CN112048629A - Preparation method of Al-Ti-Nb-B refiner for casting aluminum-silicon alloy - Google Patents

Preparation method of Al-Ti-Nb-B refiner for casting aluminum-silicon alloy Download PDF

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CN112048629A
CN112048629A CN202010417456.3A CN202010417456A CN112048629A CN 112048629 A CN112048629 A CN 112048629A CN 202010417456 A CN202010417456 A CN 202010417456A CN 112048629 A CN112048629 A CN 112048629A
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refiner
alloy
powder
aluminum
prepared
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李谦
黎阳
路洪州
罗群
张馨云
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CITIC Metal Co Ltd
University of Shanghai for Science and Technology
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CITIC Metal Co Ltd
University of Shanghai for Science and Technology
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/026—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium

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Abstract

The invention discloses a preparation method of an Al-Ti-Nb-B refiner for casting aluminum-silicon alloy, which comprises the following steps: a. weighing raw materials; and B, smelting the Al-Ti-Nb-B refiner. The Al-Ti-Nb-B refiner prepared by the invention is Nb2O5The Nb source is introduced, so that the raw material cost is greatly reduced; in terms of preparation effect, the grain size of alpha-Al in the aluminum-silicon alloy can be refined to 220 microns, and the industrial approval standard is met. Nb is introduced into the refiner through thermite reaction, and second phase MB in the Al-Ti-Nb-B refiner is realized2And MAl3The fine dispersion distribution of the Al-Ti-Nb-B refiner improves the refining performance of the Al-Ti-Nb-B refiner. The method can greatly reduce the preparation cost of the Al-Ti-Nb-B refiner, is simple and convenient, and is suitable for industrial large-scale production.

Description

Preparation method of Al-Ti-Nb-B refiner for casting aluminum-silicon alloy
Technical Field
The invention relates to a refiner for casting aluminum-silicon alloy and a preparation method thereof, in particular to a refiner for Al-Ti-Nb-B casting aluminum-silicon alloy and a preparation method thereof, which are applied to the technical field of aluminum alloy smelting.
Background
Cast aluminum-silicon alloys are widely used in industry due to their good mechanical properties and excellent casting properties. The alloy is subjected to grain refinement, so that a compact alloy structure can be obtained, the hot cracking and segregation tendency of a casting can be reduced, the porosity is reduced, and the comprehensive performance of the alloy can be improved. The most common and effective refinement method is the addition of grain refiners, with Al-5Ti-B being one of the most widely used refiners. However, this refiner is not suitable for refining high silicon content aluminum silicon alloys (greater than 5 wt.% Si), primarily because elemental silicon interacts with elemental titanium to form a toxic titanium silicide, rendering the refiner ineffective.
The Al-Nb-B refiner can effectively refine the high-silicon-content aluminum-silicon alloy and can effectively avoid the formation of toxic niobium silicide, thereby maintaining the refining effect of the Al-Nb-B refiner. However, Nb is relatively large in atomic mass, so that NbAl3、NbB2And the thinning particles are easy to settle and lose efficacy, and the phenomenon of remarkable thinning decline appears. In addition, the Nb powder for preparing the Al-Nb-B refiner is expensive, and the refining cost of the Al-Nb-B refiner is increased.
The Al-Ti-Nb-B refiner which appears recently can effectively refine the Al-Si alloy with high silicon content, the properties of Ti and Nb are similar, and the phase (TiAl) is refined3And NbAl3、TiB2And NbB2) Are miscible. By simultaneously introducing two refining elements of Ti and Nb into the grain refiner, the advantages and the disadvantages of the Al-Ti-B, Al-Nb-B refiner are integrated, and finally the Al-Ti-Nb-B refiner capable of effectively refining the high-silicon-content aluminum-silicon alloy is obtained. The invention provides an Al-Ti-Nb-B refiner for casting aluminum-silicon alloy, a preparation method and application thereof in Chinese patent of the prior art, application publication No. CN 108251675A, and provides a method for preparing the Al-Ti-Nb-B refiner, wherein the refiner prepared by the technology can refine the grain size of alpha-Al in the aluminum-silicon alloy to 150-450 microns, which shows that the aluminum-silicon alloy can be effectively refined by adding Al-Ti-Nb-B alloy, but the technology has the following defects:
1. the preparation raw materials of the preparation method are Al blocks, Ti particles, B particles and Nb powder, and the price is high, so that the preparation cost is not low.
