CN109868384A - A kind of material and preparation method thereof changing alloy phase - Google Patents

A kind of material and preparation method thereof changing alloy phase Download PDF

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CN109868384A
CN109868384A CN201910213402.2A CN201910213402A CN109868384A CN 109868384 A CN109868384 A CN 109868384A CN 201910213402 A CN201910213402 A CN 201910213402A CN 109868384 A CN109868384 A CN 109868384A
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sodium
nitrate
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赵浩峰
夏俊
张椿英
于鹏
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Anhui Institute of Information Engineering
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Abstract

The invention discloses a kind of materials for changing alloy phase, be grouped as by the group of following weight ratio: sodium thiosulfate 13-18%, aluminum sulfate 4-9%, aluminum nitrate 0.6-1.2%, sodium acetate 5-11%, sodium nitrate 13-16%, aluminium oxide 3-7%, potassium chloride 2-6%, biotite compound powder 15-19%, remaining is sodium chloride;RE composite can change the form and size of the harmful phase of impurity element formation, thus reduce the harm of impurity phase, and auxiliary improves fine degenerate effect.Praseodymium nitrate, phosphotungstic acid react in ethanol system generates rare earth phosphotungstate, and using black clouds female powder as its carrier, the defect that Rare Earth Elements of Praseodymium catalytic activity reduces under high temperature can be eliminated, Rare Earth Elements of Praseodymium and strontium in biotite compound powder can effectively refine coarse primary silicon, black clouds female powder helps degasification slagging-off, therefore in the present invention material for preparing while Metamorphism treatment can also degasification slagging-off, promote smelting efficiency.

Description

A kind of material and preparation method thereof changing alloy phase
Technical field
The present invention relates to alloy inoculant field, in particular to a kind of material and preparation method thereof for changing alloy phase.
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.It is industrial general also using elemental phosphorous work For alterant, but in elemental phosphorous addition high temperature aluminium alloys liquid can fierce burning, generate a large amount of smog, pollute air, while also making Aluminum alloy melt absorbs more gases, makes occur hole in casting, be unfavorable for aluminium alloy castings strength enhancing and subsequent forging It makes.
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, and iron pipe lower end is apart from crucible bottom 100~150 millimeters of portion so that the stroke of bubble floating lengthens, while being unlikely to again the field trash for being sunken to aluminum alloy melt bottom It stirs.It should make iron pipe slowly transverse shifting in aluminum alloy melt when being passed through gas, so that molten bath has bubble to pass through everywhere.To the greatest extent Amount expands the surface area of bubble, and due to gas because the bubble formed in this way is smaller using lower venting pressure and speed Steep small, ascent rate is also slow, thus can remove more be mingled with and gas.Meanwhile to guarantee good refining effect, refining temperature The selection of degree should be appropriate, and temperature is excessively high, and the bubble generated is larger and floats quickly, and refining effect is made to be deteriorated.Aluminium when temperature is too low The viscosity of aluminium alloy is larger, and the gas being unfavorable in aluminum alloy melt is sufficiently discharged, and 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 CN201310626657.4 is related to the alterant and its Modification Manners of a kind of ADC12 aluminium alloy, it is related to And the alterant and its Modification Manners of aluminium alloy.Purpose is to solve the alterant thinning effect shakiness of existing ADC12 aluminium alloy The problem of fixed, easily decline, ADC12 aluminium alloy as-cast structure are coarse α-Al dendrite and gill shape Eutectic Silicon in Al-Si Cast Alloys, poor mechanical property. The alterant of ADC12 aluminium alloy is made of Al-5Ti-B intermediate alloy and Al-10RE intermediate alloy.Modification Manners: one, melting; Two, it refines;Three, Al-5Ti-B intermediate alloy is added;Four, Al-10RE intermediate alloy is added;Five, it is poured.Advantage: one, refinement effect Fruit is stablized;Two, solve the problems, such as ADC12 aluminium alloy seriously isolate, poor mechanical property, tensile strength improves 25%~ 30%;Three, alterant is easily obtained, and saves cost.
