CN102301020A - Heat resistant aluminum alloy, and method for manufacturing same - Google Patents

Heat resistant aluminum alloy, and method for manufacturing same Download PDF

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Publication number
CN102301020A
CN102301020A CN2010800059113A CN201080005911A CN102301020A CN 102301020 A CN102301020 A CN 102301020A CN 2010800059113 A CN2010800059113 A CN 2010800059113A CN 201080005911 A CN201080005911 A CN 201080005911A CN 102301020 A CN102301020 A CN 102301020A
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alloy
heat
aluminium alloy
sample
homogeneous sosoloid
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CN2010800059113A
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CN102301020B (en
Inventor
成始英
韩范释
金永稷
崔凤宰
柳镛文
金东沃
盧相澔
韩昌洙
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Korea Automotive Technology Institute
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Korea Automotive Technology Institute
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Priority claimed from KR1020090006698A external-priority patent/KR101205793B1/en
Priority claimed from KR1020090006688A external-priority patent/KR101164898B1/en
Priority claimed from KR1020090006692A external-priority patent/KR20100087586A/en
Priority claimed from KR1020090006693A external-priority patent/KR101205792B1/en
Priority claimed from KR1020090006694A external-priority patent/KR101254569B1/en
Priority claimed from KR1020090006697A external-priority patent/KR20100087590A/en
Priority claimed from KR1020090006691A external-priority patent/KR101254570B1/en
Priority claimed from KR1020090006689A external-priority patent/KR20100087583A/en
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Publication of CN102301020A publication Critical patent/CN102301020A/en
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    • 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
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/057—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2201/00—Treatment for obtaining particular effects
    • C21D2201/03—Amorphous or microcrystalline structure
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/004—Dispersions; Precipitations

Abstract

The present invention relates to a heat resistant aluminum alloy in which two types of alloy elements are bonded to aluminum while forming a homogeneous solid solution strengthening phase. The heat resistant aluminum alloy according to the present invention has innovative heat resistant properties in that the alloy elements cooperate to form a homogeneous solid solution, and the homogeneous solid solution strengthening phase, which is formed to have no solvus line with respect to the aluminum serving as a matrix metal, is not coarsened or phase-decomposed by the reaction to the aluminum even at the high temperature of 300 DEG C.

Description

Heat-resisting aluminium alloy and manufacture method thereof
Technical field
The present invention relates to a kind of heat-resisting aluminium alloy and manufacture method thereof, more specifically, relate to a kind of heat-resisting aluminium alloy that comprises aluminium and add element, wherein adding element does not have solvus (solvus line) with respect to aluminium or has solvus less than 1wt.%, it forms homogeneous sosoloid, therefore even at high temperature also keep stable, also relate to the method that is used to make this heat-resisting aluminium alloy in addition.
Background technology
The heat-resisting aluminium alloy of exploitation has heat-resistant quality at present, it is by the form of precipitated phase that Al-Si-transition element intermetallic (intermetallic) compound or Al-X (X is selected from Fe, Cu, Cr, Mn, Ti) intermetallic compound are produced in solid phase with the form by solidifying the crystalline phase that (promptly from liquid to the solid phase transformation) produce with by thermal treatment, disperses on aluminium and/or aluminium alloy matrix and control realizes.
Yet, by having there is the thermotolerance deterioration in the stable on heating this alloy of enhanced under 200 ℃ or higher temperature problem in crystallization on aluminium and/or the aluminium alloy matrix and/or precipitation intermetallic compound.
Fig. 1 is the synoptic diagram that the hot properties that is added into the element in the heat-resisting aluminium alloy in the association area is shown.As shown in the figure, remain on for a long time at traditional heat-resisting aluminium alloy under the situation of 200 ℃ or higher temperature, crystalline and/or sedimentary intermetallic compound with form new intermediate phase as the reactive aluminum of matrix so that keep thermodynamic(al)equilibrium, otherwise intermetallic compound can roughen.Therefore, may run into problems such as crackle and/or transformation for example occur, it makes the thermotolerance variation conversely.Therefore, the use of above-mentioned alloy under 200 ℃ or higher hot conditions is restricted.
Simultaneously, the aluminium mixture has thermotolerance, and it is to obtain by the nitride in the strengthening phase, boride, oxide compound and/or carbide are dispersed on the aluminium alloy matrix.This aluminium matrix composite demonstrates than the better thermotolerance of refractory alloy of using intermetallic compound.
Yet aluminium matrix composite is had any problem aspect the strengthening phase controlling equably, and the powder-base matrix material has the shortcoming of price competitiveness difference simultaneously.Taking place under the situation of surface reaction between the aluminium of matrix metal type and/or aluminium alloy and the strengthening phase, the characteristic of aluminum matrix composite is significantly degenerated.
In other words, for above-mentioned refractory alloy with controlled intermetallic compound and matrix material strengthening phase, intermetallic compound or strengthening phase may non-desirably reactions, cause the problem of degenerating greatly such as the thermotolerance of refractory alloy thus.
In addition, the various aluminium alloys of selling on the market comprise the refractory alloy in the association area of present exploitation, comprise at least 10 kinds usually and add elements.Therefore, utilize again at aluminium alloy under the situation of (or recycle), aluminium may be undesirably during refuse with add element reaction, this causes initiatively selecting the difficulty of (or screening) conversely, thereby has limited its utilization again.
Summary of the invention
Therefore, the present invention is intended to address the above problem, an object of the present invention is to provide a kind of with aluminium with there is not the heat-resisting aluminium alloy alloying element manufacturing, that have stable strengthening phase of solvus with respect to aluminium, this strengthening phase can be not at high temperature with as the reactive aluminum of matrix metal and roughen or phase decomposition; In addition, also provide a kind of method of making above-mentioned alloy.
Another object of the present invention is to provide a kind of alloying element that can keep stablizing the predetermined content of strengthening phase.
To achieve these goals, provide a kind of heat-resisting aluminium alloy, wherein, will not have two types alloying element combination of solvus, form homogeneous sosoloid strengthening phase simultaneously with respect to aluminium.
Alloying element is to comprise wherein with the amount with respect to 0.5 to 10wt.% (weight percent) of aluminium.
In addition, provide a kind of method of making heat-resisting aluminium alloy, comprising: alloying element is added in the aluminium melts of being made up of molten aluminum, and after alloying element fusion is in this melts the casting metal, obtain aluminium alloy.