2. In the prior art, Ti-Nb-B intermediate alloy is firstly smelted, and the step needs to be carried out under the protection of inert gas, so that the operation is complicated.
The high-cost preparation method and the complicated preparation process can limit the use amount and the use effect of the cast aluminum-silicon alloy to a certain extent, so that with the promotion of light weight of automobiles, a method which has low preparation cost and simple and convenient operation and can effectively refine the aluminum-silicon alloy with high silicon content is urgently needed.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a preparation method of an Al-Ti-Nb-B refiner for casting aluminum-silicon alloy, and the refiner for casting aluminum-silicon alloy with high silicon content prepared by the method has good refining effect and low preparation cost; the preparation method is simple and convenient, has low preparation cost and is suitable for industrial large-scale production.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of an Al-Ti-Nb-B refiner for casting aluminum-silicon alloy comprises the following steps:
a. weighing raw materials:
using Nb2O5As Nb source, Al block as Al source, K2TiF6Powder as Ti source, KBF4Powder is used as a source B; the preparation method comprises the following steps of carrying out raw material batching according to the component proportion for preparing the target Al-Ti-Nb-B refiner, wherein the raw material batching adopts the following mass percentage:
Nb2O5：1～7％；
Al：66～88％；
K2TiF6：5～20％；
KBF4：5～7％；
the total amount of the raw materials is 100 percent;
weighing Nb2O5Powder, Al block, K2TiF6Powder, KBF4Taking the powder as a raw material; additionally weighing at least 1% of the Al as the burning loss;
smelting an Al-Ti-Nb-B refiner:
b-1, melting the raw material Al block weighed in the step a at 750-1100 ℃ to obtain an aluminum melt;
b-2. weighing Nb in the step a2O5Powder, K2TiF6Powder, KBF4Uniformly mixing the powder, adding the powder into the aluminum melt prepared in the step b-1, and stirring for 1-3 minutes; stirring for 1-3 minutes at intervals of 10-20 minutes from the first stirring until the Al-Ti-Nb-B alloy melt with uniform components is obtained after heat preservation smelting for 1-8 hours;
b-3, after the scum of the Al-Ti-Nb-B alloy melt prepared in the step B-2 is fished out, casting the Al-Ti-Nb-B alloy melt in a cast iron mould, and demoulding after solidification to obtain the Al-Ti-Nb-B alloy.
As a preferable embodiment of the present invention, in the step B-3, the Al-Ti-Nb-B alloy is prepared to contain a refined particle phase MAL3And MB2Wherein M is Nb or Ti, and the rest is aluminum solid solution alpha-Al.
In the step b-3, the mass percentage of the refined particle phase is 1.2-5.7%, and the refined particle phase is refined particle particles with the particle size not greater than 5 micrometers and is dispersed in the alpha-Al matrix.
As a preferred embodiment of the present invention, in the step B-3, Al-Ti-Nb-B alloy is prepared containing refined particle phases (Ti, Nb) Al3The particle size is not more than 5 microns, and the particles are dispersed in the alloy in an irregular shape; refining particle phase (Ti, Nb) B2The particle size is not more than 1 micron, and the particles are dispersed in the alloy in an irregular shape.
In the step B-3, the composition of the prepared Al-Ti-Nb-B alloy composition is 92.16-94.40 wt.% of alpha-Al and 4.35-5.63 wt.% of (Ti, Nb) Al in percentage by mass3And 1.25-2.37 wt.% of (Ti, Nb) B2。
In the step B-3, the prepared Al-Ti-Nb-B alloy is used as an Al-Ti-Nb-B refiner for casting aluminum-silicon alloys, wherein the Si content is not less than 5 wt.%.
