mm/s, and vertically moving down speed is 0.72mm/s, and sediment pan makees level every 75s with identical speed
Back and forth movement, until sedimentary powder thickness stops deposition when reaching 12.5cm, the grain diameter control of jet deposition powder exists
20~30 μm；
(5) jet deposition powder is cooled to room temperature after the completion of depositing, by jet deposition powder: sodium salt degeneration agent: propylene
The weight ratio of acid esters adhesive is that sodium salt degeneration agent is added in 7.5:2:1, acrylate adhesive is added after being sufficiently mixed, after stirring
The 20MPa extrusion molding in mold stands 30h, demoulds up to alloy improved materials.
Metamorphism treatment is carried out to A356 aluminium alloy using above-mentioned alloy improved materials, the specific steps are as follows:
(1) melting in induction furnace by A356 aluminium alloy adjusts 755 DEG C of smelting temperature, smelting time 35min；
(2) after A356 aluminium alloy is completely melt, under 600rpm stirring condition, in 750 DEG C of investment alloy improved materials, add
Enter amount and be the 3.4wt% of A356 aluminium alloy, and alloy improved materials are completely forced into solution liquid level hereinafter, being subsequently agitated for 35s, stops
It only stirs and stands heat preservation 12min；Stand heat preservation when solution is ultrasonically treated, frequency 27kHz, processing the time be
13min is cast in casting mold after melt is cooled to 735 DEG C；
(3) it is demoulded after casting natural cooling, 430 DEG C of solid solution 55min, water cooling, 140 DEG C of timeliness 60h, air-cooled aluminium to obtain the final product closes
Gold.
Comparative examples 1: other are same as Example 3, the difference is that RE composite replaces with neodymium nitrate.
Comparative examples 2: other are same as Example 3, the difference is that kaolinite clay powder uses simple substance aluminium powder
Replacement.
Comparative examples 3: other are same as Example 3, the difference is that by sodium alterant and again in preparation process
It closes ceramic powder to be added in aluminum melt together, stands 10min after 750rpm stirring 5.5min and cast, pouring temperature is 815 DEG C,
It injects in clay sand mold, cooled to room temperature, demoulds up to rotten material.
Comparative examples 4: using alterant and Modification Manners pair disclosed in Chinese patent CN201711456432.3
A356 aluminium alloy carries out Metamorphism treatment, and gained aluminium alloy is compareed for subsequent mechanical property test.
1, Mechanics Performance Testing
By the A356 aluminium alloy castings prepared in Examples 1 to 3 and comparative examples 1~4 carry out 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 4 samples.As a result
It is shown in Table 1.
1 A356 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 | 22.4±1.3 | 20.5±1.1 |
| Embodiment 2 | 25.2±1.6 | 18.7±1.3 |
| Embodiment 3 | 22.2±2.0 | 21.1±1.5 |
| Comparative examples 1 | 55.2±2.1 | 44.7±2.2 |
| Comparative examples 2 | 41.3±2.8 | 36.4±1.7 |
| Comparative examples 3 | 44.3±2.9 | 39.9±2.3 |
| Comparative examples 4 | 49.2±1.7 | 40.7±2.6 |
Table 1 combine table 2 the result shows that, comparative examples 1 due to use neodymium nitrate, higher than 500 DEG C high-temperature calcination with
Neodymia is had been converted under melting, neodymia catalytic activity is weaker, the modification effect for improving sodium, strontium alterant can not be assisted,
Therefore, compared with Example 3, modification effect is poor, and crystal is larger, and the mechanical property of alloy is caused to significantly reduce.But embodiment 1
~3 crystal size illustrates the Metamorphism treatment of change alloy phase material prepared in the present invention significantly less than comparative examples 4
Significant effect is better than the combination of aluminium, antimony, tellurium three-phase intermediate alloy alterant, and crystal more refines, and modification effect is stablized, so that
The mechanical property of A356 aluminium alloy castings is also significantly greater than comparative examples 4, and without adding a variety of alterants, operation letter repeatedly
Just, aluminium oxide and silica are rich in kaolinite clay, silica again can be with aluminium new life aluminium oxide, these aluminium oxide and oxidation
Boron, titanium oxide, silica are scattered in aluminium alloy, further improve the hardness of alloy.Comparative examples 3 improve material in alloy
The combination of raw material is not adjusted in the preparation process of material according to alterant property, sodium alterant activity is burnt under high temperature founding
Damage is serious, causes its modification effect significantly lower than comparative examples 1~3.
