CN109750180A - A kind of alloy auxiliary material and preparation method thereof - Google Patents
A kind of alloy auxiliary material and preparation method thereof Download PDFInfo
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- CN109750180A CN109750180A CN201910214129.5A CN201910214129A CN109750180A CN 109750180 A CN109750180 A CN 109750180A CN 201910214129 A CN201910214129 A CN 201910214129A CN 109750180 A CN109750180 A CN 109750180A
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Abstract
The invention discloses a kind of alloy auxiliary materials, be grouped as by the group of following weight ratio: barium nitrate 3-8%, sodium nitrate 11-15%, aluminium carbonate 3-9%, manganese acetate 0.5-1.5%, aluminum nitrate 3-11%, potassium chloride 11-15%, sodium chloride 8-12%, sepiolite composite powder 12-18%, surplus is cryolite；RE composite, manganese acetate can change the form and size of the harmful phase of impurity element formation, and a variety of alterant elements in sepiolite compound powder can effectively refine coarse primary silicon, while Metamorphism treatment can also degasification slagging-off, promote smelting efficiency.The gap shrinks between powder raw material are made using the method for squeezing calcining in preparation method, be conducive to the metal salts such as sodium, strontium, aluminium, potassium, neodymium and form metal complex, the modification effect of multiple element is superimposed, and complex compound is more stable, the scaling loss for preventing or slowing down independent alterant when high melt extends effective deteriorating time.
Description
Technical field
The present invention relates to alloy inoculant field, in particular to a kind of alloy auxiliary material and preparation method thereof.
Background technique
Silicon mutually president's slabbing under the conditions of autonomous growth, or even the polygonal that appearance is coarse in alusil alloy eutectic
Plate silicon phase, the silicon of these forms mutually isolate Al matrix for serious, cause stress to be concentrated at the tip of Si phase and edges and corners, close
Gold is easy to crack along the boundary of crystal grain or plate Si itself and form crackle, and alloy is made to become fragile, and mechanical performance is especially prolonged
Rate significant decrease is stretched, machining function is also bad.In order to change the existence of silicon, the mechanical property of alloy is improved, for a long time
Since always use Modification Treatment Technique.
There is the member of modification effect to be known as Eutectic Silicon in Al-Si Cast Alloys: sodium (Na), strontium (Sr), sulphur (S), lanthanum (La), cerium (Ce), antimony (Sb),
Tellurium (Te) etc..Current study is concentrated mainly on sodium, strontium, on several alterants such as rare earth, widely applied Al-5Ti-1B, Al-
10Sr fining modifier, there are titanium silicides to poison thinning effect, Sr aggravates " poisoning " mutual between alloy melt air-breathing and Sr, B now
As.It is industrial general also using elemental phosphorous as alterant, but the fierce burning of meeting in elemental phosphorous addition high temperature aluminium alloys liquid, it generates
A large amount of smog pollute air, while also enabling aluminum alloy to liquid and absorbing more gases, make occur hole in casting, are unfavorable for aluminium conjunction
The strength enhancing of golden casting and subsequent forging, and for intermediate alloy, as alterant, there are deterrorations using phosphorus and aluminum
Height, deteriorating time is long, the defect of preparation process complexity, and therefore, urgent need develops a kind of rare-earth base alterant and solves the above problems.
It is typically all using the method for swimming during aluminum alloy melt casting come degasification, principle is to be passed through certain in aluminum alloy melt
Not hydrogeneous gas generates bubble, takes the hydrogen of dissolution out of aluminum alloy melt in floating-upward process using these bubbles, escapes into atmosphere.
Preferable refining effect in order to obtain should make the iron pipe for importing gas be pressed into molten bath depths as far as possible, so that the stroke of bubble floating
It lengthens, while the field trash for being sunken to aluminum alloy melt bottom being unlikely to stir again.Iron pipe should be made in aluminum alloy melt when being passed through gas
Inside slowly transverse shifting, so that molten bath has bubble to pass through everywhere.As far as possible using lower venting pressure and speed, because this
The bubble that sample is formed is smaller, expands the surface area of bubble, and since bubble is small, ascent rate is also slow, thus can remove more
Be mingled with and gas.Meanwhile to guarantee good refining effect, the selection of refining temperature should be appropriate, and temperature is excessively high, generates
Bubble is larger and floats quickly, and refining effect is made to be deteriorated.The viscosity of aluminum alloy melt is larger when temperature is too low, is unfavorable for aluminum alloy melt
In gas be sufficiently discharged, equally can also reduce refining effect.
It also can effectively degasification with ultrasonication aluminum alloy melt.Its principle is by being passed through elasticity into aluminum alloy melt
Wave causes " hole " phenomenon in aluminum alloy melt, thus destroys the continuity of aluminum alloy melt structure, produces countless micro-
Vacuum cave, the hydrogen being dissolved in aluminum alloy melt, which just promptly escapes into, becomes bubble core in these holes, continues after growing up in bubble
Shape escapes aluminum alloy melt, to reach degassing purpose.
