CN101205581A - Secondary aluminum prepared by using Al-Ti-C-Sr alloy refiner and preparation thereof - Google Patents

Secondary aluminum prepared by using Al-Ti-C-Sr alloy refiner and preparation thereof Download PDF

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CN101205581A
CN101205581A CNA2007101569503A CN200710156950A CN101205581A CN 101205581 A CN101205581 A CN 101205581A CN A2007101569503 A CNA2007101569503 A CN A2007101569503A CN 200710156950 A CN200710156950 A CN 200710156950A CN 101205581 A CN101205581 A CN 101205581A
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secondary aluminum
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葛炳灶
陈晓龙
李宏
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Zhejiang Jinfei Kaida Wheel Co ltd
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Abstract

The invention discloses a secondary aluminum produced by using Al-Ti-C-Sr alloy refining agent and the preparation method thereof. The compositions of the prepared secondary aluminum by weight percent are: Sr of 0.02 to 0.03 percent, Si of 6.5 to 7.5 percent, Mg of 0.25 to 0.4 percent; the content of the impurities meets the ZL101A standard; Fe of less than or equal to 0.2 percent, Cu of less than or equal to 0.1percent, Zn of less than or equal to 0.1 percent, Mn of less than or equal to 0.1 percent, the total of the impurities of less than 0.7 percent, and the remainder is aluminum. The compositions of the Al-Ti-C-Sr alloy refining agent by weight percentage are: Al of 81.5 to 86.5 percent, Ti of 4 to 7 percent, C of 0.3 to 0.5, and Sr of 10 to 11 percent. With the alloy refining agent in the invention for production of the secondary aluminum, the invention has a simple method and no pollution to the environment; the excellent fining function and deterioration function of the fining agent are fully played through the rational proportion of Sr element in the fining agent; the obtained secondary aluminum has high yield and excellent performance.

Description

Use secondary aluminum of Al-Ti-C-Sr alloy refinement agent preparation and preparation method thereof
Technical field
The invention belongs to the secondary aluminum field of material preparation.Specifically, the secondary aluminum and preparation method thereof that relates to a kind of Al-Ti-C-Sr of use alloy refinement agent preparation.
Background technology
Aluminium waste has very high recovery value.Aluminium is best suited in reclaiming and the regenerated metal.The rate of recovery height of automotive industry, building industry, electronic industry and packaging industry aluminium is between 67%~92%.Compare with producing primary aluminum, producing secondary aluminum has remarkable advantage aspect environment protection.Produce secondary aluminum from the aluminium scrap material, CO2 emissions reduces 91% than producing primary aluminum with water power, reduces more than 97% than producing primary aluminum with the fuel oil generating.Under output the same terms, the investment of founding the factory of producing secondary aluminum is only for producing 1/10th of primary aluminium.
In the production of secondary aluminum, aluminium alloy fining agent commonly used has Al-Ti-B and Al-Ti-C etc., and alterant has sodium salt, aluminium strontium master alloy, rare earth etc.Pass through to adopt special process from people such as Banerji in 1986, successfully produced since the Al-Ti-C master alloy fining agent, the research work of Al-Ti-C alloy refinement agent has had new progress, the researchist has explored multiple different preparation method, as the liquid-solid reaction method, SHS (Self-propagating High-temperature Synthesis, self propagating high temperature is synthetic) casting, XD (Exothermic Desposition, the thermopositive reaction method) method, VLS (Vapor-liquid-solid, gas-liquid-solid contact reaction method) method, rapid solidification method, contact reaction method etc., but these method production cost height, the equipment complexity, the condition harshness is difficult to realize industrial applications.
The Al-Ti-B-Sr master alloy has also been studied in present domestic laboratory, poisons problem mutually but B, Sr add existence simultaneously.
A kind of preparation method is disclosed in the Granted publication number patent of invention for CN1298463C " method for preparing aluminium titanium carbon master alloy grain-refining agent under the ultrasonic field effect ".If strontium element wherein directly adds, when carrying out pyroreaction, will constantly react with airborne water vapour, produce hydrogen and useless strontium oxide, in the finished product, produce pin hole.Need frequency of utilization to reach the ultrasonic generator of 15-25KHz in this production technique, the purchase cost of this kind equipment and use cost are very expensive, are unfavorable for factory's use of large-scale production.