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 kaolinite clay powder, degasification operation is completed while Metamorphism treatment, degassing effect is preferable, so that in final alloy-steel casting
Hole is not present.Without using kaolinite clay powder in comparative examples 2, slagging-off deaeration step is not also carried out, causes to close
Golden casting Hole number is more, so that the mechanical property of alloy significantly reduces.Although using refining step in comparative examples 4
Suddenly, it but since the performance of the compound optimal modification effect of three-phase alterant relies on antimony, the abundant melting of tellurium element is scattered in solution, lacks
One can not, therefore deterioration latency stage is long, causes solution air-breathing serious so that inevitably there is hole in casting, and there are zinc,
The formation of the impurity segregations phenomenon such as calcium, copper, hole and segregation is 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 3,4 and embodiment 3 according to the alloy preparation method in embodiment 3
A356 aluminium alloy is handled, the measurement of deteriorating time range is carried out, the method is as follows:
After A356 aluminum alloy melting, it is separately added into different rotten agent materials, mixing time 60s stands rotten protect
The warm time is 1min, 5min, 10min, 15min, and 20min, 40min, 80min, 160min, 240min, 360min are measured respectively
The crystal size of Eutectic Silicon in Al-Si Cast Alloys in the alloy prepared under 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 4 | Comparative examples 3 | Embodiment 3 |
| 1 | 98.7μm | 89.7μm | 48.7μm |
| 5 | 91.4μm | 77.3μm | 28.3μm |
| 10 | 83.5μm | 63.6μm | 20.3μm |
| 15 | 76.5μm | 47.9μm | 21.1μm |
| 20 | 66.3μm | 42.1μm | 19.8μm |
| 40 | 41.8μm | 38.9μm | 20.4μm |
| 80 | 40.2μm | 38.7μm | 21.5μm |
| 160 | 43.4μm | 40.8μm | 23.3μm |
| 240 | 51.8μm | 41.6μm | 25.8μm |
| 360 | 73.8μm | 55.8μm | 30.4μm |
As seen from the results in Table 4, the rotten agent material prepared in embodiment 3 can quickly generate rotten after of short duration incubation period
Effect, this is because be powder bonding extrusion molding, it is rapidly dissolvable after addition to be scattered in metal liquid, and jet deposition powder
The tiny molten grain in end is more conducive to alterant element dispersion, and the mutual cooperation of sodium, antimony, rare earth neodymium element is so that alloy improved materials exist
Reach rotten stationary phase when 5~10min, the sustainable 6h or more of stable modification effect, effective deteriorating time range spans are big, can
Meet effective rotten duration demand of most of aluminium alloy smeltings；
And the rotten material prepared in comparative examples 4 just starts to generate apparent modification effect in 40min or so, works
Slowly, modification effect is gradually deteriorated after 80min, and effective deteriorating time is only 1h or so, this is because two kinds of intermediate alloys plus
Enter and melt dispersion and needs the time, and to maximize the cooperation for playing modification effect and needing the two, so it is slower to work, and
The scaling loss process of two kinds of intermediate alloys is different, once one of scaling loss excessively if the modification effect of another alterant also can
It has a greatly reduced quality, therefore rotten effective time is also shorter.
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, and
Dissolution dispersion is slower after aluminum melt is added in casting alloy, therefore the action of its modification effect is more slow, and modification effect is relatively implemented
Example 3 is worse, and modification effect tends towards stability after 20 min, and the duration is up to 6h, this is because its modification effect mainly comes
From strontium alterant and rare earth, but due to alloy improved materials mesometamorphism agent total amount reduction after sodium alterant scaling loss, go bad effect
Fruit is deteriorated.