For metal impurities, general being of processing method adverse factor is favorable factor.It i.e. will by alloyage process
It becomes the second beneficial phase, in favor of the performance of material property.It is to utilize difference in most cases if having to removal
Element boiling point difference carries out high-temperature low-pressure and selectively distills, to achieve the purpose that remove metal impurities.
Chinese patent CN201711303259.3 be related to it is a kind of for the refinement of hypoeutectic silumin alloy, alterant and
Preparation method and application, it is characterized in that chemical constituent is Al-1Ti-3B-10RE, each component mass percent are as follows: Ti:0.9-
1.1%, B:2.8-3.2%, RE:10-12%, surplus Al；The component of RE are as follows: rich La mixed light rare earth accounts for 40%, Y 60%.
Rare earth element active function combination melting magnetic agitation, quickly solidification solves in fining modifier (Al, Ti) B2、AlB2Reunite
Problem.The effect of refinement α-Al and the mechanical property of alloy can be obviously improved.
Although the alterant of foregoing invention Central Asia eutectic aluminum-silicon casting alloy can enable aluminum alloy to α-coarse in as-cast structure
Al dendrite and gill shape Eutectic Silicon Refinement are rotten, but refining slagging-off degasification must be individually carried out before and after Metamorphism treatment, and remove the gred degasification
Effect directly affects last Mechanical Properties of Aluminum Alloys, thus while slagging-off deaeration step is many and diverse, influences aluminium alloy production efficiency,
But it can not save.Ti and B in foregoing invention are conventional alterant, and Metamorphism treatment effect is it is contemplated that hypoeutectic aluminium
The promotion of alloy mechanical property is limited.
Summary of the invention
The technical problems to be solved by the invention: for can not Metamorphism treatment simultaneously during current A357 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 auxiliary material, solution
The above problem.
In order to solve the above technical problems, the present invention provides technical solution below:
A kind of alloy auxiliary material, is grouped as by the group of following weight ratio: barium nitrate 3-8%, sodium nitrate 11-15%, carbon
Sour aluminium 3-9%, manganese acetate 0.5-1.5%, aluminum nitrate 3-11%, potassium chloride 11-15%, sodium chloride 8-12%, sepiolite are compound
Powder 12-18%, surplus are cryolite；
Sepiolite composite powder strontium carbonate containing 18-25wt%, 14-18wt% tantalum carbide, 18-26wt% rare earth are compound
Object, 9-12wt% tar, remaining is sepiolite powder；The RE composite is made of rare-earth base phosphotungstate and sepiolite powder.
Preferably, the barium nitrate, sodium nitrate, aluminium carbonate, manganese acetate, aluminum nitrate, potassium chloride, sodium chloride, cryolite,
Strontium carbonate, tantalum carbide purity be all larger than 99.9wt%, partial size is 200~300 mesh, and the tar is high temperature coal-tar, described
Sepiolite is α sepiolite.
A kind of preparation method of above-mentioned alloy auxiliary material includes following specific steps:
(1) RE composite is prepared as follows: in 1000mL dehydrated alcohol be added 200-210g sepiolite powder and
20-23g phosphotungstic acid, is placed on magnetic stirring apparatus, the ethanol solution 1000mL of the 25-30g containing neodymium nitrate is instilled dropwise, in 20 DEG C of perseverances
Temperature stirring 36-39h dries 10-12h to doing in 70-80 DEG C of baking oven, obtains RE composite after solvent volatilization；
(2) preparation of sepiolite composite powder, it is dilute according to 18-25wt% strontium carbonate, 14-18wt% tantalum carbide, 18-26wt%
Native compound, 9-12wt% tar, remaining is sepiolite powder ingredient, and the mix powder outside tar removing is existed in star ball mill
It is stirred evenly under inert gas, while further refinement；
(3) tar is added while stirring into mix powder, mixture after mixing evenly is put into grinding tool and is suppressed
Blocking, compression moulding pressure is 60~90MPa, will be put into roaster after the mixture block environmental sealing pressed with aluminium foil,
1110-1210 DEG C after sintering 1-2 hours, cooled to room temperature then takes out and grinds on grinder, until particle size exists
It 10~15 microns, can be stand-by；
(4) according to barium nitrate 3-8wt%, sodium nitrate 11-15wt%, aluminium carbonate 3-9wt%, manganese acetate 0.5-1.5wt%,
Aluminum nitrate 3-11wt%, potassium chloride 11-15wt%, sodium chloride 8-12wt%, sepiolite composite powder 12-18wt%, remaining is fluorine
Sodium aluminate ingredient, it is then uniform in ground and mixed in the ball mill, by mixture extrusion forming, 30~45MPa of squeeze pressure；
(5) batch briquetting is put into the vacuum drying oven of argon gas again and is sintered, after heat preservation 1-2 hours, taken at 180-190 DEG C
It is cooled to room temperature out, partial size is then ground on grinder at 20~30 microns to get alloy auxiliary material；
Preferably, the sepiolite powder ingredient are as follows: 0.01~0.067wt%MnO, 21.22~33.74wt%MgO, 0.18
~0.33wt%Al2O3, 0.05~0.116wt%K2O, 0.034~0.117wt%Na2O, 0.068~0.097wt%NiO,
0.042~0.321wt%FeO, 0.727~1.543wt%Fe2O3, 0.784~1.449wt%CaO, 0.092~0.231wt%
Cr2O3,0.022~0.067wt%BaO, surplus SiO2；The partial size of sepiolite powder is 100~200 mesh, the aluminium foil and mixed
The weight ratio for closing object block is 1:100~1000.