As a preferred technical scheme of the invention, in the step B-3, the prepared Al-Ti-Nb-B alloy is Al-2.50Ti-2.50Nb-0.50B or Al-1.67Ti-3.33 Nb-0.50B.
In the step b-1, the Al block is melted at 800-1000 ℃ to obtain the aluminum melt.
As the preferable technical scheme of the invention, in the step B-2, the Al-Ti-Nb-B alloy melt with uniform components is obtained by heat preservation smelting for 3-6 hours.
The principle of the invention is as follows:
nb is industrially employable2O5And Al to prepare the Al-Nb intermediate alloy with uniform structure components. Inspired by this, use Nb2O5The Al-Ti-Nb-B refiner is used for replacing Nb powder, not only can reduce the preparation cost, but also is expected to eliminate MAL in Al-Ti-Nb-B alloy3And MB2Agglomeration and sedimentation of the particles. However, Nb2O5The powder as the Nb source can not be used for preparing the Al-Nb-B refiner, but can be used as the Nb source for preparing the effective Al-Ti-Nb-B quaternary refiner. Ti source and B source as fluoride saltIs introduced mainly due to the formation of eutectic melting salts, see fig. 1, and K2TiF6The addition of (b) results in a strong heat release and a high mass transfer efficiency. The invention aims to provide a preparation method of an Al-Ti-Nb-B refiner for casting aluminum-silicon alloy, which mainly comprises the step of preparing a raw material K2TiF6、KBF4The amount of (c) is controlled in the shaded area of fig. 1, and the eutectic point molten salt is formed more easily as the eutectic point is closer.
By Nb2O5The reaction for preparing Al-Ti-Nb-B as Nb source is as follows:
a Ti source: al +3/4K2TiF6＝1/2KF+KAlF4+3/4[Ti]Wherein Al is Ti 4: 3;
nb source: al +3/10Nb2O5＝3/5[Nb]+1/2Al2O3Wherein, Al is Nb is 5: 3;
and (B) source: al + KBF4＝KAlF4+[B]Wherein, Al and B are 1: 1.
The overall reaction is as follows:
Al+1/15KBF4+1/5K2TiF6+1/5Nb2O5＝2/15KF+1/3KAlF4+1/5[Ti]+2/5[Nb]+1/3Al2O3+[B]
FIG. 2 shows Δ G of the four reaction formulae. As shown in FIG. 2, K2TiF6Δ G of (a) decreases with increasing temperature; nb2O5And KBF4Δ G of (a) increases with increasing temperature; the Δ G of the overall reaction formula does not change much with temperature and is relatively low, and the reaction proceeds more easily.
The invention uses an Al-Ti-Nb-B-O system database to calculate the content of Al-2.50Ti-0.50B alloy in different Nb2O5The phase composition at the time of addition amount is shown in FIG. 3, and the logarithmic contour line of oxygen concentration in the liquid phase and the refined phase MB are also calculated2And MAl3The content contour line of (c). As the temperature increases, the oxygen concentration in the liquid gradually increases. Abscissa Nb in FIG. 32O5Is converted into Nb content, with Nb2O5Increase, MB2And MAl3The contents of (A) are also increasing, both refinements being explicitly given in FIG. 3The content of the phase can be selected from Nb2O5The amount of increase.
The invention aims to provide a preparation method of an Al-Ti-Nb-B refiner for casting aluminum-silicon alloy, which mainly comprises the step of preparing a raw material K2TiF6、KBF4The proportion of the Al-Ti-Nb-B refiner is controlled in a shadow area of a graph 1 to obtain low-melting-point molten salt with good fluidity, improve mass transfer efficiency and ensure the uniformity of components and tissues of the Al-Ti-Nb-B refiner, thereby obtaining the high-quality Al-Ti-Nb-B refiner. According to the figure 2, the preparation method disclosed by the invention has the advantage that the reaction is easier to carry out at the smelting temperature of 750-1100 ℃. FIG. 3 calculates the Al-2.50Ti-0.50B alloy at different Nb2O5Phase composition at the time of addition amount, logarithmic contour of oxygen concentration in liquid phase, and refined phase MB2And MAl3The content contour line of (A) shows that the phase MB can be refined at different temperatures2And MAl3Requirement of the content value, determination of Nb2O5The amount of increase.