The alterant of ADC12 aluminium alloy is made of Al-5Ti-B intermediate alloy and Al-10RE intermediate alloy in foregoing invention, Although α-Al dendrite and gill shape Eutectic Silicon Refinement coarse in ADC12 aluminium alloy as-cast structure can be made rotten, Metamorphism treatment Before must individually carry out refining slagging-off degasification, slagging-off degassing effect directly affect last Mechanical Properties of Aluminum Alloys, thus while The deaeration step that removes the gred is many and diverse, influences aluminium alloy production efficiency, but can not save.Al-5Ti-B intermediate alloy in foregoing invention It is conventional alterant with Al-10RE intermediate alloy, Metamorphism treatment effect is it is contemplated that ADC12 Mechanical Properties of Aluminum Alloys It is promoted limited.
Summary of the invention
The technical problems to be solved by the invention: for the place that can not go bad simultaneously during current ADC12 aluminium alloy smelting Reason and slagging-off degasification and the ineffective problem of common alterant, the present invention provide a kind of material for changing alloy phase, in solution State problem.
In order to solve the above technical problems, the present invention provides technical solution below:
A kind of material changing alloy phase, is grouped as: sodium thiosulfate 13-18%, aluminum sulfate by the group of following weight ratio 4-9%, aluminum nitrate 0.6-1.2%, sodium acetate 5-11%, sodium nitrate 13-16%, aluminium oxide 3-7%, potassium chloride 2-6%, black clouds Female compound powder 15-19%, remaining is sodium chloride;
The biotite compound powder zirconium carbide containing 18-25wt%, 23-29wt% RE composite, 3-9wt% carbonic acid Strontium, 11-14wt% tar, remaining is black clouds female powder;The RE composite is made of praseodymium nitrate, phosphotungstic acid and black clouds female powder.
Preferably, the RE composite is prepared as follows: it is black that 200-210g being added in 1000mL dehydrated alcohol Mica powder and 20-25g phosphotungstic acid, are placed on magnetic stirring apparatus, instill the ethanol solution 1000mL of the 20-25g containing praseodymium nitrate dropwise, 36-39h is stirred in 20 DEG C of constant temperature, 10-12h is dried after solvent volatilization in 70-80 DEG C of baking oven to over dry, it is compound to obtain rare earth Object;The sodium thiosulfate, aluminum sulfate, aluminum nitrate, sodium acetate, sodium nitrate, aluminium oxide, potassium chloride, sodium chloride, praseodymium nitrate, phosphorus Wolframic acid, zirconium carbide, strontium carbonate purity be all larger than 99.95wt%, partial size is 50~100 mesh.
A kind of preparation method of the material of above-mentioned change alloy phase includes following specific steps:
(1) preparation of biotite compound powder: according to 18-25wt% zirconium carbide, 23-29wt% RE composite, 3- 9wt% strontium carbonate, 11-14wt% tar, remaining is black clouds female powder ingredient, is then stirring evenly, will stir in blender Uniform mixture is put into roaster, after heat preservation 1-2 hours, is air-cooled to room temperature at 890-930 DEG C, is then taken out in grinder Upper grinding can be stand-by until particle size is at 10~15 microns;
(2) according to following weight percent ingredient: sodium thiosulfate 13-18%, aluminum sulfate 4-9%, aluminum nitrate 0.6- 1.2%, sodium acetate 5-11%, sodium nitrate 13-16%, aluminium oxide 3-7%, potassium chloride 2-6%, biotite compound powder 15- 19%, remaining is sodium chloride, is then stirring evenly in blender, the mixture stirred evenly is put into roaster, 120-140 DEG C after heat preservation 1-2 hours, taking-up is cooled to room temperature, and partial size is then ground on grinder at 20~30 microns, i.e., The material of alloy phase must be changed.
Preferably, the biotite meal component are as follows: 0.14~0.33wt%Na2O, 6.64~11.92wt%MgO, 6.67 ~8.23wt%Al2O3, 9.18~11.32wt%K2O, 2.43wt%S, 2.93wt%P, 5.23~8.33wt%FeO, surplus For SiO2;The partial size of black clouds female powder is 40~60 mesh.
