A kind of aluminium titanium boron carbon zirconium rare earth fining agent, its preparation method and its application
Technical field
The present invention relates to a kind of aluminium titanium boron carbon zirconium rare earth fining agent, its preparation method and its applications, belong to alloy field.
Background technology
With the development of society, market proposes higher requirement to the metallurgy, composition and performance of Al-alloy products,
Aluminium processing industry needs to produce the Al-alloy products of qualified metallurgical quality, uniform ingredients and function admirable.
Conventionally produced aluminium intermediate alloy grain refiner kind has:Aluminium titanium boron, aluminium titanium carbon, aluminium titanium boron carbon rare earth etc..
At present, the preparation of aluminium intermediate alloy grain refiner be susceptible to TiB2 particles it is bigger than normal reunite, TiAl3 it is coarse be unevenly distributed,
The problems such as time is long, the timeliness time is short, alloy inner clamps sundries is on the high side is refined, causes the later stage that cannot fully meet to internal group
It knits and the crystal grain refinement of high aluminium and aluminium alloy is required to require.
The content of the invention
During in order to solve uneven aluminium intermediate alloy grain refiner structure in the prior art, refinement time length, timeliness
Between it is short, alloy inner clamps sundries is on the high side the defects of, the present invention provide a kind of aluminium titanium boron carbon zirconium rare earth fining agent, its preparation method and
It is applied.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows:
A kind of aluminium titanium boron carbon zirconium rare earth fining agent, it is composed of the following components:Titanium 3-5%, boron 0.3-0.5%, carbon 0.08-
0.15%th, zirconium 0.08-0.22%, rare earth 0.8-1.2%, impurity F e≤0.10%, impurity V≤0.03%, impurity Si≤
0.08%th, other impurity summation≤0.15% and the aluminium of surplus, other single impurity contents are respectively less than 0.03%, described hundred
Divide than being mass percent.
The fining agent refinement time of the present invention is fast (10s), and it is comprehensive to enhance alloy for refinement duration length (being more than 12h)
Energy (intensity, fracture toughness etc.) and grain refining efficiency, suitable for the various refinement feed postitions such as refinement in online refinement and stove.
In current aluminium intermediate alloy grain refiner, there are no the hexa-atomic alloy refinement agent of aluminium base, applicant's warps
Research is found:Zirconium is preferable getter, it can consumingly absorbed nitrogen, hydrogen, carrier of oxygen, more effectively control containing inside alloy
Tolerance, and zirconium has an impact the recrystallization of aluminium, and zr element has significant stabilization to the Deformation structure of alloy, can be effectively
It reduces TiAl3 particles, the column of Ti2Al20RE particles and spicule, TiB2 aggregations and leads to the problem of harmful Al4C3 phases,
Simultaneously applicant further found that Trace Zr adds in, have clear improvement to the corrosion resistance of alloy.
The raw material of above-mentioned aluminium titanium boron carbon zirconium rare earth fining agent includes:Mass ratio is 1000:(200-320):(40-50):
(0.8-6):(3-20):Aluminium ingot, potassium fluotitanate, potassium fluoborate, graphite carburant, potassium fluorozirconate and the mischmetal of (8-12),
Wherein, the purity of aluminium ingot is not less than 99.7%, and carbon content is 65-99% in graphite carburant.
In order to further improve the uniformity of product, while shorten the refinement time, extend refinement timeliness, titanium in potassium fluotitanate
Content >=19.2%, Boron contents are 8.0-8.7% in potassium fluoborate.
Above-mentioned preparation method used tool can be automatic stirring main frequency furnace and batch mixer.
In the application rpm be rpm the meaning.