A kind of aluminium alloy preparation method carries out Metamorphism treatment to A357 alloy using above-mentioned alloy auxiliary material, specific to walk
It is rapid as follows:
(1) melting in induction furnace by A357 alloy adjusts 740-760 DEG C of smelting temperature, smelting time 30min；
(2) it after A357 alloy is completely melt, under 500~700rpm stirring condition, is slowly uniformly added at 750-760 DEG C
Alloy auxiliary material, additional amount are 1.2~4.4wt% of A357 alloy, continue stirring 10 after being added completely into alloy auxiliary material
~20min stops stirring and standing heat preservation 10-20min；Stand heat preservation when solution is ultrasonically treated, frequency be 30~
60kHz, processing time are 10~20min, and melt is cooled to 725-735 DEG C, is cast in casting mold；
(3) it is demoulded after natural cooling, 380~440 DEG C of solid solution 30min are air-cooled, 120~140 DEG C of timeliness 20~40h, air-cooled
Up to aluminium alloy.
Preferably, the alloy auxiliary material is prepared using method described in claim 4.
Preferably, the component of the A357 alloy are as follows: Si 6.7~7.4wt%, Fe 0.05~0.08wt%, Cu 0.04
~0.08wt%, Mg 0.56~0.66wt%, Mn 0.01~0.03wt%, Zn≤0.03wt%, Ti 0.05~
0.23wt%, impurity content≤0.1wt%, surplus Al.
It is that the present invention obtains the utility model has the advantages that
(1) RE composite, manganese acetate can change barium nitrate, sodium nitrate, aluminium carbonate, aluminum nitrate, potassium chloride, chlorination
The impurity elements shape such as zinc, lead in sodium, sepiolite composite powder, cryolite, strontium carbonate, tantalum carbide, sepiolite powder and A357 alloy
At harmful phase form and size, thus reduce impurity phase harm, auxiliary improve barium nitrate, sodium nitrate, aluminium carbonate, nitric acid
Aluminium, potassium chloride, sodium chloride, sepiolite composite powder and cryolite change tissue morphology, mention to the fine degenerate effect of Eutectic Silicon in Al-Si Cast Alloys
Height changes the Metamorphism treatment efficiency of alloy phase material；A large amount of silica can react generation in melting with Al in sepiolite powder
Aluminum oxide and elementary silicon, aluminum oxide is mingled with the wearability that can further promote alloy, and conjunction can be improved in elementary silicon
The content of Eutectic Silicon in Al-Si Cast Alloys in gold, changes the composition ratio of alloy, further increases the mechanical property of silumin.
(2) neodymia can be resolved under neodymium nitrate hydrate heat-flash, and neodymia is mixed valence steady oxide, catalysis
Activity is low, reacts neodymium nitrate, phosphotungstic acid in ethanol system in the present invention and generates rare earth phosphotungstate, and is made with sepiolite powder
For the carrier of rare earth phosphotungstate, the defect that rear earth element nd catalytic activity reduces under high temperature can be eliminated, high temperature melting is significantly improved
RE composite catalysis under the conditions of refining changes the form and size of impurity element harmful phase, improves Aluminum alloy modification processing indirectly
Mechanical property afterwards.
(3) rear earth element nd in sepiolite compound powder, strontium element and sodium element cooperate, and can effectively refine thick
Big primary silicon overcomes number of drawbacks existing for alloy phosphor alterative, and rapid-action with going bad, the incubation time is short, effectively rotten
Time range is big, dissolves rapidly, and modification effect stablizes excellent feature, crystalline silicon phase and α-in the A357 alloy after processing
Al phase obviously refines, and crystal phase partial size can be down to 20 μm or so, so that the mechanical property of alloy is significantly improved.
(4) α sepiolite is in the fibrous crystal output of big beam, and α sepiolite powder helps degasification slagging-off, ultrasonication solution
Also can effectively degasification, prevent from generating stomata in aluminium alloy castings, therefore the material prepared in the present invention is in the same of Metamorphism treatment
When can also degasification slagging-off, save slagging-off deaeration step, promote smelting efficiency.
(5) alloy auxiliary material is prepared using the method for squeezing calcining in preparation method, so that the gap between powder raw material
It reduces, is conducive to the metal salts such as sodium, strontium, aluminium, potassium, neodymium and forms metal complex, the modification effect of multiple element is superimposed, and is high
Under temperature, complex compound is more stable, prevents or slows down the scaling loss of independent alterant when high melt, extends effective deteriorating time.