5, aluminium alloy luminescent properties
The luminous power under aluminium alloy dark room conditions is detected, the results are shown in Table 5:
5 aluminate base long persistence luminescent material performance test results of table
For 5 result of table as it can be seen that comparative examples 4 are without rare earth element and without luminous power, the present invention becomes aluminium alloy
Matter processing is simultaneously because introduce rare earth neodymium molybdic acid sodium salt, and aluminium alloy has stronger photism in the presence of strontium element
Energy.
In conclusion the kaolinite clay powder and rare earth neodymium element in molybdic acid RE composite can change other raw materials and
The form and size for the harmful phase that calcium, zinc, copper, lead and other elements are formed in A356 aluminium alloy, prevent impurity phase segregation, save simultaneously
Slug removing step；Rare earth neodymium element can also assist improving sodium, strontium alterant to the fine degenerate effect of Eutectic Silicon in Al-Si Cast Alloys, change tissue shape
State improves the Metamorphism treatment efficiency for changing alloy phase material；It can resolve into neodymia under neodymium nitrate hydrate heat-flash, and neodymia
For mixed valence steady oxide, improve sodium, the catalytic activity of strontium alterant modification effect reduces, in the present invention by neodymium nitrate,
Sodium molybdate reacts in ethanol system generates rare earth molybdenum acid sodium-salt, and using kaolinite clay powder as the load of rare earth molybdenum acid sodium-salt
Body can eliminate the defect that rear earth element nd catalytic activity under high temperature reduces, and improve Aluminum alloy modification indirectly treated mechanical property
Energy.Meanwhile the neodymium element in rare earth neodymium molybdic acid sodium salt has relatively strong blue red fluorescence characteristic, therefore can aluminium alloy be produced
Object carries luminescent properties, without coating luminescent material again, can be used for indoor or automobile decoration under dark condition.Kaolinite clay
Powder effectively can help degasification to remove the gred, ultrasonication solution also can effectively degasification, prevent from generating in hypereutectic aluminium alloy castings
Stomata, thus the material prepared in the present invention while Metamorphism treatment can also degasification slagging-off, save slagging-off deaeration step, promoted
Smelting efficiency, a large amount of silica and aluminium oxide are contained in kaolinite clay powder, and silica can be reacted in melting with Al
Aluminum oxide and elementary silicon are generated, aluminum oxide is mingled with the hardness that can further promote alloy, and elementary silicon can be improved
The content of Eutectic Silicon in Al-Si Cast Alloys in alloy, changes the composition ratio of alloy, further increases the mechanical property of A356 aluminium alloy.The present invention adopts
Sodium, strontium, RE multiple modification are prepared with raw material melting once, and raw material is added in two portions when melting, is firstly added oxalic acid aluminium, second
Sour manganese, strontium nitrate and fine aluminium form aluminium-strontium master alloy as strontium alterant, are used as original without aluminium-strontium master alloy is additionally prepared
Material, adds composite ceramic, rare earth neodymium sodium molybdate salt is dispersed into aluminium ladder intermediate alloy solution, then use jet deposition work
Skill prepares jet deposition powder, increases inert gas pressure on technological parameter, improves shearing force, reduces nozzle diameter, increases spray
It penetrates that distance is equal so that deposited particles are tiny, and will not bond, becomes powdered, since Models of Spray Deposition condensation is fast, be not easy to send out