In order to be further reduced impurity, uniformity is improved, shortens the refinement time, extend refinement timeliness, above-mentioned aluminium titanium boron carbon
The preparation method of zirconium rare earth fining agent, including following steps connected in order:
1) time is mixed with the speed of 50 ± 5rpm in potassium fluotitanate, potassium fluoborate, potassium fluorozirconate, graphite carburant
10-20min;
2) aluminium ingot is melted;
3) after aluminium ingot is completely melt, under conditions of temperature is 750-850 DEG C, the material obtained by step 1) is added in into aluminium
It is reacted in liquid, reaction time 20-30min;
4) slag after reaction, is scooped;
5) solvent for adding in quality of ingot aluminum 2% is stirred degassing refining, and solvent is blown into argon gas in aluminium alloy and is carried out
Refining degassing, refining time are 20-25 minutes, argon pressure 0.1-0.3Mpa, mixing speed 300-400rpm, stirring temperature
800-850 DEG C of degree;
6) slag hitting, fishing slag being carried out with Fluorspar Powder after stirring degassing refining, cleaning is completed, and cooling stands 10-20min,
Cool the temperature to 720-750 DEG C;
7) rare earth will be added in step 6) resulting material, rare earth is added in bell jar, and adition process middle bell jar is in aluminium alloy
It is moved with the speed of 10 ± 2cm/min, until rare earth is all dissolved into aluminium alloy;
8) aluminium alloy obtained by step 7) is warming up to 800 ± 20 DEG C, is then imported by chute equipped with 30-40pp i oxygen
In the filter box for changing aluminium ceramic filter, on-line filtration processing is carried out to aluminium alloy, the aluminium alloy after filtering connects by continuous casting
Milling train is rolled into aluminium titanium boron carbon zirconium rare earth fining agent.
In order to further improve the uniformity of product, impurity content is reduced, solvent for use is potassium chloride, nitric acid in step 5)
Magnesium, sodium chloride and calcium nitrate mass ratio are (5-15):(10-15):(1-3):The mixture of (0.2-0.3).
This technological process simple possible, impurity content is extremely low, effectively prevents iron loss, so as to ensure in alloy
Portion's cleannes reduce oxidation impurities.
The present invention is more significant compared with other fining agents by the reasonable addition of Zr elements and the control of preparation condition
Ground reduces the column of TiAl3 and spicule, reduces TiB2 aggregations, reduce the harmful Al4C3 phases of generation, reduce
TiAl3 phases granular size is distributed and reduces air content inside alloy.
The application of above-mentioned aluminium titanium boron carbon zirconium rare earth fining agent is aluminium 0.5-0.8kg per ton.
The unmentioned technology of the present invention is with reference to the prior art.
The present invention is by the reasonable addition of zr element and prepares the control of condition, compared with other fining agents relatively efficiently
Reduce the column of TiAl3 and spicule, reduce TiB2 aggregations, reduce the harmful Al4C3 phases of generation, reduce TiAl3
Phase granular size, the problem of being distributed and reducing air content inside alloy;Gained aluminium titanium boron carbon zirconium rare earth fining agent of the invention is thin
It is fast (10s) to change the time, refinement duration length (being more than 12h), enhances alloy comprehensive performance (intensity, fracture toughness etc.) and thin
Change ability, suitable for the various refinement feed postitions such as refinement in online refinement and stove;It is detected by metallographic, arbitrary 1cm2Vertical cut
TiAl in face3、Ti2Al20RE is substantially evenly distributed disperse, average-size<20 μm, single particle full-size<120 μm, Al3Zr
≤ 20 μm are substantially evenly distributed, and TiB2, TiC are distributed generally uniform disperse, average-size≤2 μm, Al2O3And salt attachment
Length summation<800 μm, while hydrogen content can be controlled in 0.2-0.3ml/100gAl, better meets later stage aluminium and aluminium alloy is thin
The requirement of change.
Description of the drawings
Fig. 1 is the schematic diagram before fine aluminium refinement in embodiment 1;
Fig. 2 is the schematic diagram of (20s) after fine aluminium refinement in embodiment 1.