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 alloy auxiliary material:
One, the preparation of raw material:
Using A357 alloy as melting object, component are as follows: Si 6.7wt%, Fe 0.05wt%, Cu 0.04wt%, Mg
0.56wt%, Mn 0.01wt%, Zn 0.03wt%, Ti 0.05wt%, impurity content≤0.1wt%, surplus Al.
Barium nitrate, sodium nitrate, aluminium carbonate, manganese acetate, aluminum nitrate, potassium chloride, sodium chloride, cryolite, strontium carbonate, carbonization
The purity of tantalum is all larger than 99.9wt%, and partial size is 200 mesh, and tar is high temperature coal-tar.
Sepiolite is α sepiolite, sepiolite powder ingredient are as follows: 0.01wt%MnO, 21.22wt%MgO, 0.18wt%Al2O3,
0.05wt%K2O, 0.034wt%Na2O, 0.068wt%NiO, 0.042wt%FeO, 0.727wt%Fe2O3, 0.784wt%
CaO, 0.092wt%Cr2O3,0.022wt%BaO, surplus SiO2；The partial size of sepiolite powder is 100 mesh.
Two, the preparation of alloy auxiliary material
(1) RE composite is prepared as follows: 200g sepiolite powder and 20g phosphorus being added in 1000mL dehydrated alcohol
Wolframic acid is placed on magnetic stirring apparatus, instills the ethanol solution 1000mL of the 25g containing neodymium nitrate dropwise, stirs 36h in 20 DEG C of constant temperature,
10h is dried after solvent volatilization in 70 DEG C of baking ovens to doing, obtains RE composite；
(2) preparation of sepiolite composite powder, according to 18wt% strontium carbonate, 14wt% tantalum carbide, 18wt% RE composite,
9wt% tar, remaining is sepiolite powder ingredient, and the mix powder outside tar removing is stirred under an inert gas in star ball mill
It mixes uniformly, while further refinement；
(3) tar is added while stirring into mix powder, mixture after mixing evenly is put into grinding tool and is suppressed
Blocking, compression moulding pressure is 60MPa, will be put into roaster after the mixture block environmental sealing pressed with aluminium foil, the aluminium
The weight ratio of foil and mixture block is 1:100, and after 1110 DEG C are sintered 1 hour, cooled to room temperature then takes out and grinding
It is ground on machine, it, can be stand-by until particle size is at 10 microns；
(4) according to barium nitrate 3wt%, sodium nitrate 11wt%, aluminium carbonate 3wt%, manganese acetate 0.5wt%, aluminum nitrate
3wt%, potassium chloride 11wt%, sodium chloride 8wt%, sepiolite composite powder 12wt%, remaining be cryolite ingredient, then
Ground and mixed is uniform in ball mill, by mixture extrusion forming, squeeze pressure 30MPa；
(5) batch briquetting is put into the vacuum drying oven of argon gas again and is sintered, after 180 DEG C keep the temperature 1 hour, take out cooling
To room temperature, partial size is then ground on grinder at 20 microns to get alloy auxiliary material；
Metamorphism treatment is carried out to A357 alloy using above-mentioned alloy auxiliary material, the specific steps are as follows:
(1) melting in induction furnace by A357 alloy adjusts 740 DEG C of smelting temperature, smelting time 30min；
(2) after A357 alloy is completely melt, under 500rpm stirring condition, alloy auxiliary is slowly uniformly added at 750 DEG C
Material, additional amount are the 1.2wt% of A357 alloy, continue to stir 10min after being added completely into alloy auxiliary material, stop stirring simultaneously
Stand heat preservation 10min；Solution is ultrasonically treated when standing heat preservation, frequency 30kHz, the processing time is 10min, by melt
725 DEG C are cooled to, is cast in casting mold；
(3) it is demoulded after natural cooling, 380 DEG C of solid solution 30min are air-cooled, 120 DEG C of timeliness 20h, air-cooled up to aluminium alloy.
Embodiment 2: it is prepared as follows alloy auxiliary material:
One, the preparation of raw material:
Using A357 alloy as melting object, component are as follows: Si 7.4wt%, Fe 0.08wt%, Cu 0.08wt%, Mg
0.66wt%, Mn 0.03wt%, Zn 0.02wt%, Ti 0.23wt%, impurity content≤0.1wt%, surplus Al.
Barium nitrate, sodium nitrate, aluminium carbonate, manganese acetate, aluminum nitrate, potassium chloride, sodium chloride, cryolite, strontium carbonate, carbonization
The purity of tantalum is all larger than 99.9wt%, and partial size is 300 mesh, and tar is high temperature coal-tar.
Sepiolite is α sepiolite, sepiolite powder ingredient are as follows: 0.067wt%MnO, 33.74wt%MgO, 0.33wt%
Al2O3, 0.116wt%K2O, 0.117wt%Na2O, 0.097wt%NiO, 0.321wt%FeO, 1.543wt%Fe2O3,
1.449wt%CaO, 0.231wt%Cr2O3,0.067wt%BaO, surplus SiO2；The partial size of sepiolite powder is 200 mesh.