Raw oxidation retains the activity of aluminium ladder intermediate alloy, and founding to greatest extent, once completes at powder, improves preparation efficiency；Due to sodium
Alterant bonds extrusion molding intolerant to scaling loss after directly mixing with pulverized powder, remain sodium alterant to greatest extent
Activity, while be conducive to weigh when cut and using when fater disintegration be scattered in melt.Aluminium oxide, boron oxide, oxidation
Titanium, silica etc. are then present in alloy improved materials as dispersed phase, and when use improves the hardness of A356 aluminium alloy；Sodium, strontium
Alterant fast onset modification effect under the catalysis of rare earth neodymium, incubation period is short, with the scaling loss of sodium alterant, strontium and rare earth neodymium
Alterant plays long-acting metamorphism, reaches Metamorphism treatment effect stability, and processing effective time is long and without preclinical effect, warp
The mechanical property for handling later alloy, which has, more to be significantly improved.Sodium alterant itself has excellent modification effect, but exists
Deteriorating time is short and poisoning effect, and rare earth neodymium modification effect itself is unobvious, but sodium and strontium alterant can be assisted to improve rotten effect
Fruit, strontium alterant itself has the shortcomings that air-breathing, expensive, but deteriorating time is long, and modification effect is good, and kaolinite clay is made
For carrier can degasification, overcome the defect of strontium alterant, coarse primary silicon and α-Al phase can be effectively refined after triplicity,
Overcome number of drawbacks existing for single alterant, rapid-action with going bad, the incubation time is short, and effective deteriorating time range is big, fast
Instant solution, modification effect stablize excellent feature, and crystalline silicon phase is mutually obvious thin with α-Al in the A356 aluminium alloy after processing
Change, 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 (6)
1. a kind of alloy improved materials, it is characterised in that: be made of, spray jet deposition powder, sodium salt degeneration agent and adhesive
Deposited powder: sodium salt degeneration agent: 5~10:1 of weight ratio~3:1 of adhesive；
The jet deposition powder is by oxalic acid aluminium 4.3-7.7wt%, manganese acetate 1.5-2.8wt%, strontium nitrate 21-26wt%, multiple
Ceramic powder 22-37wt% is closed, surplus is made of fine aluminium, and the sodium salt degeneration agent is by hexafluoro sodium aluminate 26-38wt%, potassium fluoroaluminate
28-34wt%, potassium chloride 15-21wt%, surplus are sodium chloride composition；
The composite ceramic is by 15-18wt% graphite, 20-28wt% silica, 5-8wt% molybdic acid RE composite, 5-
8wt% boron oxide, 5-8wt% pitch, surplus are the preparation of kaolinite clay powder；The molybdic acid RE composite is by neodymium nitrate/molybdenum
Sour sodium calcined material and kaolinite clay powder composition.
2. a kind of alloy improved materials according to claim 1, it is characterised in that: the oxalic acid aluminium, manganese acetate, nitric acid
Strontium, hexafluoro sodium aluminate, potassium fluoroaluminate, potassium chloride, sodium chloride, graphite, silica, boron oxide, sodium molybdate, neodymium nitrate, fine aluminium
Purity is all larger than 99.9wt%, and partial size is 100~150 mesh, in the neodymium nitrate/sodium molybdate calcined material containing 44.89~
65.32wt% rare earth neodymium molybdic acid sodium salt, the grain diameter of the jet deposition powder are 5~30 μm；Described adhesive is poly- ammonia
One of ester adhesive, epoxy resin, acrylate adhesive, the pitch are bitumen, coal tar pitch, asphalt
One of.