A kind of aluminium alloy preparation method carries out Metamorphism treatment to ADC12 alloy using above-mentioned change alloy phase material, specifically Steps are as follows:
(1) melting in induction furnace by ADC12 alloy adjusts 740-765 DEG C of smelting temperature, smelting time 30min;
(2) after ADC12 alloy is completely melt, under 300~500rpm stirring condition, slowly uniformly add at 750-765 DEG C Enter to change the material of alloy phase, additional amount is the 0.5wt% of ADC12 alloy, is continued after being added completely into the material for changing alloy phase 15~25min is stirred, stops stirring and standing heat preservation 10-20min;Solution is ultrasonically treated when standing heat preservation, frequency is 50~100kHz, processing time are 10~20min, and melt is cooled to 725-735 DEG C, is cast in casting mold;
(3) demoulded after natural cooling, 450~550 DEG C of solid solution 1h, water cooling, 110~130 DEG C of timeliness 18~48h, it is air-cooled i.e. Obtain aluminium alloy.
Preferably, the change alloy phase material is prepared using method described in claim 4.
Preferably, the component of the ADC12 alloy are as follows: Si 10~11wt%, Fe 0.8~1wt%, Cu 1.6~ 2.0wt%, Mg0.1wt%, Mn 0.6wt%, Zn 0.5~0.9wt%, Ni 0.6~0.8wt%, Sn 0.08~ 0.22wt%, impurity content≤0.2wt%, surplus Al.
It is that the present invention obtains the utility model has the advantages that
(1) RE composite can change sodium thiosulfate, aluminum sulfate, aluminum nitrate, sodium acetate, sodium nitrate, aluminium oxide, chlorine The harmful phase that the impurity elements such as zinc, magnesium are formed in change potassium, sodium chloride, zirconium carbide, strontium carbonate, black clouds female powder and ADC12 alloy Form and size, thus reduce the harm of impurity phase, and auxiliary improves potassium chloride, aluminium oxide, sodium thiosulfate, zirconium carbide, sulfuric acid Aluminium, aluminum nitrate, sodium acetate, sodium chloride, sodium nitrate, strontium carbonate change tissue morphology, improve to the fine degenerate effect of Eutectic Silicon in Al-Si Cast Alloys Change the Metamorphism treatment efficiency of alloy phase material;A large amount of silica can react generation three in melting with Al in black clouds female powder Al 2 O and elementary silicon, aluminum oxide is mingled with the wearability that can further promote alloy, and alloy can be improved in elementary silicon The content of middle Eutectic Silicon in Al-Si Cast Alloys changes the composition ratio of alloy, further increases the mechanical property of silumin.
(2) praseodymium nitrate hydrate is heated to 500 DEG C or so, can resolve into praseodymium oxide, and praseodymium oxide is stablized for mixed valence Oxide, catalytic activity is low, reacts praseodymium nitrate, phosphotungstic acid in ethanol system in the present invention and generates rare earth phosphotungstate, and Using black clouds female powder as the carrier of rare earth phosphotungstate, the defect that Rare Earth Elements of Praseodymium catalytic activity reduces under high temperature can be eliminated, is shown Form and size that the RE composite catalysis under the conditions of improving high melt changes impurity element harmful phase are write, improves aluminium indirectly Alloy modification treated mechanical property.
(3) Rare Earth Elements of Praseodymium in biotite compound powder and strontium can effectively refine coarse primary silicon, overcome alloy Elemental phosphorous generated phosphorus spontaneous combustion problems are directly added in melting process.Black clouds female powder helps degasification slagging-off, and ultrasonication is molten Body also can effectively degasification, prevent from generating stomata in aluminium alloy castings, therefore the material prepared in the present invention is in Metamorphism treatment Simultaneously can also degasification slagging-off, promoted smelting efficiency.
(4) it carries out ADC12 alloy modification treatment effect using the present invention to stablize, and it is long and without latent to handle effective time Phase, crystalline silicon phase and α-Al are mutually obviously refined in the ADC12 alloy after processing, and crystal phase partial size can be down to 20 μm or so, make The mechanical property for obtaining alloy is significantly improved.
Specific embodiment
Below by the description to embodiment, specific embodiments of the present invention will be described in further detail, with side Those skilled in the art is helped to have more complete, accurate and deep understanding to inventive concept of the invention, technical solution.
Embodiment 1: it is prepared as follows the material for changing alloy phase:
One, the preparation of raw material:
Biotite meal component are as follows: 0.14wt%Na2O, 6.64wt%MgO, 6.67wt%Al2O3, 9.18wt%K2O, 2.43wt%S, 2.93wt%P, 5.23wt%FeO, surplus SiO2;The partial size of black clouds female powder is 40 mesh.