Based on above-mentioned situation, do not pay attention to the good metamorphism of Sr in the alloy refinement agent in the past, in order to remedy the deficiency of Al-Ti-B-Sr master alloy, give full play to the good metamorphism of the superior detailed performance and the Sr of Al-Ti-C fining agent, the present invention proposes the be combined with each other method of a kind of new A l-Ti-C-Sr alloy refinement of preparation agent of Sr and Al-Ti-C alloy, and this alloy refinement agent is used to prepare secondary aluminum, obtain the secondary aluminum of excellent performance.
Summary of the invention
The purpose of this invention is to provide secondary aluminum of a kind of Al-Ti-C-Sr of use alloy refinement agent preparation and preparation method thereof.
The invention provides a kind of secondary aluminum, form by following component, by weight percentage,
Strontium 0.2%-0.3%,
Silicon 6.5%-7.5%,
Magnesium 0.25%-0.4%,
Impurity is not more than 0.7%,
Surplus is an aluminium.
Its tensile strength is 220-250Mpa, and unit elongation is 7%-13%, and hardness is 70-90HB.
The agent of homemade Al-Ti-C-Sr alloy refinement is used in the preparation of secondary aluminum, and the agent of described Al-Ti-C-Sr alloy refinement is made up of following component, be by weight percentage,
Aluminium: 81.5%-86.5%, titanium: 4%-7%, carbon: 0.3%-0.5%, strontium: 10%-11%.
Be preferably aluminium: 84.7%, titanium: 5%, carbon: 0.3%, strontium: 10%, or be preferably aluminium: 81.5%, titanium: 7%, carbon: 0.5%, strontium: 11%.
The invention provides a kind of preparation method of above-mentioned secondary aluminum, comprise with aluminium content being that the aluminium waste that contains of 90-92wt% is packed in the plumbago crucible, then it is formed melts in crucible electrical resistance furnace internal heating to 740 ℃ ± 5 ℃ of temperature ranges fusings, waiting to contain aluminium waste all melts back insulation and adds aluminum refining agent after 15 minutes and carry out the refining degasification, after finishing, refining takes surperficial slag off, the Al-Ti-C-Sr alloy refinement agent of preheating is added melt, the agent of Al-Ti-C-Sr alloy refinement is 2: 1000 with the part by weight that contains aluminium waste, be incubated that naturally cooling is cooled to 700-730 ℃ after 15 minutes, be cast in after skimming in the metal mold of preheating.
This method further comprises the agent of the described Al-Ti-C-Sr alloy refinement of preparation, may further comprise the steps:
(1) Graphite Powder 99 700 ℃ ± 5 ℃ following preheating 30~60min in crucible electrical resistance furnace, K 2TiF 680 ℃ of preheating 30~60min in loft drier;
(2) melt commercial-purity aluminium with medium-frequency induction furnace;
(3) molten aluminium is superheated to 800~900 ℃, adds the potassium fluotitanate and the Graphite Powder 99 of preheating;
(4) stir melt with graphite whisker;
(5) sprinkle aluminium alloy covering agent at bath surface, insulation 20min;
(6) be warming up to more than 1200 ℃ insulation 15min;
(7) take surperficial salt deposit and slag off;
(8) be cooled to 800~900 ℃, add the good Al-10Sr alloy of preheating, (the Al-10Sr alloy is chosen in and generates TiAl 3, add molten aluminium again behind the TiC particle);
(9) stir with graphite whisker the insulation back;
(10) water and cast from the sand mold.
This method further comprises preparation Al-10Sr alloy, may further comprise the steps:
1) melts commercial-purity aluminium with plumbago crucible;
2) treat fine aluminium fusing after, be warming up to 830 ℃;
3) the technical pure strontium is added molten aluminium;
4) insulation 15min;
5) melt carries out refining with rare gas element after stirring;
6) be poured in the metal mold of preheating after skimming.
Wherein, the composition of described aluminium alloy covering agent is by weight percentage: 30% NaCl, 40% KCl, NaF30%.
The rare gas element that uses is high-purity argon gas, and purity is 99.9%.