In combination with FIGS. 1-3, the present invention selects K2TiF6、KBF4、Nb2O5The Ti source, the B source and the Nb source are introduced, and the mass percentage, the smelting temperature and the heat preservation time of each raw material are limited.
In summary, taking the preparation of 1 ton of Al-1.67Ti-3.33Nb-0.50B refiner as an example, the preparation method of the invention uses Nb2O5The refining cost is 21734.0 yuan/ton of aluminum; in the traditional preparation method, Nb powder is used as an Nb source, and the refining cost is 47432.3 yuan/ton of aluminum, so the method is low in preparation cost, simple and convenient to operate and capable of effectively refining the high-silicon-content aluminum-silicon alloy.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. although the prior art uses Nb2O5The Al-Nb-B refiner can not be prepared by using the powder as a Nb source, but Nb is adopted in the preparation method of the invention2O5The powder is used as a Nb source to prepare the effective Al-Ti-Nb-B quaternary refiner, has obvious refining effect, and can refine the grain size of alpha-Al in the aluminum-silicon alloy to 220 micronsMeets the industry approval standard;
2. the grain size of the refined particle phase of the refiner prepared by the method is less than 5 microns, and the refined particle phase is dispersed in an alpha-Al matrix;
3. the method can greatly reduce the preparation cost of the Al-Ti-Nb-B refiner, is simple and convenient, and is suitable for industrial large-scale production.
Drawings
FIG. 1 is K2TiF6-KBF4Eutectic point molten salt phase diagram.
FIG. 2 is a drawing showing Nb2O5A graph showing the relationship DeltaG-T between the stepwise reaction and the total reaction in the reaction for producing Al-Ti-Nb-B as a Nb source.
FIG. 3 shows Al-2.50Ti-0.50B alloy in different Nb2O5Phase composition at the time of addition amount, logarithmic contour of oxygen concentration in liquid phase, and refined phase MB2And MAl3Content contour plot of (a).
FIG. 4 is an XRD pattern of Al-Ti-Nb-B refiner of example 1 of the present invention.
FIG. 5 is a microstructure of Al-Ti-Nb-B refiner in example 1 of the present invention.
FIG. 6 shows the polarized metallographic structure of an Al-10Si alloy obtained without adding an Al-Ti-Nb-B refiner in example 1 of the present invention.
FIG. 7 shows the polarized metallographic structure of the Al-10Si alloy after the Al-Ti-Nb-B refiner was added in example 1 of the present invention.
FIG. 8 is an XRD pattern of Al-Ti-Nb-B refiner of example 2 of the present invention.
FIG. 9 is a microstructure of Al-Ti-Nb-B refiner in example 2 of the present invention.
FIG. 10 shows the polarized metallographic structure of an Al-10Si alloy obtained by adding an Al-Ti-Nb-B refiner in example 2 of the present invention.
FIG. 11 is an XRD pattern of Al-Ti-Nb-B refiner of example 3 of the present invention.
FIG. 12 is a microstructure of an Al-Ti-Nb-B refiner in example 3 of the present invention.
FIG. 13 is a polarized metallographic structure of an Al-10Si alloy obtained by adding an Al-Ti-Nb-B refiner in example 3 of the present invention.