The component of ADC12 alloy are as follows: Si 10wt%, Fe 0.8wt%, Cu 1.6wt%, Mg 0.1wt%, Mn 0.6wt%, Zn0.5wt%, Ni 0.6wt%, Sn 0.08wt%, impurity content≤0.2wt%, surplus Al.
Sodium thiosulfate, aluminum sulfate, aluminum nitrate, sodium acetate, sodium nitrate, aluminium oxide, potassium chloride, sodium chloride, praseodymium nitrate, phosphorus Wolframic acid, zirconium carbide, strontium carbonate purity be all larger than 99.95wt%, partial size is 50 mesh.
Two, change the preparation of the material of alloy phase
(1) RE composite is prepared as follows: 200g black clouds female 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 20g containing praseodymium 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 over dry, obtains RE composite;
(2) preparation of biotite compound powder: according to 18wt% zirconium carbide, 23wt% RE composite, 3wt% carbonic acid Strontium, 11wt% tar, remaining is black clouds female powder ingredient, is then being stirred evenly in blender, the mixture that will be stirred evenly It is put into roaster, after 890 DEG C keep the temperature 1 hour, is air-cooled to room temperature, then takes out and ground on grinder, until particle ruler It is very little at 10 microns, can be stand-by;
(3) according to following weight percent ingredient: sodium thiosulfate 13%, aluminum sulfate 4%, aluminum nitrate 0.6%, sodium acetate 5%, sodium nitrate 13%, aluminium oxide 3%, potassium chloride 2%, biotite compound powder 15%, remaining is sodium chloride, is then being stirred It mixes in device and stirs evenly, the mixture stirred evenly is put into roaster, after 120 DEG C keep the temperature 1 hour, taking-up is cooled to room Then temperature is ground to the material that partial size changes alloy phase at 20 microns on grinder.
Metamorphism treatment is carried out to ADC12 alloy using above-mentioned change alloy phase material, the specific steps are as follows:
(1) melting in induction furnace by ADC12 alloy adjusts 740 DEG C of smelting temperature, smelting time 30min;
(2) after ADC12 alloy is completely melt, under 300rpm stirring condition, change alloy is slowly uniformly added at 750 DEG C The material of phase, additional amount are the 0.5wt% of ADC12 alloy, continue to stir 15min after being added completely into the material for changing alloy phase, Stop stirring and standing heat preservation 10min;Stand heat preservation when solution is ultrasonically treated, frequency 50kHz, processing the time be Melt is cooled to 725 DEG C, is cast in casting mold by 10min;
(3) it is demoulded after natural cooling, 450 DEG C of solid solution 1h, water cooling, 110 DEG C of timeliness 18h, air-cooled aluminium alloy to obtain the final product.
Embodiment 2: it is prepared as follows the material for changing alloy phase:
One, the preparation of raw material:
Biotite meal component are as follows: 0.33wt%Na2O, 11.92wt%MgO, 8.23wt%Al2O3, 11.32wt%K2O, 2.43wt%S, 2.93wt%P, 8.33wt%FeO, surplus SiO2;The partial size of black clouds female powder is 60 mesh.
The component of ADC12 alloy are as follows: Si 11wt%, Fe 1wt%, Cu 2.0wt%, Mg 0.1wt%, Mn 0.6wt%, Zn0.9wt%, Ni 0.8wt%, Sn 0.22wt%, impurity content≤0.2wt%, surplus Al.
Sodium thiosulfate, aluminum sulfate, aluminum nitrate, sodium acetate, sodium nitrate, aluminium oxide, potassium chloride, sodium chloride, praseodymium nitrate, phosphorus Wolframic acid, zirconium carbide, strontium carbonate purity be all larger than 99.95wt%, partial size is 100 mesh.