Description of drawings
From following detailed description, will more be expressly understood above-mentioned and other purpose, feature and other advantages of the present invention in conjunction with the accompanying drawings, wherein:
Fig. 1 is the synoptic diagram that the hot properties that is added into the element in the refractory alloy in the association area is shown;
Fig. 2 be illustrate according to the homogeneous sosoloid strengthening phase in the heat-resisting aluminium alloy of the present invention the synoptic diagram of high-temperature stable characteristic;
Fig. 3 to Figure 10 illustrates the binary alloy phase diagram of various alloying elements; Particularly, Fig. 3 is chromium-tungsten (Cr-W) phasor, Fig. 4 is copper-nickel (Cu-Ni) phasor, Fig. 5 is iron-chromium (Fe-Cr) phasor, Fig. 6 is iron-manganese (Fe-Mn) phasor, and Fig. 7 is manganese-vanadium (Mn-V) phasor, and Fig. 8 is cobalt-nickel (Co-Ni) phasor, Fig. 9 is iron-nickel (Fe-Ni) phasor, and Figure 10 is copper-manganese (Cu-Mn) phasor;
Figure 11 is the optical microscopy map of the microtexture of the sample of preparation in the preparation example 1;
Figure 12 to 14 is photographs of the drawing result of sample that preparation is shown respectively in the preparation example 1 to 3 microtexture of using electron probe microanalyzer (EPMA), specifically is respectively, and Figure 12 is a preparation example 1, and Figure 13 is a preparation example 2, and Figure 14 is a preparation example 3;
Figure 15 illustrates the sample of preparation in the preparation example 1 in the optical microscopy map of 300 ℃ of heating observations of the microtexture of the sample of acquisition after 200 hours;
Figure 16 is the optical microscopy map that sample observations of the microtexture of the sample of acquisition after refuse is cast again of preparation in the preparation example 1 is shown;
Figure 17 illustrates in the preparation example 4 figure according to the mean sizes of the homogeneous sosoloid of each sample of the content preparation of the alloying element that adds;
Figure 18 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 5 is shown;
Figure 19 is the drawing result's of sample that preparation is shown in the preparation example 5 microtexture of using EPMA a photograph;
Figure 20 illustrates the sample of preparation in the preparation example 5 in the optical microscopy map of 300 ℃ of heating observations of the microtexture of the sample of acquisition after 200 hours;
Figure 21 is the optical microscopy map that sample observations of the microtexture of the sample of acquisition after refuse is cast again of preparation in the preparation example 5 is shown;
Figure 22 illustrates in the preparation example 6 figure according to the mean sizes of the homogeneous sosoloid of each sample of the content preparation of the alloying element that adds;
Figure 23 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 7 is shown;
Figure 24 is the drawing result's of sample that preparation is shown in the preparation example 7 microtexture of using EPMA a photograph;
Figure 25 illustrates the sample of preparation in the preparation example 7 in the optical microscopy map of 300 ℃ of heating observations of the microtexture of the sample of acquisition after 200 hours;
Figure 26 is the optical microscopy map that sample observations of the microtexture of the sample of acquisition after refuse is cast again of preparation in the preparation example 7 is shown;
Figure 27 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 8 is shown;
Figure 28 is the drawing result's of sample that preparation is shown in the preparation example 8 microtexture of using EPMA a photograph;
Figure 29 illustrates the sample of preparation in the preparation example 8 in the optical microscopy map of 300 ℃ of heating observations of the microtexture of the sample of acquisition after 200 hours;
Figure 30 is the optical microscopy map that sample observations of the microtexture of the sample of acquisition after refuse is cast again of preparation in the preparation example 8 is shown;
Figure 31 illustrates in the preparation example 9 figure according to the mean sizes of the homogeneous sosoloid of each sample of the content preparation of the alloying element that adds;
Figure 32 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 10 is shown;
Figure 33 is the drawing result's of sample that preparation is shown in the preparation example 10 microtexture of using EPMA a photograph;
Figure 34 illustrates the sample of preparation in the preparation example 10 in the optical microscopy map of 300 ℃ of heating observations of the microtexture of the sample of acquisition after 200 hours;
Figure 35 is the optical microscopy map that sample observations of the microtexture of the sample of acquisition after refuse is cast again of preparation in the preparation example 10 is shown;
Figure 36 illustrates in the preparation example 11 figure according to the mean sizes of the homogeneous sosoloid of each sample of the content preparation of the alloying element that adds;
Figure 37 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 12 is shown;
Figure 38 is the drawing result's of sample that preparation is shown in the preparation example 12 microtexture of using EPMA a photograph;
Figure 39 illustrates the sample of preparation in the preparation example 12 in the optical microscopy map of 300 ℃ of heating observations of the microtexture of the sample of acquisition after 200 hours;
Figure 40 is the optical microscopy map that sample observations of the microtexture of the sample of acquisition after refuse is cast again of preparation in the preparation example 12 is shown;
Figure 41 illustrates in the preparation example 13 figure according to the mean sizes of the homogeneous sosoloid of each sample of the content preparation of the alloying element that adds;
Figure 42 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 14 is shown;
Figure 43 is the drawing result's of sample that preparation is shown in the preparation example 14 microtexture of using EPMA a photograph;
Figure 44 illustrates the sample of preparation in the preparation example 14 in the optical microscopy map of 300 ℃ of heating observations of the microtexture of the sample of acquisition after 200 hours;
Figure 45 is the optical microscopy map that sample observations of the microtexture of the sample of acquisition after refuse is cast again of preparation in the preparation example 14 is shown;
Figure 46 illustrates in the preparation example 15 figure according to the mean sizes of the homogeneous sosoloid of each sample of the content preparation of the alloying element that adds;
Figure 47 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 16 is shown;
Figure 48 is the drawing result's of sample that preparation is shown in the preparation example 16 microtexture of using EPMA a photograph;
Figure 49 illustrates the sample of preparation in the preparation example 16 in the optical microscopy map of 300 ℃ of heating observations of the microtexture of the sample of acquisition after 200 hours;
Figure 50 is the optical microscopy map that sample observations of the microtexture of the sample of acquisition after refuse is cast again of preparation in the preparation example 16 is shown;
Figure 51 is the figure that illustrates in the preparation example 17 according to the mean sizes of the homogeneous sosoloid of each sample of the content preparation of the alloying element that adds.
Embodiment
Hereinafter will describe preferred implementation of the present invention with reference to the accompanying drawings in detail.
Fig. 2 is the synoptic diagram that illustrates according to the high-temperature stable characteristic of the homogeneous sosoloid strengthening phase that forms in the heat-resisting aluminium alloy of the present invention.As shown in Figure 2, heat-resisting aluminium alloy of the present invention is characterised in that, it comprises with respect to aluminium does not have solvus or the solvus alloying element less than 1wt.%, forms homogeneous sosoloid simultaneously on aluminum matrix mutually, thus even also not thermolysis or roughen (coarse) at high temperature.