Two, the preparation of alloy auxiliary material
(1) RE composite is prepared as follows: 210g sepiolite powder and 23g phosphorus being added in 1000mL dehydrated alcohol
Wolframic acid is placed on magnetic stirring apparatus, instills the ethanol solution 1000mL of the 30g containing neodymium nitrate dropwise, stirs 39h in 20 DEG C of constant temperature,
12h is dried after solvent volatilization in 80 DEG C of baking ovens to doing, obtains RE composite；
(2) preparation of sepiolite composite powder, according to 25wt% strontium carbonate, 18wt% tantalum carbide, 26wt% RE composite,
12wt% tar, remaining is sepiolite powder ingredient, under an inert gas in star ball mill by the mix powder outside tar removing
It stirs evenly, while further refinement；
(3) tar is added while stirring into mix powder, mixture after mixing evenly is put into grinding tool and is suppressed
Blocking, compression moulding pressure is 90MPa, will be put into roaster after the mixture block environmental sealing pressed with aluminium foil, the aluminium
The weight ratio of foil and mixture block is 1:1000, and after 1210 DEG C are sintered 2 hours, cooled to room temperature then takes out and grinding
It is ground on grinding machine, it, can be stand-by until particle size is at 15 microns；
(4) according to barium nitrate 8wt%, sodium nitrate 15wt%, aluminium carbonate 9wt%, manganese acetate 1.5wt%, aluminum nitrate
11wt%, potassium chloride 15wt%, sodium chloride 12wt%, sepiolite composite powder 18wt%, remaining is cryolite ingredient, is then existed
Ground and mixed is uniform in the ball mill, by mixture extrusion forming, squeeze pressure 45MPa；
(5) batch briquetting is put into the vacuum drying oven of argon gas again and is sintered, after 190 DEG C keep the temperature 2 hours, take out cooling
To room temperature, partial size is then ground on grinder at 30 microns to get alloy auxiliary material；
Metamorphism treatment is carried out to A357 alloy using above-mentioned alloy auxiliary material, the specific steps are as follows:
(4) melting in induction furnace by A357 alloy adjusts 760 DEG C of smelting temperature, smelting time 30min；
(5) after A357 alloy is completely melt, under 700rpm stirring condition, alloy auxiliary is slowly uniformly added at 760 DEG C
Material, additional amount are the 4.4wt% of A357 alloy, continue to stir 20min after being added completely into alloy auxiliary material, stop stirring simultaneously
Stand heat preservation 20min；Solution is ultrasonically treated when standing heat preservation, frequency 60kHz, the processing time is 20min, by melt
735 DEG C are cooled to, is cast in casting mold；
(6) it is demoulded after natural cooling, 440 DEG C of solid solution 30min are air-cooled, 140 DEG C of timeliness 40h, air-cooled up to aluminium alloy.
Embodiment 3: it is prepared as follows alloy auxiliary material:
One, the preparation of raw material:
Using A357 alloy as melting object, component are as follows: Si 7.1wt%, Fe 0.065wt%, Cu 0.06wt%,
Mg 0.61wt%, Mn 0.02wt%, Zn 0.01wt%, Ti 0.14wt%, impurity content≤0.1wt%, surplus Al.
Barium nitrate, sodium nitrate, aluminium carbonate, manganese acetate, aluminum nitrate, potassium chloride, sodium chloride, cryolite, strontium carbonate, carbonization
The purity of tantalum is all larger than 99.9wt%, and partial size is 250 mesh, and tar is high temperature coal-tar.
Sepiolite is α sepiolite, sepiolite powder ingredient are as follows: 0.038wt%MnO, 27.43wt%MgO, 0.25wt%
Al2O3, 0.058wt%K2O, 0.077wt%Na2O, 0.082wt%NiO, 0.153wt%FeO, 1.154wt%Fe2O3,
1.023wt%CaO, 0.165wt%Cr2O3, 0.044wt%BaO, surplus SiO2；The partial size of sepiolite powder is 150 mesh.