Two, change the preparation of the material of alloy phase
(1) RE composite is prepared as follows: 210g black clouds female powder and 25g phosphorus being added in 1000mL dehydrated alcohol Wolframic acid is placed on magnetic stirring apparatus, instills the ethanol solution 1000mL of the 25g containing praseodymium 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 over dry, obtains RE composite;
(2) preparation of biotite compound powder: according to 25wt% zirconium carbide, 29wt% RE composite, 9wt% carbonic acid Strontium, 14wt% tar, remaining is black clouds female powder ingredient, is then being stirred evenly in blender, the mixture that will be stirred evenly It is put into roaster, after 930 DEG C keep the temperature 2 hours, is air-cooled to room temperature, then takes out and ground on grinder, until particle ruler It is very little at 15 microns, can be stand-by;
(3) according to following weight percent ingredient: sodium thiosulfate 18%, aluminum sulfate 9%, aluminum nitrate 1.2%, sodium acetate 11%, sodium nitrate 16%, aluminium oxide 7%, potassium chloride 6%, biotite compound powder 19%, remaining is sodium chloride, then It is stirred evenly in blender, the mixture stirred evenly is put into roaster, after 140 DEG C keep the temperature 2 hours, taking-up is cooled to Then room temperature is ground to the material that partial size changes alloy phase at 30 microns on grinder.
Metamorphism treatment is carried out to ADC12 alloy using above-mentioned change alloy phase material, the specific steps are as follows:
(1) melting in induction furnace by ADC12 alloy adjusts 765 DEG C of smelting temperature, smelting time 30min;
(2) after ADC12 alloy is completely melt, under 500rpm stirring condition, change alloy is slowly uniformly added at 765 DEG C The material of phase, additional amount are the 0.5wt% of ADC12 alloy, continue to stir 25min after being added completely into the material for changing alloy phase, Stop stirring and standing heat preservation 20min;Stand heat preservation when solution is ultrasonically treated, frequency 100kHz, processing the time be Melt is cooled to 735 DEG C, is cast in casting mold by 20min;
(3) it is demoulded after natural cooling, 550 DEG C of solid solution 1h, water cooling, 130 DEG C of timeliness 48h, air-cooled aluminium alloy to obtain the final product.
Embodiment 3: it is prepared as follows the material for changing alloy phase:
One, the preparation of raw material:
Biotite meal component are as follows: 0.23wt%Na2O, 8.98wt%MgO, 7.21wt%Al2O3, 10.21wt%K2O, 2.43wt%S, 2.93wt%P, 6.77wt%FeO, surplus SiO2;The partial size of black clouds female powder is 50 mesh.
The component of ADC12 alloy are as follows: Si 10.5wt%, Fe 0.9wt%, Cu 1.8wt%, Mg 0.1wt%, Mn 0.6wt%, Zn 0.7wt%, Ni 0.7wt%, Sn 0.15wt%, impurity content≤0.2wt%, surplus Al.
Sodium thiosulfate, aluminum sulfate, aluminum nitrate, sodium acetate, sodium nitrate, aluminium oxide, potassium chloride, sodium chloride, praseodymium nitrate, phosphorus Wolframic acid, zirconium carbide, strontium carbonate purity be all larger than 99.95wt%, partial size is 70 mesh.
Two, change the preparation of the material of alloy phase
(1) RE composite is prepared as follows: 205g black clouds female 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 22g containing praseodymium nitrate dropwise, stirs 38h in 20 DEG C of constant temperature, 11h is dried after solvent volatilization in 75 DEG C of baking ovens to over dry, obtains RE composite;
(2) preparation of biotite compound powder: according to 21wt% zirconium carbide, 26wt% RE composite, 6wt% carbonic acid Strontium, 12.5wt% tar, remaining is black clouds female powder ingredient, is then being stirred evenly in blender, the mixing that will be stirred evenly Material be put into roaster, 910 DEG C keep the temperature 1.5 hours after, be air-cooled to room temperature, then take out and ground on grinder, until Particle size, can be stand-by at 13 microns;
(3) according to following weight percent ingredient: sodium thiosulfate 15.5%, aluminum sulfate 6.5%, aluminum nitrate 0.9%, second Sour sodium 8%, sodium nitrate 14.5%, aluminium oxide 5%, potassium chloride 4%, biotite compound powder 17%, remaining is sodium chloride, then It is being stirred evenly in blender, the mixture stirred evenly is being put into roaster, after 130 DEG C keep the temperature 1.5 hours, taken out It is cooled to room temperature, the material that partial size changes alloy phase at 25 microns is then ground on grinder.