In brief, the invention provides a kind of heat-resisting aluminium alloy, comprising: two kinds of alloying elements, it forms homogeneous sosoloid, thus in conjunction with forming homogeneous sosoloid strengthening phase simultaneously.For above-mentioned heat-resisting aluminium alloy, can use with respect to aluminium and not have solvus or solvus alloying element less than 1wt.%, therefore,, do not form the intermetallic compound that has aluminium yet, but form homogeneous sosoloid strengthening phase even when adding to alloying element in the aluminium; Wherein this homogeneous sosoloid strengthening phase is to exist and be heat-staple with single-phase form.
Therefore, though this homogeneous sosoloid strengthening phase under 200 ℃ or higher temperature not with reactive aluminum, even also not roughen or the thermolysis when being heated to the fusing point of aluminium of this strengthening phase, the homogeneous sosoloid that forms in the aluminium can stably keep.In addition, even the heat-resisting aluminium alloy of preparation is when standing refuse, the homogeneous sosoloid strengthening phase of formation also can stably keep.These effects can by following experimental result come really with.
According to the present invention, above-mentioned two types alloying element can comprise chromium (Cr) and tungsten (W).By these alloying elements, i.e. Cr and W, the sosoloid strengthening phase of making can keep stable single phase, and have the size of 1 to 200 mu m range under up to 1800 ℃ temperature.
Perhaps, two kinds of alloying elements of the present invention's use can be copper (Cu) and nickel (Ni).By these alloying elements, i.e. Cu and Ni, the homogeneous sosoloid strengthening phase of making can keep stable, and have the crystal interface shape of size 1 to 50 mu m range under up to 873 ℃ temperature.
Perhaps, two kinds of alloying elements of the present invention's use can be iron (Fe) and chromium (Cr).It is stable mutually single that the homogeneous sosoloid strengthening phase of being made by Fe and Cr can keep under up to 1500 ℃ temperature, and have plane (facet) shape of size 1 to 60 mu m range.
Perhaps, two kinds of alloying elements of the present invention's use can be iron (Fe) and manganese (Mn).The homogeneous sosoloid strengthening phase of being made by Fe and Mn can have thermotolerance under up to 1245 ℃ temperature, and forms the small flat surface shape of size 1 to 50 mu m range.
Perhaps, two kinds of alloying elements of the present invention's use can be manganese (Mn) and vanadium (V).It is stable mutually single that the homogeneous sosoloid strengthening phase of being made by Mn and V can keep under up to 1245 ℃ temperature, and have the small flat surface shape of size 1 to 100 μ m.
Perhaps, two kinds of alloying elements of the present invention's use can be cobalt (Co) and nickel (Ni).The homogeneous sosoloid strengthening phase of being made by Co and Ni can show thermotolerance under up to 1490 ℃ temperature, and forms the needle-like shape of size 1 to 70 mu m range.
Perhaps, two kinds of alloying elements of the present invention's use can be iron (Fe) and nickel (Ni).It is stable mutually single that the homogeneous sosoloid strengthening phase of being made by Fe and Ni can keep under up to 1245 ℃ temperature, and have the particle shape of size 1 to 30 mu m range.
Perhaps, two kinds of alloying elements of the present invention's use can be copper (Cu) and manganese (Mn).It is stable mutually single that the homogeneous sosoloid strengthening phase of being made by Cu and Mn can keep under up to 873 ℃ temperature, and have the size of 1 to 10 mu m range.
As mentioned above, compare with the stable on heating heat-resisting aluminium alloy of loss under 200 ℃ or higher temperature in the association area, heat-resisting aluminium alloy of the present invention, it has the homogeneous sosoloid strengthening phase of being made up of two types alloying element of the present invention's use, can have the thermotolerance of improvement.Therefore, aluminium alloy of the present invention can exist with single under 300 ℃ or higher temperature mutually, even during with its refuse, also can stably keep single phase.This result can pass through following experimental verification.
Alloying element can comprise wherein with respect to the amount of aluminium with 0.5wt.% to 10wt.%.If the content of alloying element with respect to aluminium less than 0.5wt.%, then alloying element contain quantity not sufficient, cause the decline of the strengthening effect of homogeneous sosoloid thus.On the contrary, if the content of alloying element surpasses 10wt.% with respect to aluminium, then homogeneous sosoloid strengthening phase becomes coarse, and since the ratio of coarse strengthening phase may in casting and/or liquate (segregation), encounter problems.
In addition, because above-mentioned two kinds of alloying elements can form homogeneous sosoloid, its mixture ratio is not particularly limited.Yet according to the present invention, a kind of amount in the alloying element can be 10wt.% to 90wt.%, and be contained in wherein, another kind can be the amount with 90wt.% to 10wt.%.
According to heat-resisting aluminium alloy of the present invention, can cast this metal then and make by alloying element being added in the aluminium melt that comprises molten aluminum with therein with the alloying element fusion.In this respect, consider thermosteresis, aluminium fusing can be carried out at about 700 ℃, than the fusing point of aluminium promptly 660 ℃ exceed 30-40 ℃.
In addition, the present invention can use chromium (Cr) and tungsten (W) as alloying element.In this case, Cr and W can directly add in the aluminium melts, perhaps add with Cr-W master alloy (master alloy) form.Alloying element can also Al-Cr master alloy and the interpolation of Al-W master alloy form.
Perhaps, available copper (Cu) and nickel (Ni) are as alloying element.In this case, Cu and Ni can directly add in the aluminium melts, perhaps add with Cu-Ni master alloy form.This alloying element can also Al-Cu master alloy and the interpolation of Al-Ni master alloy form.
Perhaps, available iron (Fe) and chromium (Cr) are as alloying element.In this case, Fe and Cr can directly add in the aluminium melts, perhaps add with Fe-Cr master alloy form.This alloying element can also Al-Fe master alloy and the interpolation of Al-Cr master alloy form.
Perhaps, available iron (Fe) and manganese (Mn) are as alloying element.In this case, Fe and Mn can directly add in the aluminium melts, perhaps add with Fe-Mn master alloy form.This alloying element can also Al-Fe master alloy and the interpolation of Al-Mn master alloy form.
Perhaps, available manganese (Mn) and vanadium (V) are as alloying element.In this case, Mn and V can directly add in the aluminium melts, perhaps add with Mn-V master alloy form.This alloying element can also Al-Mn master alloy and the interpolation of Al-V master alloy form.
Perhaps, available cobalt (Co) and nickel (Ni) are as alloying element.In this case, Co and Ni can directly add in the aluminium melts, perhaps add with Co-Ni master alloy form.Alloying element can also Al-Co master alloy and the interpolation of Al-Ni master alloy form.
Perhaps, available iron (Fe) and nickel (Ni) are as alloying element.In this case, Fe and Ni can directly add in the aluminium melts, perhaps add with Fe-Ni master alloy form.This alloying element can also Al-Fe master alloy and the interpolation of Al-Ni master alloy form.