Specific embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
The manufacturing method of aluminium titanium boron carbon zirconium rare earth grain refiner (Al-Ti5-B0.2-C0.1-Zr0.1-Re1) includes suitable
The following steps that sequence connects:
1) time is mixed with the speed of 50rpm in potassium fluotitanate, potassium fluoborate, potassium fluorozirconate, graphite carburant
15min;
2) aluminium ingot is melted;
3) after aluminium ingot is completely melt, under conditions of temperature is 800 DEG C, the material obtained by step 1) is added in molten aluminum
It is reacted, reaction time 25min;
4) slag after reaction, is scooped;
5) solvent for adding in quality of ingot aluminum 2% is stirred degassing refining, and solvent is blown into argon gas in aluminium alloy and is carried out
Refining degassing, refining time are 22 minutes, argon pressure 0.2Mpa, mixing speed 350rpm, and 820 DEG C of whipping temp is molten
Agent is that potassium chloride, magnesium nitrate, sodium chloride and calcium nitrate mass ratio are 8:12:2:0.3 mixture;
6) slag hitting, fishing slag are carried out with Fluorspar Powder after stirring degassing refining, cleaning is completed, and cooling stands 15min, by temperature
Degree is down to 740 DEG C;
7) mischmetal will be added in step 6) resulting material, rare earth is added in bell jar, and adition process middle bell jar is in alloy
It is moved in liquid with the speed of 10cm/min, until rare earth is all dissolved into aluminium alloy;
8) aluminium alloy obtained by step 7) is warming up to 800 DEG C, is then imported by chute and made pottery equipped with 35pp i aluminium oxide
In the filter box of porcelain filter, on-line filtration processing is carried out to aluminium alloy, the aluminium alloy after filtering is rolled by continuous casting and continuous rolling mill
Aluminium titanium boron carbon zirconium rare earth fining agent is made.
It is raw materials used to be:1000kg99.7% aluminium ingots, 230kg potassium fluotitanates (Ti >=20%), 45kg potassium fluoborates (B:
8.5%), 8kg potassium fluorozirconates (Zr:31%), 2.5kg graphite carburant (three energy carbon Co., Ltd of Linzhang County, phosphorus content
99%), 10kg mischmetals (Zhengzhou Zhi Yi chemical products Co., Ltd, content of rare earth >=99%).
Products obtained therefrom is detected by microscope high power:Arbitrary 1cm2Longitudinal section in TiAl3、Ti2Al20RE is substantially distributed
Even disperse, average-size<20 μm, single particle full-size<120 μm, Al3Zr≤20 μm are substantially evenly distributed, TiB2, TiC
It is distributed generally uniform disperse, average-size≤2 μm, Al2O3And the length summation of salt attachment<800μm;It is examined by hydrogen meter
It surveys:Hydrogen content is controlled in 0.2ml/100gAl.
The said goods refine fine aluminium (20000 μm), addition is fine aluminium 0.5kg per ton, and 5s is just refined,
12 it is small when refinement start to disappear, after 10s, more than 99% crystal grain reaches 1 grade (180 μm).
Embodiment 2
The manufacturing method of aluminium titanium boron carbon zirconium rare earth grain refiner includes following steps connected in order:
1) time is mixed with the speed of 55rpm in potassium fluotitanate, potassium fluoborate, potassium fluorozirconate, graphite carburant
20min;
2) aluminium ingot is melted;
3) after aluminium ingot is completely melt, under conditions of temperature is 850 DEG C, the material obtained by step 1) is added in molten aluminum
It is reacted, reaction time 30min;
4) slag after reaction, is scooped;
5) solvent for adding in quality of ingot aluminum 2% is stirred degassing refining, and solvent is blown into argon gas in aluminium alloy and is carried out
Refining degassing, refining time are 25 minutes, argon pressure 0.3Mpa, mixing speed 400rpm, and 850 DEG C of whipping temp is molten
Agent is that potassium chloride, magnesium nitrate, sodium chloride and calcium nitrate mass ratio are 15:15:3:0.3 mixture;
6) slag hitting, fishing slag being carried out with Fluorspar Powder after stirring degassing refining, cleaning is completed, and cooling stands 10-20min,
Cool the temperature to 750 DEG C;
7) rare earth will be added in step 6) resulting material, rare earth is added in bell jar, and adition process middle bell jar is in aluminium alloy
It is moved with the speed of 10cm/min, until rare earth is all dissolved into aluminium alloy;
8) aluminium alloy obtained by step 7) is warming up to 800 DEG C, is then imported by chute and made pottery equipped with 40pp i aluminium oxide
In the filter box of porcelain filter, on-line filtration processing is carried out to aluminium alloy, the aluminium alloy after filtering is rolled by continuous casting and continuous rolling mill
Aluminium titanium boron carbon zirconium rare earth fining agent is made.