Metamorphism treatment is carried out to ADC12 alloy using above-mentioned change alloy phase material, the specific steps are as follows:
(1) melting in induction furnace by ADC12 alloy adjusts 755 DEG C of smelting temperature, smelting time 30min;
(2) after ADC12 alloy is completely melt, under 400rpm stirring condition, change alloy is slowly uniformly added at 758 DEG C The material of phase, additional amount are the 0.5wt% of ADC12 alloy, continue to stir 20min after being added completely into the material for changing alloy phase, Stop stirring and standing heat preservation 15min;Stand heat preservation when solution is ultrasonically treated, frequency 75kHz, processing the time be Melt is cooled to 730 DEG C, is cast in casting mold by 15min;
(3) it is demoulded after natural cooling, 500 DEG C of solid solution 1h, water cooling, 120 DEG C of timeliness 33h, air-cooled aluminium alloy to obtain the final product.
Comparative examples 1: other are same as Example 3, the difference is that RE composite replaces with praseodymium nitrate.
Comparative examples 2: other are same as Example 3, the difference is that black clouds female powder is replaced using simple substance aluminium powder.
Comparative examples 3: using metamorphism treatment method disclosed in Chinese patent CN201310626657.4 to ADC12 aluminium Alloy carries out Metamorphism treatment, and gained ADC12 aluminium alloy is compareed for subsequent mechanical property test.
By the ADC12 aluminium alloy castings prepared in Examples 1 to 3 and comparative examples 1~3 carry out mechanics properties testing and SEM observes crystal phase size.
1, Mechanics Performance Testing
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 ADC12 Mechanical Property in Aluminum Alloy Castings testing result of table
Group Tensile strength (MPa) Elongation (%) Hardness (HBW)
Embodiment 1 279 4.5 101
Embodiment 2 313 4.9 111
Embodiment 3 297 4.8 107
Comparative examples 1 225 2.3 92
Comparative examples 2 165 1.4 72
Comparative examples 3 211 3.1 88
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 praseodymium 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 3 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 ADC12 alloy-steel casting is also obviously improved.
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 no 0
Comparative examples 2 It is 3.4
Comparative examples 3 It is 0.6
Table 1 combine table 3 statistics indicate that, without using black clouds female 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 black clouds female 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.
In conclusion RE composite can change sodium thiosulfate, aluminum sulfate, aluminum nitrate, sodium acetate, sodium nitrate, oxygen What the impurity elements such as zinc, magnesium were formed in change aluminium, potassium chloride, sodium chloride, zirconium carbide, strontium carbonate, black clouds female powder and ADC12 alloy has The form and size of evil phase, thus reduce the harm of impurity phase, and auxiliary improves potassium chloride, aluminium oxide, sodium thiosulfate, carbonization Zirconium, aluminum sulfate, aluminum nitrate, sodium acetate, sodium chloride, sodium nitrate, strontium carbonate 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 black clouds female 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 Praseodymium hydrate is heated to 500 DEG C or so, can resolve into praseodymium oxide, and praseodymium oxide is mixed valence steady oxide, catalytic activity It is low, praseodymium nitrate, phosphotungstic acid reacts to generation rare earth phosphotungstate in ethanol system, and using black clouds female powder as dilute in the present invention The carrier of native phosphotungstate can eliminate the defect that Rare Earth Elements of Praseodymium catalytic activity reduces under high temperature, significantly improve high melt item RE composite catalysis under part changes the form and size of impurity element harmful phase, and improving Aluminum alloy modification indirectly, treated Mechanical property.Rare Earth Elements of Praseodymium and strontium in biotite compound powder can effectively refine coarse primary silicon, overcome alloy molten Elemental phosphorous generated phosphorus spontaneous combustion problems are directly added during melting.Black clouds female 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, promoted smelting efficiency.ADC12 alloy modification treatment effect is carried out using the present invention to stablize, and is handled Effective time is long and without incubation period, and crystalline silicon phase is mutually obviously refined with α-Al in the ADC12 alloy after processing, crystal phase partial size 20 μm or so can be down to, is more significantly improved so that the mechanical property of alloy has.
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 material for changing alloy phase, which is characterized in that be grouped as by the group of following weight ratio: sodium thiosulfate 13- 18%, aluminum sulfate 4-9%, aluminum nitrate 0.6-1.2%, sodium acetate 5-11%, sodium nitrate 13-16%, aluminium oxide 3-7%, chlorination Potassium 2-6%, biotite compound powder 15-19%, remaining is sodium chloride;
The biotite compound powder zirconium carbide containing 18-25wt%, 23-29wt% RE composite, 3-9wt% strontium carbonate, 11- 14wt% tar, remaining is black clouds female powder;The RE composite is made of praseodymium nitrate, phosphotungstic acid and black clouds female powder.