Perhaps, available copper (Cu) and manganese (Mn) are as alloying element.In this case, Cu and Mn can directly add in the aluminium melts, perhaps add with Cu-Mn master alloy form.Alloying element can also Al-Cu master alloy and these the two kinds of forms interpolations of Al-Mn master alloy.
Simultaneously, the preparation that comprises the master alloy of every kind of alloying element can be implemented by the various dissolving method in the association area.According to the present invention, master alloy can prepare by the following method: plasma arc melting (PAM) method, and it uses plasma arc as thermal source, and can fuse to atmospheric wide region in rough vacuum; Perhaps vacuum induction melting (VIM) method, it uses joule heating of eddy current generation to heat and melts conductor, this eddy current flows along the reverse direction based on electro-induction, coil current in metallic conductor, thereby is easy to by strong agitation controlled temperature and moiety in the melts.
Alloying element can add with 0.5 to 10wt.% amount with respect to aluminium.The reason of doing like this is: because the roughen of the homogeneous sosoloid strengthening phase in the heat-resisting aluminium alloy of above-mentioned manufacture method preparation, and the maximization of strengthening effect, the content range that is defined as above is to preventing that liquate from being most preferred.
Hereinafter implement the effect of following experiment with identity basis refractory alloy of the present invention.
Fig. 3 to Figure 10 illustrates the binary alloy phase diagram of each alloying element, particularly, Fig. 3 is the Cr-W alloy phase diagram, Fig. 4 is the Cu-Ni alloy phase diagram, and Fig. 5 is the Fe-Cr alloy phase diagram, and Fig. 6 is the Fe-Mn alloy phase diagram, Fig. 7 is the Mn-V alloy phase diagram, Fig. 8 is the Co-Ni alloy phase diagram, and Fig. 9 is the Fe-Ni alloy phase diagram, and Figure 10 is the Cu-Mn alloy phase diagram.
As shown in Figure 3, as can be seen, Cr and W form homogeneous sosoloid, and this homogeneous sosoloid still stabilizes to solid phase under up to 1800 ℃ temperature, and this temperature is significantly higher than the fusing point of aluminium, promptly 660 ℃.
In other words, it is stable mutually single that heat-resisting aluminium alloy with homogeneous sosoloid strengthening phase of Cr and W can keep under the temperature more than 3 times of aluminium fusing point, and can assert, even this homogeneous sosoloid strengthening phase also not roughen or decomposition under up to 1800 ℃ temperature.Therefore, above-mentioned aluminium alloy can be used as aptly traditionally in high temperature for example 1800 ℃ of following uses, diesel motor piston or aircraft parts.
In addition, Fig. 4 proves that Cu and Ni form homogeneous sosoloid, and this homogeneous sosoloid stably remains solid phase under up to 870 ℃ temperature, and this temperature is higher than the fusing point of aluminium, promptly 660 ℃.
Therefore, can assert that the heat-resisting aluminium alloy with homogeneous sosoloid strengthening phase of being made up of Cu and Ni problem coarse such as this Cu-Ni homogeneous sosoloid reinforced transformation or that decompose can not occur under about 800 ℃ temperature.
In addition, Fig. 5 proves that Fe and Cr form homogeneous sosoloid, and this homogeneous sosoloid stably remains solid phase under up to 1500 ℃ temperature, and this temperature is much higher than the fusing point of aluminium, promptly 660 ℃.
In brief, under the temperature more than 2 times of aluminium fusing point, also can keep mutually single even have the heat-resisting aluminium alloy of the homogeneous sosoloid strengthening phase of forming by Fe and Cr.Therefore, even also not roughen or the decomposition under about 1500 ℃ high temperature of Fe-Cr homogeneous sosoloid strengthening phase.Based on these characteristics, above-mentioned aluminium alloy can easily be used for the part such as the gas turbine engines cylinder body of turbo-supercharger.
In addition, as can be seen from Figure 6, Fe and Mn form homogeneous sosoloid, and this homogeneous sosoloid stably remains solid phase under up to 1245 ℃ temperature, and this temperature is significantly higher than the fusing point of aluminium, promptly 660 ℃.
In brief, under the temperature more than 2 times of aluminium fusing point, also can keep mutually single even have the heat-resisting aluminium alloy of the homogeneous sosoloid strengthening phase of forming by Fe and Mn.Therefore, even also not roughen or the decomposition under about 1245 ℃ high temperature of Fe-Cr homogeneous sosoloid strengthening phase.Based on these characteristics, above-mentioned aluminium alloy can easily be used for for example diesel engine cylinder body.
In addition, as can be seen from Figure 7, Mn becomes homogeneous sosoloid with V-arrangement, and this homogeneous sosoloid stably remains solid phase under up to 1245 ℃ temperature, and this temperature is significantly higher than the fusing point of aluminium, promptly 660 ℃.
In brief, under the temperature more than 2 times of aluminium fusing point, also can keep mutually single even have the heat-resisting aluminium alloy of the homogeneous sosoloid strengthening phase of forming by Mn and V.Therefore, even also not roughen or the decomposition under about 1245 ℃ high temperature of Mn-V homogeneous sosoloid strengthening phase.Therefore, above-mentioned aluminium alloy can easily be used for for example seamless engine cylinder-body and/or other auto parts of petrol engine.
In addition, as can be seen from Figure 8, Co and Ni form homogeneous sosoloid mutually, and this homogeneous sosoloid stably remains solid phase under up to 1490 ℃ temperature, and this temperature is than promptly 660 ℃ high 830 ℃ of the fusing points of aluminium.
In brief, also can keep single mutually than aluminium fusing point under high about 830 ℃ temperature even have the heat-resisting aluminium alloy of the homogeneous sosoloid strengthening phase of forming by Co and Ni.Therefore, though Co-Ni homogeneous sosoloid strengthening phase 300 ℃ or higher temperature or also not roughen or decomposition during refuse.When above-mentioned aluminium alloy is used for the piston etc. of diesel motor, can advantageously improve motor efficiency.
In addition, as can be seen from Figure 9, Fe and Ni form homogeneous sosoloid, and this homogeneous sosoloid stably remains solid phase under up to 1245 ℃ temperature, and it is significantly higher than the fusing point of aluminium this temperature.
In brief, also can keep single mutually than aluminium fusing point under high about 600 ℃ temperature even have the heat-resisting aluminium alloy of the homogeneous sosoloid strengthening phase of forming by Fe and Ni.Therefore, based on calculation of thermodynamics, can assert also not roughen or the decomposition under of Fe-Ni homogeneous sosoloid strengthening phase up to 1245 ℃ temperature.Above-mentioned aluminium alloy can be widely used in existing motor car engine material and the part of aircraft etc. for example.