3. a kind of preparation method of alloy improved materials as claimed in claim 1 or 2, which is characterized in that include following specific step
It is rapid:
(1) molybdic acid RE composite is prepared as follows: 10-17g sodium molybdate being added in 1000mL dehydrated alcohol, is placed in magnetic
On power blender, the ethanol solution 1000mL of the 15-23g containing neodymium nitrate is instilled dropwise, stirs 36-48h in 30 DEG C of constant temperature, solvent is waved
10-12h is dried after hair in 60-80 DEG C of baking oven to doing, 500~650 DEG C of 0.5~3h of calcining obtain sodium molybdate/neodymium nitrate calcined material,
1L dehydrated alcohol and 105-120g kaolinite clay powder are added after being cooled to room temperature, is filtered after homogenate, precipitating drying is taken to obtain
Molybdic acid RE composite；
(2) preparation of composite ceramic: compound according to 15-18wt% graphite, 20-28wt% silica, 5-8wt% molybdic acid rare earth
Object, 5-8wt% boron oxide, 5-8wt% pitch, surplus are that kaolinite clay powder carries out ingredient, and whole raw materials are placed in planet ball
The mixing of grinding jar grinding at room temperature, obtains troubled liquor with the steel ball in alcohol rinse ball grinder and tank, which is placed in vacuum and is done
In dry case, mixed powder is put into briquet in mold after vaporized alcohol is complete, compression moulding pressure is 15~55MPa, is used
It is put into roaster after graphite powder embedding, at 890-950 DEG C after heat preservation 1-2 hours, cooled to room temperature, after removal graphite powder
Ground on grinder, until particle size at 15~30 microns to get composite ceramic；
(3) oxalic acid aluminium 4.3-7.7wt%, manganese acetate 1.5-2.8wt%, strontium nitrate 21-26wt%, composite ceramic 22- are pressed
37wt%, surplus are that fine aluminium weighs raw material, and fine aluminium ingot is heated to 700-750 DEG C in heat preservation crucible, completely molten to fine aluminium ingot
Oxalic acid aluminium, manganese acetate, strontium nitrate are added after turning to aluminium solution, and 1000~3000rpm stirs 5min, removes after standing 5min
The slag that aluminium melt surface generates；Aluminum melt temperature is increased to 850-900 DEG C, while composite ceramic is added to aluminum melt again,
500~1000rpm stands 10min after stirring 3~8min；
(4) jet deposition powder, spray deposition processing parameter are as follows: atomization gas are prepared using multi-layer spray deposition plate preparation facilities
Body is industrial high-pressure inert gas, and 3.5~6.5MPa of atomization pressure, vertical spray distance is 300-400mm, catheter
Internal diameter is 2~3.5mm, and spray angle is 45 °~60 °, and pouring temperature is 795-840 DEG C, and heat preservation crucible temperature is 805-855
DEG C, sediment pan is horizontal positioned, and sediment pan horizontal movement velocity is 0.7~2.5mm/s, vertically move down speed be 0.55~
0.88mm/s, sediment pan make horizontal back and forth movement every 30s~120s with identical speed, until sedimentary powder thickness reaches 10
Stop deposition when~15cm；
(5) jet deposition powder is cooled to room temperature after the completion of depositing, sodium salt degeneration agent is proportionally added into, is added after being sufficiently mixed
Adhesive, 15~25MPa extrusion molding, 24~36h of standing demould up to alloy improved materials in mold after stirring.
4. a kind of preparation method of alloy improved materials according to claim 3, it is characterised in that: kaolinite clay powder
Ingredient are as follows: Al2O3For 32.69~35.75wt%, H2O is 9.3~13.8wt%, Fe2O3It is for 1.12~1.99wt%, MgO
0.18~0.46wt%, CaO are 0.32~1.22wt%, TiO2For 0.15~0.34wt%, K2O+Na2O be 0.44~
1.49wt%, surplus SiO2, the partial size of the kaolinite clay powder is 80~100 mesh；The inert gas be carbon dioxide,
One of argon gas, nitrogen, radon gas.
5. a kind of aluminium alloy preparation method, which is characterized in that using alloy improved materials described in claims 1 or 2 to A356
Aluminium alloy carries out Metamorphism treatment, the specific steps are as follows:
(1) melting in induction furnace by A356 aluminium alloy adjusts 750-760 DEG C of smelting temperature, smelting time 35min；
(2) after A356 aluminium alloy is completely melt, under 400~800rpm stirring condition, material is improved in 740-760 DEG C of investment alloy
Material, additional amount are 2.5~4.3wt% of A356 aluminium alloy, and alloy improved materials are completely forced into solution liquid level hereinafter, then
20~50s is stirred, stops stirring and standing heat preservation 5-20min；Stand heat preservation when solution is ultrasonically treated, frequency be 15~
40kHz, processing time are 5~20min, are cast in casting mold after melt is cooled to 730-740 DEG C；
(3) it is demoulded after casting natural cooling, 415~445 DEG C of solid solution 55min, water cooling, 130~150 DEG C of timeliness 50~70h are air-cooled
Up to aluminium alloy.