Two, the preparation of alloy auxiliary material
(1) RE composite is prepared as follows: 205g sepiolite powder and 21.5g being added in 1000mL dehydrated alcohol
Phosphotungstic acid is placed on magnetic stirring apparatus, instills the ethanol solution 1000mL of the 28g containing neodymium nitrate dropwise, is stirred in 20 DEG C of constant temperature
37.5h dries 11h to doing in 75 DEG C of baking ovens, obtains RE composite after solvent volatilization；
(2) preparation of sepiolite composite powder, according to 21wt% strontium carbonate, 16wt% tantalum carbide, 22wt% RE composite,
11.5wt% tar, remaining is sepiolite powder ingredient, by the mix powder outside tar removing in star ball mill in inert gas
Under stir evenly, while further refinement；
(3) tar is added while stirring into mix powder, mixture after mixing evenly is put into grinding tool and is suppressed
Blocking, compression moulding pressure is 75MPa, will be put into roaster after the mixture block environmental sealing pressed with aluminium foil, the aluminium
The weight ratio of foil and mixture block is 1:550, and after 1160 DEG C are sintered 1.5 hours, cooled to room temperature then takes out and grinding
It is ground on grinding machine, it, can be stand-by until particle size is at 13 microns；
(4) according to barium nitrate 5wt%, sodium nitrate 13wt%, aluminium carbonate 6wt%, manganese acetate 1wt%, aluminum nitrate 7wt%,
Potassium chloride 13wt%, sodium chloride 10wt%, sepiolite composite powder 15wt%, remaining is cryolite ingredient, then in ball milling
Ground and mixed is uniform in machine, by mixture extrusion forming, squeeze pressure 37MPa；
(5) batch briquetting is put into the vacuum drying oven of argon gas again and is sintered, after 185 DEG C keep the temperature 1.5 hours, taken out cold
But to room temperature, partial size is then ground on grinder at 25 microns to get alloy auxiliary material；
Metamorphism treatment is carried out to A357 alloy using above-mentioned alloy auxiliary material, the specific steps are as follows:
(7) melting in induction furnace by A357 alloy adjusts 750 DEG C of smelting temperature, smelting time 30min；
(8) after A357 alloy is completely melt, under 600rpm stirring condition, alloy auxiliary is slowly uniformly added at 755 DEG C
Material, additional amount are the 2.8wt% of A357 alloy, continue to stir 15min after being added completely into alloy auxiliary material, stop stirring simultaneously
Stand heat preservation 15min；Solution is ultrasonically treated when standing heat preservation, frequency 45kHz, the processing time is 15min, by melt
730 DEG C are cooled to, is cast in casting mold；
(9) it is demoulded after natural cooling, 410 DEG C of solid solution 30min are air-cooled, 130 DEG C of timeliness 30h, air-cooled up to aluminium alloy.
Embodiment 4: other are same as Example 3, the difference is that rare earth element uses lanthanum (La), cerium (Ce), antimony
(Sb), one of tellurium (Te).
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 sepiolite powder is replaced using simple substance aluminium powder.
Comparative examples 3: other are same as Example 3, the difference is that step (3) and (4) are no in preparation process
Extrusion operation is carried out, is directly calcined.
Comparative examples 4: using alterant disclosed in Chinese patent CN201711303259.3 to A357 aluminium alloy into
Row Metamorphism treatment, gained aluminium alloy are compareed for subsequent mechanical property test.
1, Mechanics Performance Testing
By the A357 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 A357 Mechanical Property in Aluminum Alloy Castings testing result of table
| Group | Tensile strength (MPa) | Elongation (%) | Hardness (HBW) |
| Embodiment 1 | 249 | 4.1 | 116 |
| Embodiment 2 | 278 | 4.6 | 128 |
| Embodiment 3 | 266 | 4.3 | 122 |
| Comparative examples 1 | 214 | 2.7 | 94 |
| Comparative examples 2 | 137 | 1.9 | 75 |
| Comparative examples 3 | 196 | 2.8 | 89 |
| Comparative examples 4 | 204 | 2.9 | 110 |
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 5 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
Table 1 combine table 2 the result shows that, comparative examples 1 due to using neodymium nitrate carry out Metamorphism treatment, with 3 phase of embodiment
Than modification effect is poor, so that α-Al phase and eutectic silicon crystal are larger, the mechanical property of alloy is caused to significantly reduce.But
The crystal size of Examples 1 to 3 illustrates the change alloy phase material prepared in the present invention significantly less than comparative examples 4
Metamorphism treatment significant effect is better than conventional alterant, and crystal more refines, and solid solution and timeliness are under preferable temperature and time, crystal
Form is uniformly tiny graininess, and modification effect is stablized, so that the mechanical property of A357 alloy-steel casting is also obviously improved.Control
Embodiment 3 does not take pressing steps in the preparation process of alloy auxiliary material, and calcined product forms not good enough, causes alloy auxiliary
Help the modification effect of material significantly lower than comparative examples 1~3.
3, hole is observed
After sample SEM scanning, each sample takes 5 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
| Group | With the presence or absence of hole | Numbers of hole |
| Embodiment 1 | It is no | 0 |
| Embodiment 2 | It is no | 0 |
| Embodiment 3 | It is no | 0 |
| Comparative examples 1 | It is | 0.4 |
| Comparative examples 2 | It is | 3.6 |
| Comparative examples 3 | It is | 0.2 |
| Comparative examples 4 | It is | 0.8 |
Table 1 combine table 3 statistics indicate that, without using sepiolite powder in comparative examples 2, also do not carry out slagging-off except jia bombardier
Suddenly, cause alloy-steel casting Hole number more, so that the mechanical property of alloy significantly reduces.It is not also carried out in Examples 1 to 3
Remove the gred degasification operation, but due to joined sepiolite powder, degasification operation is completed while Metamorphism treatment, and degassing effect preferably makes
It obtains and hole is not present in alloy-steel casting finally, although having carried out slagging-off degasification operation in comparative examples 3, there are still few
Measure stomata.Although using refinement step in comparative examples 4, but still there are hole, the formation of hole is unfavorable for subsequent
Forging molding.