In addition, as can be seen from Figure 10, Cu and Mn form homogeneous sosoloid, and this homogeneous sosoloid stably remains solid phase under up to 873 ℃ temperature, and this temperature is higher than the fusing point of aluminium, promptly 660 ℃.
In brief, even the heat-resisting aluminium alloy with homogeneous sosoloid of being made up of Cu and Mn also keeps mutually single under 300 ℃ or higher temperature, show excellent thermotolerance thus.And, because Cu-Mn homogeneous sosoloid strengthening phase is being higher than not roughen or decomposition under the temperature aluminium fusing point, about 800 ℃, aluminium and interpolation element, promptly Cu and Mn can recycle energetically.
[embodiment 1] Cr-W homogeneous sosoloid intensified type heat-resisting aluminium alloy
Preparation example 1
When the aluminium melts that comprises molten aluminum 700 ℃ of preparations is maintained at 700 ℃, Cr and W is added in this melts with the amount of 1.5wt.% respectively as alloying element, and this melts is kept 30 to 60 minutes to fuse Cr and W fully.Then, mixture is cast, obtained having the sample (calling " Cr-W homogeneous sosoloid intensified type heat-resisting aluminium alloy " in the following text) of the heat-resisting aluminium alloy of Cr-W homogeneous sosoloid strengthening phase.
Preparation example 2
When the aluminium melts that comprises molten aluminum 700 ℃ of preparations is maintained at 700 ℃, add in this melts with the amount of 1.5wt.% respectively containing the Al-Cr master alloy of Cr of 50wt.% and the Al-W master alloy that contains the W of 50wt.%, and this melts is kept 30 to 60 minutes to fuse Al-Cr master alloy and Al-W master alloy fully.Then, mixture is cast, obtained Cr-W homogeneous sosoloid intensified type heat-resisting aluminium alloy.
Preparation example 3
When the aluminium melts that comprises molten aluminum 700 ℃ of preparations is maintained at 700 ℃, will be by Cr-W master alloy plasma arc melting (PAM), be the Cr of 50wt.%: 50wt.%: W preparation with comparing adding in this melts with respect to the amount of aluminium 3wt.%, and this melts is kept 30 to 60 minutes to fuse the Cr-W master alloy fully.Then, mixture is cast, obtained the sample of Cr-W homogeneous sosoloid intensified type heat-resisting aluminium alloy.
Figure 11 is the optical microscopy map of the microtexture of the sample of preparation in the preparation example 1, wherein sample grinds with SiC emery paper #200, #400, #600, #800, #1000, #1500 and #2400, use 1 μ m Al2O3 powder fine grainding then, then by the observation by light microscope structures of samples.Can confirm that from Figure 11 heat-resisting aluminium alloy made according to the method for the present invention has the strengthening phase of the small flat surface shape that is of a size of 1 to 200 μ m.
Figure 12 to 14 is respectively the drawing result's of sample that preparation is shown in the preparation example 1 to 3 microtexture of using electron probe microanalyzer (EPMA) a photograph.
As shown in figure 12, the sample of preparation proves that the strengthening phase of small flat surface shape shown in Figure 11 is a Cr-W homogeneous sosoloid in the preparation example 1.And each sample of preparation can be found from the preparation example 2 and 3 that Figure 13 and 14 illustrates respectively, and Cr and W form homogeneous sosoloid in each sample.
Result referring to figs 12 to 14 can think, adds according to the formation of method in of the present invention heat-resisting aluminium alloy and homogeneous sosoloid irrelevant as alloying element Cr and W.
In addition,, the sample elder generation of preparation in the preparation example 1 was heated 200 hours at 300 ℃, follow microtexture by this heat treated sample of observation by light microscope in order to analyze high-temperature stability according to Cr-W homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention.Observations as shown in figure 15.
As shown in figure 15, with under the high temperature in aluminum matrix roughen or the existing intermetallic compound that stands phase decomposition compare, the strengthening phase of being made up of Cr-W homogeneous sosoloid shows as strengthening phase identical with microtexture shown in Figure 11, small flat surface shape.And, owing to do not observe the roughen or the phase decomposition of strengthening phase, even can think that the Cr-W homogeneous sosoloid strengthening phase of Cr-W homogeneous sosoloid intensified type heat-resisting aluminium alloy also is stable at 300 ℃.
Figure 16 is the observations that the sample microtexture of back acquisition is cast in the sample refuse of preparation in the preparation example 1 again.Herein, the cast samples after the refuse be basically by will be in the preparation example 1 the sample refuse of preparation to the fusing point of aluminium, and cast the sample of this processing and obtain.
As shown in figure 16, as can be seen, according to the homogeneous sosoloid that forms in the Cr-W homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention, even also not roughen or decomposition during refuse, desired in the binary alloy phase diagram just as shown in Figure 3, on the contrary, it has kept strengthening phase.From these results, can assert, when recycling, can be used for effectively reclaiming aluminium energetically, and Cr and W reach the initial level of ecological friendly type as alloying element as matrix metal according to heat-resisting aluminium alloy of the present invention.
Preparation example 4
When the aluminium melts that comprises molten aluminum 700 ℃ of preparations is maintained at 700 ℃, will be by plasma arc melting (PAM), use comparing of Cr: W to be that the Cr-W master alloy of 50wt.%: 50wt.% preparation is respectively to add in this melts with respect to the amount of aluminium 0.5wt.%, 1wt.%, 3wt.%, 5wt.%, 7wt.%, 9wt.%, 10wt.% and 11wt.%.Then, this melts is kept 30 to 60 minutes to fuse the Cr-W master alloy fully, cast this melts then, obtain the sample of Cr-W homogeneous sosoloid intensified type heat-resisting aluminium alloy.
Figure 17 illustrates in the preparation example 4 figure according to the mean sizes of the homogeneous sosoloid of each sample of the content preparation of the alloying element that adds.Behind image, utilize image analyzer from the image of analyzing, to determine to have the mean sizes of homogeneous sosoloid of the alloying element of different content by the microtexture of each sample of preparation in the opticmicroscope analyte preparation example 4.
Results verification, if add the Cr-W master alloy of 0.5wt.%, the amount of the homogeneous sosoloid of formation descends, and its size is also little of about 10 μ m.On the other hand, when the amount of adding is 10wt.% or when higher, homogeneous sosoloid be of a size of 300 μ m or more than, therefore coarse a lot.
Therefore, the content of each alloying element in adding aluminium to is under the situation of 0.5wt.% to 10wt.%, and Cr-W homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention can be included in the capacity homogeneous sosoloid that wherein forms, thereby represents good alloy effect.And, can prevent because the problem that roughen causes such as liquate.
[embodiment 2] Cu-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy
Preparation example 5
Except with the amount of Cu and each 1.5wt% of Ni as the alloying element, by having the sample (calling " Cu-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy " in the following text) of the heat-resisting aluminium alloy of Cu-Ni homogeneous sosoloid strengthening phase with the identical program preparation described in the preparation example 1.