Description of drawings
Fig. 1 Al-10Sr ALLOY O M microstructure;
Fig. 2 Al-10Sr alloy SEM microstructure;
The OM microstructure of Fig. 3 Al-Ti-C-Sr alloy refinement agent;
The SEM microstructure of Fig. 4 Al-Ti-C-Sr alloy refinement agent;
The microstructure of secondary alloy before Fig. 5 (a) uses the agent of Al-Ti-C-Sr alloy refinement to handle;
Fig. 5 (b) uses the agent of Al-Ti-C-Sr alloy refinement to handle the microstructure of back secondary alloy.
Preparation embodiment 1
The preparation of Al-10Sr alloy
Present embodiment specifies the preparation process of Al-10Sr alloy, at first melts commercial-purity aluminium with plumbago crucible; After the fine aluminium fusing, be warming up to 830 ℃; Then the technical pure strontium is added molten aluminium; Insulation 15min; Melt carries out refining with high-purity argon gas (purity 99.9%) after stirring; Be poured into after skimming in the metal mold of preheating and obtain.
Then the Al-10Sr alloy is carried out microstructure observation.Fig. 1 is an Al-10Sr ALLOY O M microstructure; Fig. 2 is an Al-10Sr master alloy SEM microstructure.By Fig. 1,2 as can be seen, and Al-10Sr master alloy tissue is made up of matrix, lath-shaped tissue and fine acicular tissue.Lath-shaped organizes width greatly about about 20 μ m.Because the adding of Sr makes molten aluminium easier to be air-breathing, and the refining agent that contains halogen can make the real yield of Sr reduce, and need take necessary degassing process when therefore preparing the Al-Sr alloy.Test is taked to carry out the degasification refining to the method for the logical argon gas of molten aluminium.Have above analytical results to show that degassing effect is obvious, alloying constituent is stable, homogeneous microstructure.
Preparation embodiment 2
The preparation of Al-Ti-C-Sr alloy refinement agent
Present embodiment is used for illustrating the agent of Al-Ti-C-Sr alloy refinement.At first with Graphite Powder 99 700 ℃ ± 5 ℃ preheating 30~60min in crucible electrical resistance furnace, K 2TiF 680 ℃ of preheating 30~60min in loft drier; Melt commercial-purity aluminium with medium-frequency induction furnace; Molten aluminium is superheated to 800~900 ℃, adds the potassium fluotitanate and the Graphite Powder 99 of preheating; Stir melt with graphite whisker; Sprinkle the aluminium alloy covering agent of melt weight 10% at bath surface, insulation 20min; Be warming up to more than 1200 ℃ insulation 15min; Take surperficial salt deposit and slag off; Be cooled to 800~900 ℃, (the Al-10Sr alloy is chosen in and generates TiAl to add the good Al-10Sr alloy of preheating 3, add molten aluminium again behind the TiC particle); Stir with graphite whisker the insulation back; Water to cast from the sand mold and obtain, it specifically consists of, and is as follows by weight percentage: aluminium: 81.5%-86.5%, titanium: 4%-7%, carbon: 0.3%-0.5%, strontium: 10%-11%.
Fig. 3 and 4 is the microstructure of Al-Ti-C-Sr alloy.As can be seen from the figure, the Al-Ti-C-Sr alloy structure is by Al matrix, lath-shaped phase, massive phase, netted phase composite.
When surpassing 0.15%, Ti element content in fine aluminium can be combined into intermetallic compound TiAl3, because of three kinds of different forms can appear in the different Ti Al3 of melt temperature and speed of cooling: when the high temperature fast speed is solidified, become petal-shaped (petal-like) with Al; When solidifying at a slow speed, high temperature becomes lath-shaped (plate); Obtain bulk (blocky) during low temperature, but three kinds of forms all has identical crystalline structure.By the energy spectrum analysis of lath-shaped phase is found, the peak of Al, two kinds of elements of Ti appears in mutually in lath-shaped, thinks that this lath-shaped is TiAl mutually 3On distributing, lath-shaped TiAl3 arranges directivity very much, along the linear arrangement that is parallel to each other.
To massive phase and part lath-shaped TiAl 3That depends on every side carries out energy spectrum analysis mutually, finds that the two is elementary composition by Al, Ti, three kinds of Sr, thinks massive phase and part lath-shaped TiAl 3What depend on every side is Al, Ti, Sr ternary compound mutually, and netted phase then is the TiC particle.