2. a kind of material for changing alloy phase according to claim 1, it is characterised in that: the RE composite is by such as The preparation of lower section method: 200-210g black clouds female powder and 20-25g phosphotungstic acid are added in 1000mL dehydrated alcohol, is placed in magnetic agitation On device, instill the ethanol solution 1000mL of the 20-25g containing praseodymium nitrate dropwise, stir 36-39h in 20 DEG C of constant temperature, after solvent volatilization 10-12h is dried in 70-80 DEG C of baking oven to over dry, obtains RE composite;The sodium thiosulfate, aluminum sulfate, aluminum nitrate, second Sour sodium, sodium nitrate, aluminium oxide, potassium chloride, sodium chloride, praseodymium nitrate, phosphotungstic acid, zirconium carbide, strontium carbonate purity be all larger than 99.95wt%, partial size are 50~100 mesh.
3. a kind of preparation method for the material for changing alloy phase as claimed in claim 1 or 2, which is characterized in that include following tool Body step:
(1) preparation of biotite compound powder: according to 18-25wt% zirconium carbide, 23-29wt% RE composite, 3-9wt% carbon Sour strontium, 11-14wt% tar, remaining is black clouds female powder ingredient, is then being stirred evenly in blender, mixed by what is stirred evenly It closes material to be put into roaster, after heat preservation 1-2 hours, is air-cooled to room temperature at 890-930 DEG C, then takes out and ground on grinder, It, can be stand-by until particle size is at 10~15 microns;
(2) according to following weight percent ingredient: sodium thiosulfate 13-18%, aluminum sulfate 4-9%, aluminum nitrate 0.6-1.2%, Sodium acetate 5-11%, sodium nitrate 13-16%, aluminium oxide 3-7%, potassium chloride 2-6%, biotite compound powder 15-19%, remaining For sodium chloride, is then stirring evenly, the mixture stirred evenly is being put into roaster, at 120-140 DEG C in blender After heat preservation 1-2 hours, taking-up is cooled to room temperature, and partial size is then ground on grinder and is closed at 20~30 microns to get change The material of metallographic.
4. a kind of preparation method of material for changing alloy phase according to claim 3, it is characterised in that: the black clouds Female powder ingredient are as follows: 0.14~0.33wt%Na2O, 6.64~11.92wt%MgO, 6.67~8.23wt%Al2O3, 9.18~ 11.32wt%K2O, 2.43wt%S, 2.93wt%P, 5.23~8.33wt%FeO, surplus SiO2;The partial size of black clouds female powder is 40~60 mesh.
5. a kind of aluminium alloy preparation method, which is characterized in that using change alloy phase material pair described in claims 1 or 2 ADC12 alloy carries out Metamorphism treatment, the specific steps are as follows:
(1) melting in induction furnace by ADC12 alloy adjusts 740-765 DEG C of smelting temperature, smelting time 30min;
(2) it after ADC12 alloy is completely melt, under 300~500rpm stirring condition, is slowly uniformly added into and changes at 750-765 DEG C Become the material of alloy phase, additional amount is the 0.5wt% of ADC12 alloy, continues to stir after being added completely into the material for changing alloy phase 15~25min stops stirring and standing heat preservation 10-20min;Stand heat preservation when solution is ultrasonically treated, frequency be 50~ 100kHz, 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, 450~550 DEG C of solid solution 1h, water cooling, 110~130 DEG C of 18~48h of timeliness, air-cooled aluminium to obtain the final product Alloy.
6. a kind of aluminium alloy preparation method according to claim 5, it is characterised in that: the change alloy phase material uses It is prepared by method described in claim 4.
7. a kind of aluminium alloy preparation method according to claim 6, it is characterised in that: the component of the ADC12 alloy are as follows: Si 10~11wt%, Fe 0.8~1wt%, Cu 1.6~2.0wt%, Mg 0.1wt%, Mn 0.6wt%, Zn 0.5~ 0.9wt%, Ni 0.08~0.22wt% of 0.6~0.8wt%, Sn, impurity content≤0.2wt%, surplus Al.
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