Figure 18 is the optical microscopy map of the observations of the microtexture of the sample of preparation in the preparation example 5, wherein sample grinds with SiC emery paper #200, #400, #600, #800, #1000, #1500 and #2400, use 1 μ m Al2O3 powder fine grainding then, then by the observation by light microscope structures of samples.Found that the strengthening phase that the Cu-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy sample of preparation has the crystal interface shape of size 1 to 50 μ m in the preparation example 5.
Figure 19 is the drawing result's of the sample that shows preparation in the preparation example 5 microtexture of using EPMA a photograph.From this figure, can confirm that the strengthening phase of crystal interface shape is a Cu-Ni homogeneous sosoloid.
In addition,, the sample elder generation of preparation in the preparation example 5 was heated 200 hours at 300 ℃, follow microtexture by this heated sample of observation by light microscope in order to analyze the high-temperature stability of Cu-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention.Observations as shown in figure 20.
As shown in figure 20, with under the high temperature in aluminum matrix roughen or the existing intermetallic compound that stands phase decomposition compare, the strengthening phase of being made up of homogeneous sosoloid shows as strengthening phase identical with microtexture shown in Figure 180, the crystal interface shape.And, owing to do not observe the coarse or phase decomposition of reinforced transformation, can think, even the Cu-Ni homogeneous sosoloid strengthening phase of Cu-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy also is stable at 300 ℃.
Figure 21 is the optical microscopy map that sample observations of the microtexture of the sample of acquisition after refuse is cast again of preparation in the preparation example 5 is shown.Herein, the cast samples after the refuse be basically by will be in the preparation example 5 the sample refuse of preparation to the fusing point of aluminium, and cast the sample of this processing and obtain.
As shown in figure 21, as can be seen, the homogeneous sosoloid that forms in the Cu-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention, even also not roughen or decomposition during refuse, as desired in the binary alloy phase diagram that shows among Fig. 4, on the contrary, it has kept strengthening phase.And, from these results, can assert, under the situation of recycling alumite, have 3.3 times characteristic and feature of the proportion of aluminium if use above-mentioned Cu-Ni homogeneous sosoloid strengthening phase, above-mentioned heat-resisting aluminium alloy can be used for selecting energetically and reclaiming aluminium as matrix metal effectively, and Cr and W reach the initial level of ecological friendly type as alloying element.
Preparation example 6
Except using Cu: the comparing of Ni be 50wt.%: 50wt.%, the Cu-Ni master alloy by plasma arc melting (PAM) preparation, by preparing the sample of Cu-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy with the same program described in the preparation example 4.
Figure 22 illustrates in the preparation example 6 figure according to the mean sizes of the homogeneous sosoloid of each sample of the content preparation of the alloying element that adds, behind the image of microtexture by each sample of preparation in the opticmicroscope analyte preparation example 6, from the image of analyzing, determine to have the mean sizes of the homogeneous sosoloid of different-alloy constituent content with image analyzer.
Results verification, if add the master alloy of 0.5wt.%, the amount of the homogeneous sosoloid of formation descends, and its size is also little of about 1 μ m, so immeasurability.On the other hand, when the amount of adding is 10wt.% or when higher, homogeneous sosoloid be of a size of 300 μ m or more than, therefore coarse a lot.Therefore, the content of each alloying element in adding aluminium to is under the situation of 0.5wt.% to 10wt.%, and Cr-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention can be included in the capacity homogeneous sosoloid that wherein forms, thereby represents good alloy effect.And, can prevent because the problem that the size roughen causes such as liquate.
[embodiment 3] Fe-Cr homogeneous sosoloid intensified type heat-resisting aluminium alloy
Preparation example 7
Except with the amount of Fe and each 1.5wt% of Cr as the alloying element, by having the sample (calling " Fe-Cr homogeneous sosoloid intensified type heat-resisting aluminium alloy " in the following text) of the heat-resisting aluminium alloy of Fe-Cr homogeneous sosoloid strengthening phase with the same program preparation described in the preparation example 1.
Figure 23 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 7 is shown, wherein sample grinds with SiC emery paper #200, #400, #600, #800, #1000, #1500 and #2400, use 1 μ m Al2O3 powder fine grainding then, then by the observation by light microscope structures of samples.Found that the heat-resisting aluminium alloy sample of preparation has the strengthening phase of the small flat surface shape of size 1 to 60 μ m in the preparation example 7.
Figure 24 is the drawing result's of sample that preparation is shown in the preparation example 7 microtexture of using EPMA a photograph.Can confirm that from this figure the strengthening phase of small flat surface shape is a Fe-Cr homogeneous sosoloid.
In addition,, the sample elder generation of preparation in the preparation example 7 was heated 200 hours at 300 ℃, follow microtexture by this heated sample of observation by light microscope in order to analyze the high-temperature stability of Fe-Cr homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention.Observations as shown in figure 25.
As shown in figure 25, with under the high temperature in aluminum matrix roughen or the existing intermetallic compound that stands phase decomposition compare, the strengthening phase of being made up of Fe-Cr homogeneous sosoloid shows as the strengthening phase of the small flat surface shape identical with the microtexture shown in Figure 23.And, owing to do not observe the roughen or the phase decomposition of strengthening phase, can think, even the Fe-Cr homogeneous sosoloid strengthening phase of Fe-Cr homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention also is stable at 300 ℃.
Figure 26 is that the optical microscopy map of the observations of the microtexture of the sample of acquisition is afterwards cast in the sample refuse that preparation in the preparation example 7 is shown again.Herein, cast samples be basically sample by preparation in the refuse preparation example 7 to the fusing point of aluminium, and cast the sample of this processing and obtain.
As shown in figure 26, as can be seen, the homogeneous sosoloid even also not roughen or the decomposition during refuse that form in the Fe-Cr homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention, binary alloy phase diagram as shown in Figure 5 is desired, on the contrary, it has kept strengthening phase.And, can assert, under the situation that reclaims alumite, have 2.78 times characteristic and feature of the proportion of aluminium if use above-mentioned Fe-Cr homogeneous sosoloid strengthening phase, above-mentioned heat-resisting aluminium alloy can be used for selecting energetically and reclaiming aluminium as matrix metal effectively, and Fe and Cr reach the initial level of ecological friendly type as alloying element.
[embodiment 4] Fe-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy
Preparation example 8
Except with the amount of Fe and each 1.5wt.% of Mn as the alloying element, by having the sample (calling " Fe-Mn is solid-state molten intensified type heat-resisting aluminium alloy evenly " in the following text) of the heat-resisting aluminium alloy of Fe-Mn homogeneous sosoloid strengthening phase with preparation example 1 described same program preparation.