Preparation embodiment 3
Use the agent of Al-Ti-C-Sr alloy refinement that secondary alloy is carried out thinning processing
Raw material
Raw material is secondary aluminum material, Al-Ti-C-Sr alloy refinement agent (the Sr weight percent is greater than 10%) and other materials.
Preparation equipment and instrument
Heating installation is crucible electrical resistance furnace, baking oven, and other instrument has Slag Tool, Bell jar, stirring tool and metal mold etc.
The secondary alloy melting
Fusion process is: with plumbago crucible 740 ℃ of fusing secondary alloys in crucible electrical resistance furnace, treat that secondary alloy all melts back insulation 15 minutes, carries out the refining degasification with aluminum refining agent.After finishing, refining takes surperficial slag off, the Al-Ti-C-Sr alloy refinement agent of preheating is added the secondary alloy melt, the weight ratio of agent of Al-Ti-C-Sr alloy refinement and secondary alloy is 2: 1000, is incubated that naturally cooling is cooled to 720 ℃ after 15 minutes, is cast in after skimming in the metal mold of preheating.
Microstructure analysis
Fig. 5 (a) handles the microstructure of front and back secondary alloy for Al-Ti-C-Sr.As can be seen from the figure, the secondary alloy α-Al that does not add Al-Ti-C-Sr is dendroid, and crystal grain is thick, and Eutectic Silicon in Al-Si Cast Alloys also is thick synusia shape; α-Al the crystal grain that adds the secondary alloy of Al-Ti-C-Sr is oval, the obvious refinement of crystal grain, and synusia shape Eutectic Silicon in Al-Si Cast Alloys is metamorphosed into point-like or fibrous.From tissue, the Al-Ti-C-Sr alloy has refinement and rotten dual function to secondary alloy.
Mechanical property after the secondary alloy thermal treatment of Al-Ti-C-Sr refinement
Respectively the secondary alloy that does not add Al-Ti-C-Sr and interpolation Al-Ti-C-Sr is done T5 thermal treatment, i.e. incomplete artificial aging after the solution treatment.Concrete heat treatment process parameter sees Table 1.
Table 1 secondary alloy T5 heat treatment process parameter
As-heat-treated condition Solution treatment Artificial aging
Heating temperature, ℃ Soaking time, h Heat-eliminating medium and temperature, ℃ Heating temperature, ℃ Soaking time, h The type of cooling
T5 535±5 10 Water 60~70 150±5 3 Air cooling
After the T5 thermal treatment, do not carry out the tensile property test to adding the Al-Ti-C-Sr fining agent with the secondary alloy that has added the Al-Ti-C-Sr fining agent, tension specimen is with reference to " metallic substance tensile test at room temperature method " (State Standard of the People's Republic of China GB/T228-2002) processing.
Do not add the secondary alloy of Al-Ti-C-Sr fining agent and the mechanical property of secondary alloy after T5 thermal treatment of interpolation Al-Ti-C-Sr fining agent and see Table 2 (referring to the MA examining reports).
Table 2 does not add Al-Ti-C-Sr and adds secondary alloy (T5) mechanical property of Al-Ti-C-Sr
Figure S2007101569503D00071
Figure S2007101569503D00081
As shown in Table 2, the average tensile strength of regeneration+Al-Ti-C-Sr alloy increases 59.7MPa than secondary alloy after the T5 thermal treatment, and elongation increases by 24%.
Above analysis revealed, the Al-Ti-C-Sr fining agent has the stronger refinement ability that goes bad to secondary alloy.
Though above be example the refinement metamorphism of Al-Ti-C-Sr fining agent is illustrated with the secondary alloy, but the technician in alloy field can clearly realize that, this Al-Ti-C-Sr fining agent can be used for the treating processes of various secondary aluminums and play identical good refinement metamorphism, should indicatedly be, those skilled in the art can carry out various changes and modification to the foregoing description, but these do not break away from the scope that spirit of the present invention and appended claim are put down in writing.

Claims (12)

1. a secondary aluminum that uses the agent of Al-Ti-C-Sr alloy refinement to make is characterized in that, form by following component, by weight percentage,
Strontium: 0.02%-0.03%,
Silicon: 6.5%-7.5%
Magnesium: 0.25%-0.4%
Impurity: content is not more than 0.7%
Surplus is an aluminium.