FIG. 14 is a graph of the grain size of α -Al in Al-10Si alloys after the addition of different Al-Ti-Nb-B refiners.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1:
in this embodiment, a method for preparing an Al-Ti-Nb-B refiner for casting aluminum-silicon alloy includes the following steps:
a. weighing raw materials:
using Nb2O5As Nb source, Al block as Al source, K2TiF6Powder as Ti source, KBF4Powder is used as a source B; the preparation method comprises the following steps of carrying out raw material batching according to the component proportion for preparing the target Al-Ti-Nb-B refiner, wherein the raw material batching adopts the following mass percentage:
weighing 395.35 g of Al block, K2TiF666.87 g of powder, KBF431.06 g of powder, Nb2O519.07 g of powder is used as a raw material, and 1 percent of the mass of Al is additionally weighed as the burning loss;
smelting an Al-Ti-Nb-B refiner:
b-1, melting the raw material Al block weighed in the step a at 1000 ℃ to obtain an aluminum melt;
b-2. weighing Nb in the step a2O5Powder, K2TiF6Powder, KBF4Uniformly mixing the powder, adding the powder into the aluminum melt prepared in the step b-1, and stirring for 1-3 minutes; stirring for 1-3 minutes at intervals of 10-20 minutes from the first stirring until the mixture is subjected to heat preservation smelting for 6 hours, so as to obtain an Al-Ti-Nb-B alloy melt with uniform components;
b-3, after the scum of the Al-Ti-Nb-B alloy melt prepared in the step B-2 is fished out, casting the Al-Ti-Nb-B alloy melt in a cast iron mould, and demoulding after solidification to obtain the Al-Ti-Nb-B alloy. The alloy finally prepared by the method of the embodiment is marked as Al-2.50Ti-2.50 Nb-0.50B-1000-6 h alloy.
Experimental test analysis:
experimental test analysis was performed on the Al-Ti-Nb-B alloys prepared in this example, see fig. 4-7.
The microstructure of the refiner prepared in this example was analyzed by X-ray diffraction and, as shown in FIG. 4, had a phase composition of 92.91 wt.% alpha-Al, 5.10 wt.% (Ti, Nb) Al3And 1.99 wt.% of (Ti, Nb) B2。
The microstructure of the refiner prepared in this example was analyzed by scanning electron microscopy and shown in FIG. 5, (Ti, Nb) Al3The particle size is less than 5 microns, and the particles are dispersed in the alloy in an irregular shape; (Ti, Nb) B2The particle size is less than 1 micron, and the particles are dispersed in the alloy in an irregular shape.
The Al-Ti-Nb-B refiner prepared by the method of the embodiment is used for testing the performance of the refiner for casting the aluminum-silicon alloy, and the casting method of the aluminum-silicon alloy comprises the following steps:
(1) heating and melting 200 g of Al-10Si alloy to be refined in a graphite crucible through a resistance furnace, and heating the melt to 800 ℃;
(2) 4.0816 g of Al-2.50Ti-2.50 Nb-0.50B-1000-6 h alloy prepared by the method of the present example was added to the melt according to the total content of Ti and Nb in the final system of 0.1 wt.%, and stirred with a corundum stirring rod preheated in advance for 30 seconds;
(3) starting from the addition of Al-2.50Ti-2.50 Nb-0.50B-1000-6 h alloy, preserving the heat for 30 minutes, cooling to 740 ℃, and casting in a phi 30mm cast iron die preheated at 250 ℃.
(4) For comparison, the Al-10Si alloy without the refiner is cast by the same casting process, the polarized metallographic structure of the alloy is shown in FIG. 6, and the grain size of the Al-10Si alloy without the Al-2.50Ti-2.50 Nb-0.50B-1000-6 h alloy is 1013 micrometers according to GB/T3246.2-2012 and calculated by an average intercept method.
The polarized metallographic structure of the Al-10Si alloy treated with the Al-2.50Ti-2.50 Nb-0.50B-1000-6 h refiner is shown in FIG. 7, and after Al-2.50Ti-2.50 Nb-0.50B-1000-6 h is added, the grain size of alpha-Al is reduced to 220 microns, which is only 21.7% of the grain size of alpha-Al when not added. The refiner for the cast aluminum-silicon alloy with high silicon content prepared by the method has good refining effect and low preparation cost; the preparation method is simple and convenient, has low preparation cost and is suitable for industrial large-scale production.