Figure 27 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 8 is shown, wherein sample grinds with SiC emery paper #200, #400, #600, #800, #1000, #1500 and #2400, use 1 μ m Al2O3 powder fine grainding then, then by the observation by light microscope structures of samples.Find that from Figure 27 the heat-resisting aluminium alloy sample of preparation has the strengthening phase of the small flat surface shape of size 1 to 50 μ m in the preparation example 8.
Figure 28 is the drawing result's of sample that preparation is shown in the preparation example 8 microtexture of using EPMA a photograph.Can confirm that small flat surface shape strengthening phase shown in Figure 27 is a Fe-Mn homogeneous sosoloid.
In addition,, the sample elder generation of preparation in the preparation example 8 was heated 200 hours at 300 ℃, follow microtexture by this heated sample of observation by light microscope in order to analyze the high-temperature stability of Fe-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention.Observations as shown in figure 29.
As shown in figure 28, with under the high temperature in aluminum matrix roughen or the existing intermetallic compound that stands phase decomposition compare, the strengthening phase of being made up of Fe-Mn homogeneous sosoloid shows as the strengthening phase of the small flat surface shape identical with the microtexture shown in Figure 27.And, owing to do not observe the roughen or the phase decomposition of strengthening phase, can think, even the Fe-Mn homogeneous sosoloid strengthening phase of Fe-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention also is stable at 300 ℃.
Figure 30 is that the optical microscopy map of the observations of the microtexture of the sample of acquisition is afterwards cast in the sample refuse that preparation in the preparation example 8 is shown again.Herein, the cast samples that obtains after the refuse be basically by will be in the preparation example 8 the sample refuse of preparation to the fusing point of aluminium, cast the sample of this processing then and obtain.
As shown in figure 30, as can be seen, even homogeneous sosoloid also not roughen or the decomposition during refuse that forms in the Fe-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention, binary alloy phase diagram just as shown in Figure 6 is desired, and it has kept strengthening phase on the contrary.And, can assert, under the situation that reclaims alumite, if the proportion of using above-mentioned Fe-Cr homogeneous sosoloid strengthening phase is 2.8 times characteristic and feature of aluminium, above-mentioned heat-resisting aluminium alloy can be used for selecting energetically and reclaiming aluminium as matrix metal effectively, and Fe and Mn reach the initial level of ecological friendly type as alloying element.
Preparation example 9
Comprise Fe except using: the comparing of Mn be 50wt.%: 50wt.%, the Fe-Mn master alloy by plasma arc melting (PAM) preparation, by preparing the sample of heat-resisting aluminium alloy with the same program described in the preparation example 4.
Figure 31 illustrates in the preparation example 9 according to the alloying element that adds, the figure of the mean sizes of the homogeneous sosoloid of each sample of preparation.Each sample of preparation is by after the microstructural image of opticmicroscope, with the mean sizes of image analyzer homogeneous sosoloid of the alloying element of definite different content from the image of analyzing in the analyte preparation example 9.
Results verification, if add the Fe-Mn master alloy of 0.5wt.%, the amount of the homogeneous sosoloid of formation descends, and its size is also little of about 5 μ m or lower.On the other hand, when the amount of adding is 10wt.% or when higher, homogeneous sosoloid be of a size of 250 μ m or more than, therefore coarse a lot.Therefore, the content of each alloying element in adding aluminium to is under the situation of 0.5wt.% to 10wt.%, and Fe-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention can be included in the capacity homogeneous sosoloid that wherein forms, thereby represents good alloy effect.And, can prevent because the problem that roughen causes such as liquate.
[embodiment 5] Mn-V homogeneous solid solution build heat-resisting aluminium alloy
Preparation example 10
Except with the amount of Mn and each 1.5wt.% of V as the alloying element, by with preparation example 1 in the same program preparation described have the sample (calling " Mn-V homogeneous sosoloid intensified type heat-resisting aluminium alloy " in the following text) of the heat-resisting aluminium alloy of Mn-V homogeneous sosoloid strengthening phase.
Figure 32 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 10 is shown, wherein sample grinds with SiC emery paper #200, #400, #600, #800, #1000, #1500 and #2400, use 1 μ m Al2O3 powder fine grainding then, then by the observation by light microscope structures of samples.Find that from Figure 32 the Mn-V homogeneous sosoloid intensified type heat-resisting aluminium alloy sample of preparation has the strengthening phase of the small flat surface shape of size 1 to 100 μ m in the preparation example 10.
Figure 33 illustrates the photograph that the sample for preparing in the preparation example 10 uses the microtexture drawing result of EPMA.Can confirm that the small flat surface shape strengthening phase that shows among Figure 32 is a Mn-V homogeneous sosoloid.
In addition,, the sample elder generation of preparation in the preparation example 10 was heated 200 hours at 300 ℃, follow microtexture by this heated sample of observation by light microscope in order to analyze the high-temperature stability of Mn-V homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention.Observations as shown in figure 34.
As shown in figure 34, with under the high temperature in aluminum matrix roughen or the existing intermetallic compound that stands phase decomposition compare, the strengthening phase of being made up of Mn-V homogeneous sosoloid shows as the strengthening phase of the small flat surface shape identical with the microtexture shown in Figure 32.And, owing to do not observe the roughen or the phase decomposition of strengthening phase, can think, even the Mn-V homogeneous sosoloid strengthening phase of Mn-V homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention also is stable at 300 ℃.
Figure 35 is that the optical microscopy map of the observations of the microtexture of the sample of acquisition is afterwards cast in the sample refuse that preparation in the preparation example 10 is shown again.Herein, the cast samples that obtains after the refuse be basically by will be in the preparation example 10 the sample refuse of preparation to the fusing point of aluminium, cast the sample of this processing then and obtain.
As shown in figure 35, as can be seen, even Mn-V homogeneous sosoloid also not roughen or the decomposition during refuse that forms in the Mn-V homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention, binary alloy phase diagram just as shown in Figure 7 is desired, on the contrary, it has kept strengthening phase.And, can assert, under the situation that reclaims alumite, if the proportion of using above-mentioned Fe-Cr homogeneous sosoloid strengthening phase is 2.4 times characteristic and feature of aluminium, above-mentioned heat-resisting aluminium alloy can be used for selecting energetically and reclaiming aluminium as matrix metal effectively, and Fe and V reach the initial level of ecological friendly type as alloying element.
Preparation example 11
Comprise Mn except using: comparing of V is to prepare the sample of heat-resisting aluminium alloy by the same program described in the preparation example 4 50wt.%: 50wt.%, the Mn-V master alloy by plasma arc melting (PAM) preparation.