6. a kind of aluminium alloy preparation method according to claim 5, it is characterised in that: the A356 al alloy component is by weight
Amount percentage be Si 4.1~7.2%, Fe 0.02~0.06%, Ti 0.13~0.19%, Mg≤0.22%, Cu≤
0.13%, Mn≤0.12%, Zn≤0.03%, Ca≤0.02%, surplus Al.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111101030A (en) * | 2020-01-09 | 2020-05-05 | 徐罗斌 | Preparation method of composite aluminum alloy chemical material |
| CN111855723A (en) * | 2020-06-11 | 2020-10-30 | 宁夏大学 | Direct three-dimensional display method for texture morphology of coarse aluminum cellular crystal |
| CN113699398A (en) * | 2021-08-24 | 2021-11-26 | 湘潭大学 | Short-process preparation method of high-strength high-toughness corrosion-resistant deformation ZnCuTi plate |
| CN117026003A (en) * | 2023-10-10 | 2023-11-10 | 北京航空航天大学 | Aluminum-based composite material stirring casting preparation method based on composite modification refinement |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343699A (en) * | 2008-09-03 | 2009-01-14 | 营口经济技术开发区金达合金铸造有限公司 | Aluminum-silicon alloy refining agent and preparation thereof |
| CN102644010A (en) * | 2012-04-11 | 2012-08-22 | 北京工业大学 | Al-Ti-B-Er refiner and preparation method thereof |
| CN103173642A (en) * | 2011-12-23 | 2013-06-26 | 秦皇岛开发区美铝合金有限公司 | Refining agent for aluminum alloy in smelting process for automobile hub |
| CN107119203A (en) * | 2017-04-19 | 2017-09-01 | 济南大学 | A kind of method for preparing Yb, La and SiC composite inoculating A356.2 alloys |
-
2019
- 2019-04-10 CN CN201910286137.0A patent/CN109943742A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343699A (en) * | 2008-09-03 | 2009-01-14 | 营口经济技术开发区金达合金铸造有限公司 | Aluminum-silicon alloy refining agent and preparation thereof |
| CN103173642A (en) * | 2011-12-23 | 2013-06-26 | 秦皇岛开发区美铝合金有限公司 | Refining agent for aluminum alloy in smelting process for automobile hub |
| CN102644010A (en) * | 2012-04-11 | 2012-08-22 | 北京工业大学 | Al-Ti-B-Er refiner and preparation method thereof |
| CN107119203A (en) * | 2017-04-19 | 2017-09-01 | 济南大学 | A kind of method for preparing Yb, La and SiC composite inoculating A356.2 alloys |
Non-Patent Citations (2)
| Title |
|---|
| 周进华等: "《铁合金》", 30 April 1993, 冶金工业出版社 * |
| 山东省机械工业学校主编: "《铸造合金及熔炼》", 30 September 1979, 北京：机械工业出版社 * |
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| CN111855723A (en) * | 2020-06-11 | 2020-10-30 | 宁夏大学 | Direct three-dimensional display method for texture morphology of coarse aluminum cellular crystal |
| CN111855723B (en) * | 2020-06-11 | 2023-11-14 | 宁夏大学 | Direct three-dimensional display method for coarse aluminum cellular crystal structure morphology |
| CN113699398A (en) * | 2021-08-24 | 2021-11-26 | 湘潭大学 | Short-process preparation method of high-strength high-toughness corrosion-resistant deformation ZnCuTi plate |
| CN117026003A (en) * | 2023-10-10 | 2023-11-10 | 北京航空航天大学 | Aluminum-based composite material stirring casting preparation method based on composite modification refinement |
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