Example 2:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a method for preparing an Al-Ti-Nb-B refiner for casting aluminum-silicon alloy includes the following steps:
a. weighing raw materials:
using Nb2O5As Nb source, Al block as Al source, K2TiF6Powder as Ti source, KBF4Powder is used as a source B; the preparation method comprises the following steps of carrying out raw material batching according to the component proportion for preparing the target Al-Ti-Nb-B refiner, wherein the raw material batching adopts the following mass percentage:
weighing 394.46 g of Al block, K2TiF644.67 g of powder, KBF431.06 g of powder, Nb2O525.41 g of powder is used as a raw material, and 1 percent of the mass of Al is additionally weighed as the burning loss;
smelting an Al-Ti-Nb-B refiner:
b-1, melting the raw material Al block weighed in the step a at 800 ℃ to obtain an aluminum melt;
b-2. weighing Nb in the step a2O5Powder, K2TiF6Powder, KBF4Uniformly mixing the powder, adding the powder into the aluminum melt prepared in the step b-1, and stirring for 1-3 minutes; stirring for 1-3 minutes at intervals of 10-20 minutes from the first stirring until the mixture is subjected to heat preservation smelting for 3 hours, so as to obtain an Al-Ti-Nb-B alloy melt with uniform components;
b-3, after the scum of the Al-Ti-Nb-B alloy melt prepared in the step B-2 is fished out, casting the Al-Ti-Nb-B alloy melt in a cast iron mould, and demoulding after solidification to obtain the Al-Ti-Nb-B alloy. The alloy finally prepared by the method of the embodiment is marked as Al-1.67Ti-3.33 Nb-0.50B-800-3 h.
Experimental test analysis:
experimental test analysis was performed on the Al-Ti-Nb-B alloys prepared in this example, see fig. 8-10. The Al-Ti-Nb-B refiner prepared by the method of the present example was used as a refiner for casting Al-Si alloy, and the performance test method was the same as that of example 1.
The microstructure of the refiner prepared in this example was analyzed by X-ray diffraction and, as shown in FIG. 8, had a phase composition of 92.16 wt.% alpha-Al, 5.63 wt.% (Ti, Nb) Al3And 2.21 wt.% of (Ti, Nb) B2。
The microstructure of the refiner prepared in this example was analyzed by scanning electron microscopy, as shown in FIG. 9, (Ti, Nb) Al3The particle size is less than 5 microns, and the particles are dispersed in the alloy in an irregular shape; (Ti, Nb) B2The particle size is less than 1 micron, and the particles are dispersed in the alloy in an irregular shape.
The polarized metallographic structure of the Al-10Si alloy treated with the Al-1.67Ti-3.33 Nb-0.50B-800-3 h refiner is shown in FIG. 10, and after Al-1.67Ti-3.33 Nb-0.50B-800-3 h is added, the grain size of alpha-Al is reduced to 234 micrometers, which is only 23.1% of the grain size of alpha-Al when not added.
Example 3:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing an Al-Ti-Nb-B refiner for casting aluminum-silicon alloy includes the following steps:
a. weighing raw materials:
using Nb2O5As Nb source, Al block as Al source, K2TiF6Powder as Ti source, KBF4Powder is used as a source B; the preparation method comprises the following steps of carrying out raw material batching according to the component proportion for preparing the target Al-Ti-Nb-B refiner, wherein the raw material batching adopts the following mass percentage:
weighing 394.46 g of Al block, K2TiF644.67 g of powder, KBF431.06 g of powder, Nb2O525.41 g of powder is used as a raw material, and 1 percent of the mass of Al is additionally weighed as the burning loss;
smelting an Al-Ti-Nb-B refiner:
b-1, melting the raw material Al block weighed in the step a at 800 ℃ to obtain an aluminum melt;
b-2. weighing Nb in the step a2O5Powder, K2TiF6Powder, KBF4Uniformly mixing the powder, adding the powder into the aluminum melt prepared in the step b-1, and stirring for 1-3 minutes; stirring for 1-3 minutes at intervals of 10-20 minutes from the first stirring until the mixture is subjected to heat preservation smelting for 6 hours, so as to obtain an Al-Ti-Nb-B alloy melt with uniform components;
b-3, after the scum of the Al-Ti-Nb-B alloy melt prepared in the step B-2 is fished out, casting the Al-Ti-Nb-B alloy melt in a cast iron mould, and demoulding after solidification to obtain the Al-Ti-Nb-B alloy. The alloy finally prepared by the method of the embodiment is marked as Al-1.67Ti-3.33 Nb-0.50B-800-6 h.