4, the measurement and comparison of deteriorating time range
By the rotten agent material prepared in comparative examples 4 and embodiment 3 according to the alloy preparation method in embodiment 3 at
A357 aluminium alloy is managed, the measurement of deteriorating time range is carried out, the method is as follows:
After A357 aluminum alloy melting, it is separately added into different rotten agent materials, mixing time 30s stands rotten protect
The warm time is 1min, 5min, 10min, 15min, and 20min, 40min, 80min, 160min are measured respectively under different deteriorating times
The crystal size of Eutectic Silicon in Al-Si Cast Alloys in the alloy of preparation, 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 | Embodiment 3 |
| 1 | 90.3μm | 48.2μm |
| 5 | 75.3μm | 27.5μm |
| 10 | 41.5μm | 19.7μm |
| 15 | 30.1μm | 14.6μm |
| 20 | 33.2μm | 15.3μm |
| 40 | 40.2μm | 16.2μm |
| 80 | 68.7μm | 17.9μm |
| 160 | 99.4μm | 26.8μm |
As seen from the results in Table 4, the rotten agent material prepared in embodiment 3 it is rotten breed 1min after can quickly generate change
Matter effect, and reach rotten stationary phase in 10min, the sustainable 160min of stable modification effect, effective deteriorating time range
Span is big, can meet effective rotten duration demand of most of aluminium alloy smeltings, and the rotten material prepared in comparative examples 4
Just start to generate apparent modification effect in 10min, effective deteriorating time is only 30min or so, under high melt, with rotten
The extension of time, alterant scaling loss gradually increase, and modification effect is deteriorated, and rotten significant effect is worse than embodiment 3 when 160min.
In conclusion RE composite, manganese acetate can change barium nitrate, sodium nitrate, aluminium carbonate, aluminum nitrate, potassium chloride,
The impurity such as zinc, lead member in sodium chloride, sepiolite composite powder, cryolite, strontium carbonate, tantalum carbide, sepiolite powder and A357 alloy
Element formed harmful phase form and size, thus reduce impurity phase harm, auxiliary improve barium nitrate, sodium nitrate, aluminium carbonate,
Aluminum nitrate, potassium chloride, sodium chloride, sepiolite composite powder and cryolite change tissue shape to the fine degenerate effect of Eutectic Silicon in Al-Si Cast Alloys
State improves the Metamorphism treatment efficiency for changing alloy phase material；A large amount of silica can be anti-with Al in melting in sepiolite powder
Aluminum oxide and elementary silicon should be generated, aluminum oxide is mingled with the wearability that can further promote alloy, and elementary silicon can
The content for improving Eutectic Silicon in Al-Si Cast Alloys in alloy, changes the composition ratio of alloy, further increases the mechanical property of silumin.Nitric acid
Neodymia can be resolved under neodymium hydrate heat-flash, and neodymia is mixed valence steady oxide, catalytic activity is low, in the present invention
Neodymium nitrate, phosphotungstic acid are reacted in ethanol system and generate rare earth phosphotungstate, and using sepiolite powder as rare earth phosphotungstate
Carrier, the defect that rear earth element nd catalytic activity under high temperature reduces can be eliminated, significantly improve the rare earth under the conditions of high melt
Complex catalysts change the form and size of impurity element harmful phase, improve Aluminum alloy modification treated mechanical property indirectly.
Rear earth element nd, strontium element and sodium element in sepiolite compound powder cooperate, and can effectively refine coarse primary silicon,
Overcome number of drawbacks existing for alloy phosphor alterative, rapid-action with going bad, the incubation time is short, and effective deteriorating time range is big,
Dissolution, modification effect stablize excellent feature rapidly, and crystalline silicon phase is mutually obvious thin with α-Al in the A357 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.α sepiolite is in the threadiness of big beam
Crystal output, α sepiolite powder help degasification slagging-off, ultrasonication solution also can effectively degasification, prevent in aluminium alloy castings
Generate stomata, therefore the material prepared in the present invention while Metamorphism treatment can also degasification slagging-off, save slagging-off deaeration step,
Promote smelting efficiency.Alloy auxiliary material is prepared using the method for squeezing calcining in preparation method, so that between powder raw material
Gap reduces, and is conducive to the metal salts such as sodium, strontium, aluminium, potassium, neodymium and forms metal complex, the modification effect of multiple element is superimposed, and
Under high temperature, complex compound is more stable, prevents or slows down the scaling loss of independent alterant when high melt, extends effective deteriorating time.
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 alloy auxiliary material, which is characterized in that be grouped as by the group of following weight ratio: barium nitrate 3-8%, sodium nitrate
11-15%, aluminium carbonate 3-9%, manganese acetate 0.5-1.5%, aluminum nitrate 3-11%, potassium chloride 11-15%, sodium chloride 8-12%,
Sepiolite composite powder 12-18%, surplus are cryolite；
Sepiolite composite powder strontium carbonate containing 18-25wt%, 14-18wt% tantalum carbide, 18-26wt% RE composite, 9-
12wt% tar, remaining is sepiolite powder；The RE composite is made of rare-earth base phosphotungstate and sepiolite powder.