It is raw materials used to be:1000kg99.7% aluminium ingots, 260kg potassium fluotitanates (Ti >=20%), 50kg potassium fluoborates (B:
8.5%), 10kg potassium fluorozirconates (Zr:31%), 2kg graphite carburant (three energy carbon Co., Ltd of Linzhang County, phosphorus content
99%), 12kg mischmetals (Zhengzhou Zhi Yi chemical products Co., Ltd, content of rare earth >=99%)
Products obtained therefrom is detected by microscope high power:Arbitrary 1cm2Longitudinal section in TiAl3、Ti2Al20RE is substantially distributed
Even disperse, average-size<20 μm, single particle full-size<120 μm, Al3Zr≤20 μm are substantially evenly distributed, TiB2, TiC
It is distributed generally uniform disperse, average-size≤2 μm, Al2O3And the length summation of salt attachment<800μm;It is examined by hydrogen meter
It surveys:Hydrogen content is controlled in 0.2ml/100gAl.
The said goods refine fine aluminium (20000 μm), addition is fine aluminium 0.5kg per ton, and 10s just occurs carefully
Change, 12 it is small when refinement start to disappear, after 20s, more than 99% crystal grain reaches 1 grade (180 μm).
Embodiment 3
The manufacturing method of aluminium titanium boron carbon zirconium rare earth grain refiner includes following steps connected in order:
1) time is mixed with the speed of 50rpm in potassium fluotitanate, potassium fluoborate, potassium fluorozirconate, graphite carburant
10min;
2) aluminium ingot is melted;
3) after aluminium ingot is completely melt, under conditions of temperature is 750 DEG C, the material obtained by step 1) is added in molten aluminum
It is reacted, reaction time 20min;
4) slag after reaction, is scooped;
5) solvent for adding in quality of ingot aluminum 2% is stirred degassing refining, and solvent is blown into argon gas in aluminium alloy and is carried out
Refining degassing, refining time are 20 minutes, argon pressure 0.1Mpa, mixing speed 300rpm, and 800 DEG C of whipping temp is molten
Agent is that potassium chloride, magnesium nitrate, sodium chloride and calcium nitrate mass ratio are 5:10:1:0.2 mixture;
6) slag hitting, fishing slag are carried out with Fluorspar Powder after stirring degassing refining, cleaning is completed, and cooling stands 10min, by temperature
Degree is down to 720 DEG C;
7) rare earth will be added in step 6) resulting material, rare earth is added in bell jar, and adition process middle bell jar is in aluminium alloy
It is moved with the speed of 10cm/min, until rare earth is all dissolved into aluminium alloy;
8) aluminium alloy obtained by step 7) is warming up to 800 DEG C, is then imported by chute equipped with 30ppi aluminium oxide ceramics
In the filter box of filter, on-line filtration processing is carried out to aluminium alloy, the aluminium alloy after filtering is by continuous casting and continuous rolling mill, rolling
Into aluminium titanium boron carbon zirconium rare earth fining agent.
It is raw materials used to be:1000kg99.7% aluminium ingots, 250kg potassium fluotitanates (Ti >=20%), 48kg potassium fluoborates (B:
8.5%), 6kg potassium fluorozirconates (Zr:31%), 1.2kg graphite carburant potassium, 10kg potassium fluorozirconates, 2kg graphite carburants (Linzhang
County three can carbon Co., Ltd, phosphorus content 99%), 11kg mischmetals (Zhengzhou Zhi Yi chemical products Co., Ltd, content of rare earth
>=99%);
Products obtained therefrom is detected by microscope high power:Arbitrary 1cm2Longitudinal section in TiAl3、Ti2Al20RE is substantially distributed
Even disperse, average-size<20 μm, single particle full-size<120 μm, Al3Zr≤20 μm are substantially evenly distributed, TiB2, TiC
It is distributed generally uniform disperse, average-size≤2 μm, Al2O3And the length summation of salt attachment<800μm;It is examined by hydrogen meter
It surveys:Hydrogen content is controlled in 0.2ml/100gAl.
The said goods refine fine aluminium (20000 μm), addition is fine aluminium 0.5kg per ton, and 5s is just refined,
12 it is small when refinement start to disappear, after 10s, more than 99% crystal grain reaches 1 grade (180 μm).