Experimental test analysis:
experimental test analysis was performed on the Al-Ti-Nb-B alloys prepared in this example, see fig. 11-13. The Al-Ti-Nb-B refiner prepared by the method of the present example was used as a refiner for casting Al-Si alloy, and the performance test method was the same as that of example 1.
The microstructure of the refiner prepared in this example was analyzed by X-ray diffraction and, as shown in FIG. 11, had a phase composition of 92.70 wt.% alpha-Al, 5.36 wt.% (Ti, Nb) Al3And 1.94 wt.% of (Ti, Nb) B2。
The microstructure of the refiner prepared in this example was analyzed by scanning electron microscopy, as shown in FIG. 12, (Ti, Nb) Al3The particle size is less than 5 microns, and the particles are dispersed in the alloy in an irregular shape; (Ti, Nb) B2The particle size is less than 1 micron, and the particles are dispersed in the alloy in an irregular shape.
The polarized metallographic structure of the Al-10Si alloy treated with the Al-1.67Ti-3.33 Nb-0.50B-800-6 h refiner is shown in FIG. 13, and after Al-1.67Ti-3.33 Nb-0.50B-800-6 h is added, the grain size of alpha-Al is reduced to 290 microns, which is only 28.6% of the grain size of alpha-Al when not added.
From the above examples, it can be seen that the Al-Ti-Nb-B refiner prepared under different conditions is added to the crystal grains of alpha-Al in the Al-10Si alloyThe rule of influence of the size pairs is shown in fig. 14. FIG. 14 is a graph of the grain size of α -Al in Al-10Si alloys after the addition of different Al-Ti-Nb-B refiners. As can be seen from fig. 14, after the Al-Ti-Nb-B refiner prepared by the method of the above embodiment of the present invention is added, the grain refining effect of α -Al in the Al-10Si alloy is significant. The above embodiments of the present invention are based on Nb2O5The Al-Ti-Nb-B refiner is prepared by Nb2O5The Nb source is introduced, so that the raw material cost is greatly reduced; in terms of preparation effect, the grain size of alpha-Al in the aluminum-silicon alloy can be refined to 220 microns, and the industrial approval standard is met. Nb is introduced into the refiner through thermite reaction, and second phase MB in the Al-Ti-Nb-B refiner is realized2And MAl3The fine dispersion distribution of the Al-Ti-Nb-B refiner improves the refining performance of the Al-Ti-Nb-B refiner.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications may be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution patterns, as long as the purpose of the present invention is met, and the technical principle and inventive concept of the method for preparing Al-Ti-Nb-B refiner for casting Al-si alloy according to the present invention shall fall within the protection scope of the present invention.