2. a kind of alloy auxiliary material according to claim 1, it is characterised in that: the barium nitrate, sodium nitrate, carbonic acid
Aluminium, manganese acetate, aluminum nitrate, potassium chloride, sodium chloride, cryolite, strontium carbonate, tantalum carbide purity be all larger than 99.9wt%, grain
Diameter is 200~300 mesh, and the tar is high temperature coal-tar, and the sepiolite is α sepiolite.
3. a kind of preparation method of alloy auxiliary material as claimed in claim 1 or 2, which is characterized in that include following specific step
It is rapid:
(1) RE composite is prepared as follows: 200-210g sepiolite powder and 20- being added in 1000mL dehydrated alcohol
23g phosphotungstic acid, is placed on magnetic stirring apparatus, the ethanol solution 1000mL of the 25-30g containing neodymium nitrate is instilled dropwise, in 20 DEG C of constant temperature
36-39h is stirred, 10-12h is dried after solvent volatilization in 70-80 DEG C of baking oven to doing, obtains RE composite；
(2) preparation of sepiolite composite powder, it is multiple according to 18-25wt% strontium carbonate, 14-18wt% tantalum carbide, 18-26wt% rare earth
Object, 9-12wt% tar are closed, remaining is sepiolite powder ingredient, by the mix powder outside tar removing in star ball mill in inertia
It is stirred evenly under gas, while further refinement；
(3) tar is added while stirring into mix powder, mixture after mixing evenly is put into briquet in grinding tool,
Compression moulding pressure is 60~90MPa, will be put into roaster after the mixture block environmental sealing pressed with aluminium foil, in 1110-
1210 DEG C after sintering 1-2 hours, cooled to room temperature then takes out and grinds on grinder, until particle size 10~
It 15 microns, can be stand-by；
(4) according to barium nitrate 3-8wt%, sodium nitrate 11-15wt%, aluminium carbonate 3-9wt%, manganese acetate 0.5-1.5wt%, nitric acid
Aluminium 3-11wt%, potassium chloride 11-15wt%, sodium chloride 8-12wt%, sepiolite composite powder 12-18wt%, remaining is fluoaluminic acid
Sodium ingredient, it is then uniform in ground and mixed in the ball mill, by mixture extrusion forming, 30~45MPa of squeeze pressure；
(5) batch briquetting is put into the vacuum drying oven of argon gas again and is sintered, at 180-190 DEG C after heat preservation 1-2 hours, taken out cold
But to room temperature, partial size is then ground on grinder at 20~30 microns to get alloy auxiliary material.
4. a kind of preparation method of alloy auxiliary material according to claim 3, it is characterised in that: the sepiolite powder
Ingredient are as follows: 0.01~0.067wt%MnO, 21.22~33.74wt%MgO, 0.18~0.33wt%Al2O3, 0.05~
0.116wt%K2O, 0.034~0.117wt%Na2O, 0.068~0.097wt%NiO, 0.042~0.321wt%FeO,
0.727~1.543wt%Fe2O3, 0.784~1.449wt%CaO, 0.092~0.231wt%Cr2O3,0.022~
0.067wt%BaO, surplus SiO2；The partial size of sepiolite powder is 100~200 mesh, the weight ratio of the aluminium foil and mixture block
For 1:100~1000.
5. a kind of aluminium alloy preparation method, which is characterized in that using alloy auxiliary material described in claims 1 or 2 to A357
Alloy carries out Metamorphism treatment, the specific steps are as follows:
(1) melting in induction furnace by A357 alloy adjusts 740-760 DEG C of smelting temperature, smelting time 30min；
(2) after A357 alloy is completely melt, under 500~700rpm stirring condition, alloy is slowly uniformly added at 750-760 DEG C
Auxiliary material, additional amount are 1.2~4.4wt% of A357 alloy, be added completely into after alloy auxiliary material continue stirring 10~
20min stops stirring and standing heat preservation 10-20min；Stand heat preservation when solution is ultrasonically treated, frequency be 30~
60kHz, processing time are 10~20min, and melt is cooled to 725-735 DEG C, is cast in casting mold；
(3) demoulded after natural cooling, 380~440 DEG C of solid solution 30min are air-cooled, 120~140 DEG C of timeliness 20~40h, it is air-cooled to obtain the final product
Aluminium alloy.
6. a kind of aluminium alloy preparation method according to claim 5, it is characterised in that: the alloy auxiliary material is using power
Benefit requires method described in 4 to be prepared.
7. a kind of aluminium alloy preparation method according to claim 6, it is characterised in that: the component of the A357 alloy are as follows:
Si6.7~7.4wt%, Fe0.05~0.08wt%, Cu0.04~0.08wt%, Mg0.56~0.66wt%, Mn0.01~
0.03wt%, Zn≤0.03wt%, Ti0.05~0.23wt%, impurity content≤0.1wt%, surplus Al.
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