2. secondary aluminum as claimed in claim 1 is characterized in that, tensile strength is 220-250Mpa, and unit elongation is 7%-13%, and hardness is 70-90HB.
3. secondary aluminum as claimed in claim 1 or 2 is characterized in that, the Al-Ti-C-Sr alloy refinement agent for preparing described secondary aluminum use is made up of following component, by weight percentage,
Aluminium: 81.5%-86.5%
Titanium: 4%-7%
Carbon: 0.3%-0.5%
Strontium: 10%-11%.
4. secondary aluminum as claimed in claim 3 is characterized in that, the agent of described Al-Ti-C-Sr alloy refinement is made up of following component, be by weight percentage,
Aluminium: 84.7%;
Titanium: 5%;
Carbon: 0.3%;
Strontium: 10%.
5. secondary aluminum as claimed in claim 3 is characterized in that, the agent of described Al-Ti-C-Sr alloy refinement is made up of following component, be by weight percentage,
Aluminium: 81.5%
Titanium: 7%;
Carbon: 0.5%;
Strontium: 11%.
6. method for preparing each described secondary aluminum among the claim 1-5, comprise with aluminium content being that the aluminium waste that contains of 90-92wt% is packed in the plumbago crucible, then it is formed melts in crucible electrical resistance furnace internal heating to 740 ℃ ± 5 ℃ of temperature ranges fusings, waiting to contain aluminium waste all melts back insulation and adds aluminum refining agent after 15 minutes and carry out the refining degasification, after finishing, refining takes surperficial slag off, the Al-Ti-C-Sr alloy refinement agent of preheating is added melt, the agent of Al-Ti-C-Sr alloy refinement is 2: 1000 with the part by weight that contains aluminium waste, be incubated that naturally cooling is cooled to 700-730 ℃ after 15 minutes, be cast in after skimming in the metal mold of preheating.
7. the method for preparing secondary aluminum as claimed in claim 6, the composition of wherein said Al-Ti-C-Sr alloy refinement agent is as follows by weight percentage: aluminium: 81.5%-86.5%, titanium: 4%-7%, carbon: 0.3%-0.5%, strontium: 10%-11%.
8. the method for preparing secondary aluminum as claimed in claim 6 further comprises the agent of the described Al-Ti-C-Sr alloy refinement of preparation, may further comprise the steps:
(1) Graphite Powder 99 700 ℃ ± 5 ℃ following preheating 30~60min in crucible electrical resistance furnace, K 2TiF 680 ℃ of preheating 30~60min in loft drier;
(2) melt commercial-purity aluminium with medium-frequency induction furnace;
(3) molten aluminium is superheated to 800~900 ℃, adds the potassium fluotitanate and the Graphite Powder 99 of preheating;
(4) stir melt with graphite whisker;
(5) sprinkle 10% aluminium alloy covering agent of melt weight at bath surface, insulation 20min;
(6) be warming up to more than 1200 ℃ insulation 15min;
(7) take surperficial salt deposit and slag off;
(8) be cooled to 800~900 ℃, add the good Al-10Sr alloy of preheating;
(9) stir with graphite whisker the insulation back;
(10) water and cast from the sand mold.
9. the method for preparing secondary aluminum as claimed in claim 7 further comprises preparation Al-10Sr alloy, may further comprise the steps:
(1) melts commercial-purity aluminium with plumbago crucible;
(2) treat fine aluminium fusing after, be warming up to 830 ℃;
(3) the technical pure strontium is added molten aluminium;
(4) insulation 15min;
(5) melt carries out refining with rare gas element after stirring;
(6) be poured in the metal mold of preheating after skimming.
10. the method for preparing secondary aluminum as claimed in claim 8, the composition of wherein said aluminium alloy covering agent is by weight percentage: 30% NaCl, 40% KCl, NaF30%.
11. the method for preparing secondary aluminum as claimed in claim 9, the described rare gas element that uses is high-purity argon gas.
12. prepare the method for secondary aluminum as claimed in claim 8 or 9, described reaction process is all carried out under enclosed environment, enters neutralizing tower after generated reactive gas filters through filtering net and handles.
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CN103173643A (en) * 2013-02-01 2013-06-26 天津立中合金集团有限公司 Novel secondary aluminum modifying refiner and method for smelting secondary aluminum by utilizing refiner
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