Claims (9)

1. A preparation method of an Al-Ti-Nb-B refiner for casting aluminum-silicon alloy is characterized by comprising the following steps: the method comprises the following steps:
a. weighing raw materials:
using Nb2O5As Nb source, Al block as Al source, K2TiF6Powder as Ti source, KBF4Powder is used as a source B; the preparation method comprises the following steps of carrying out raw material batching according to the component proportion for preparing the target Al-Ti-Nb-B refiner, wherein the raw material batching adopts the following mass percentage:
Nb2O5：1～7％；
Al：66～88％；
K2TiF6：5～20％；
KBF4：5～7％；
the total amount of the raw materials is 100 percent;
weighing Nb2O5Powder, Al block, K2TiF6Powder, KBF4Taking the powder as a raw material; additionally weighing at least 1% of the Al as the burning loss;
smelting an Al-Ti-Nb-B refiner:
b-1, melting the raw material Al block weighed in the step a at 750-1100 ℃ to obtain an aluminum melt;
b-2. weighing Nb in the step a2O5Powder, K2TiF6Powder, KBF4Uniformly mixing the powder, adding the powder into the aluminum melt prepared in the step b-1, and stirring for 1-3 minutes; stirring for 1-3 minutes at intervals of 10-20 minutes from the first stirring until the Al-Ti-Nb-B alloy melt with uniform components is obtained after heat preservation smelting for 1-8 hours;
b-3, after the scum of the Al-Ti-Nb-B alloy melt prepared in the step B-2 is fished out, casting the Al-Ti-Nb-B alloy melt in a cast iron mould, and demoulding after solidification to obtain the Al-Ti-Nb-B alloy.
2. The method for producing an Al-Ti-Nb-B refiner for casting aluminum-silicon alloys according to claim 1, characterized in that: in the step B-3, the Al-Ti-Nb-B alloy is prepared to contain refined particle phase MAL3And MB2Wherein M is Nb or Ti, and the rest is aluminum solid solution alpha-Al.
3. The method for producing an Al-Ti-Nb-B refiner for casting aluminum-silicon alloys according to claim 2, characterized in that: in the step b-3, the mass percent of the refined particle phase is 1.2-5.7%, and the refined particle phase is refined particle particles with the particle size not more than 5 microns and is dispersed in the alpha-Al matrix.
4. The method for producing an Al-Ti-Nb-B refiner for casting Al-Si alloy according to claim 2, characterized in thatCharacterized in that: in the step B-3, the Al-Ti-Nb-B alloy is prepared to contain refined particle phase (Ti, Nb) Al3The particle size is not more than 5 microns, and the particles are dispersed in the alloy in an irregular shape; refining particle phase (Ti, Nb) B2The particle size is not more than 1 micron, and the particles are dispersed in the alloy in an irregular shape.
5. The method for producing an Al-Ti-Nb-B refiner for casting aluminum-silicon alloys according to claim 2, characterized in that: in the step B-3, the Al-Ti-Nb-B alloy composition is 92.16-94.40 wt.% of alpha-Al and 4.35-5.63 wt.% of (Ti, Nb) Al according to the mass percentage3And 1.25-2.37 wt.% of (Ti, Nb) B2。
6. The method for producing an Al-Ti-Nb-B refiner for casting aluminum-silicon alloys according to claim 1, characterized in that: in the step B-3, the prepared Al-Ti-Nb-B alloy is used as an Al-Ti-Nb-B refiner for casting aluminum-silicon alloys, wherein the mass percentage content of Si is not lower than 5 wt.%.
7. The method for producing an Al-Ti-Nb-B refiner for casting aluminum-silicon alloys according to claim 1, characterized in that: in the step B-3, the Al-Ti-Nb-B alloy prepared is Al-2.50Ti-2.50Nb-0.50B or Al-1.67Ti-3.33 Nb-0.50B.
8. The method for producing an Al-Ti-Nb-B refiner for casting aluminum-silicon alloys according to claim 1, characterized in that: in the step b-1, melting the Al block at 800-1000 ℃ to obtain an aluminum melt.
9. The method for producing an Al-Ti-Nb-B refiner for casting aluminum-silicon alloys according to claim 1, characterized in that: and in the step B-2, smelting for 3-6 hours in a heat preservation mode to obtain the Al-Ti-Nb-B alloy melt with uniform components.
CN202010417456.3A 2020-01-17 2020-05-18 Preparation method of Al-Ti-Nb-B refiner for casting aluminum-silicon alloy Pending CN112048629A (en)

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