Figure 36 illustrates the mean sizes figure of the homogeneous sosoloid of each sample for preparing according to the alloying element that adds in the preparation example 11.Each sample of preparation is by after the microstructural image of opticmicroscope, with the mean sizes of image analyzer homogeneous sosoloid of the alloying element of definite different content from the image of analyzing in the analyte preparation example 11.
Results verification, if add the Mn-V master alloy of 0.5wt.%, the amount of the homogeneous sosoloid of formation descends, and its size is also little of about 4 μ m or lower.On the other hand, when the amount of adding is 10wt.% or when above, homogeneous sosoloid be of a size of about 300 μ m or more than, therefore coarse a lot.Therefore, the content of each alloying element in adding aluminium to is under the situation of 0.5wt.% to 10wt.%, and Mn-V homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention can be included in the capacity homogeneous sosoloid that wherein forms, thereby represents good alloy effect.And, can prevent because the problem that the size roughen causes such as liquate.
[embodiment 6] Co-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy
Preparation example 12
Except the amount of using Co and each 1.5wt.% of Ni as the alloying element, by with preparation example 1 in program preparation that describe, identical have the sample (calling " Co-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy " in the following text) of the heat-resisting aluminium alloy of Co-Ni homogeneous sosoloid strengthening phase.
Figure 37 is the optical microscopy map that shows the observations of the microtexture of the sample of preparation in the preparation example 12, wherein sample grinds with SiC emery paper #200, #400, #600, #800, #1000, #1500 and #2400, use 1 μ m Al2O3 powder fine grainding then, then by the observation by light microscope structures of samples.Find that from Figure 37 the heat-resisting aluminium alloy sample of preparation has the acicular strengthening phase of size 1 to 70 μ m in the preparation example 12.
Figure 38 is the drawing result's of sample that preparation is shown in the preparation example 12 microtexture of using EPMA a photograph.Can confirm that the needle-like strengthening phase shown in Figure 37 is a Co-Ni homogeneous sosoloid.
In addition,, the sample elder generation of preparation in the preparation example 12 was heated 200 hours at 300 ℃, follow microtexture by this heated sample of observation by light microscope in order to analyze the high-temperature stability of Co-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention.Observations as shown in figure 39.
As shown in figure 39, with under the high temperature in aluminum matrix roughen or the existing intermetallic compound that stands phase decomposition compare, the strengthening phase of being made up of Co-Ni homogeneous sosoloid shows as the acicular strengthening phase identical with the microtexture shown in Figure 37.And, owing to do not observe the roughen or the phase decomposition of strengthening phase, can think, even the Co-Ni homogeneous sosoloid strengthening phase of Co-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention also is stable at 300 ℃.
Figure 40 is that the optical microscopy map of the observations of the microtexture of the sample of acquisition is afterwards cast in the sample refuse that preparation in the preparation example 12 is shown again.Herein, the cast samples that obtains after the refuse be basically by will be in the preparation example 12 the sample refuse of preparation to the fusing point of aluminium, cast the sample of this processing then and obtain.
As shown in figure 40, as can be seen, even homogeneous sosoloid also not roughen or the decomposition during refuse that forms in the Co-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention, binary alloy phase diagram just as shown in Figure 8 is desired, on the contrary, it has kept strengthening phase.And, can assert that reclaiming under the situation of alumite, if use above-mentioned characteristic, above-mentioned heat-resisting aluminium alloy can be used for selecting energetically and reclaiming aluminium as matrix metal effectively, and Co and Ni reach the initial level of ecological friendly type as alloying element.
Preparation example 13
Comprise Co except using: comparing of Ni is to prepare the sample of heat-resisting aluminium alloy by the same program described in the preparation example 4 50wt.%: 50wt.%, the Co-Ni master alloy by plasma arc melting (PAM) preparation.
Figure 41 illustrates in the preparation example 13 figure according to the mean sizes of the homogeneous sosoloid of each sample of the alloying element preparation of adding.After the microstructural image by each sample of preparation in the opticmicroscope analyte preparation example 13, with the mean sizes of image analyzer homogeneous sosoloid of the alloying element of definite different content from the image of analyzing.
Results verification, if add the Co-Ni master alloy of 0.5wt.%, the amount of the homogeneous sosoloid of formation descends, and its size is also little of about 5 μ m or following.On the other hand, when the amount of adding is 10wt.% or when above, homogeneous sosoloid be of a size of about 300 μ m or more than, therefore coarse a lot.Therefore, the content of each alloying element in adding aluminium to is under the situation of 0.5wt.% to 10wt.%, and Co-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention can be included in the capacity homogeneous sosoloid that wherein forms, thereby represents good alloy effect.And, can prevent because the problem that roughen causes such as liquate.
[embodiment 7] Fe-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy
Preparation example 14
Except the amount of using Fe and each 1.5wt.% of Ni as the alloying element, by with preparation example 1 in the same program preparation described have the sample (calling " Fe-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy " in the following text) of the heat-resisting aluminium alloy of Fe-Ni homogeneous sosoloid strengthening phase.
Figure 42 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 14 is shown, wherein sample grinds with SiC emery paper #200, #400, #600, #800, #1000, #1500 and #2400, use 1 μ m Al2O3 powder fine grainding then, then by the observation by light microscope structures of samples.Find that from Figure 42 the heat-resisting aluminium alloy sample of preparation has the granular strengthening phase of size 1 to 30 μ m in the preparation example 12.
Figure 43 is the drawing result's of sample that preparation is shown in the preparation example 14 microtexture of using EPMA a photograph.Can confirm that the particulate state strengthening phase shown in Figure 42 is a Fe-Ni homogeneous sosoloid.
In addition,, the sample elder generation of preparation in the preparation example 14 was heated 200 hours at 300 ℃, follow microtexture by this heated sample of observation by light microscope in order to analyze the high-temperature stability of Fe-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention.Observations as shown in figure 44.
As shown in figure 44, with under the high temperature in aluminum matrix roughen or the existing intermetallic compound that stands phase decomposition compare, the strengthening phase of being made up of Fe-Ni homogeneous sosoloid shows as the granular strengthening phase identical with the microtexture shown in Figure 42.And, owing to do not observe the roughen or the phase decomposition of strengthening phase, can think, even the Fe-Ni homogeneous sosoloid strengthening phase of Fe-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention also is stable at 300 ℃.
Figure 45 is that the optical microscopy map of the observations of the microtexture of the sample of acquisition is afterwards cast in the sample refuse that preparation in the preparation example 14 is shown again.Herein, the cast samples that obtains after the refuse be basically by will be in the preparation example 14 the sample refuse of preparation to the fusing point of aluminium, cast the sample of this processing then and obtain.
As shown in figure 45, as can be seen, even homogeneous sosoloid also not roughen or the decomposition during refuse that forms in the Fe-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention, binary alloy phase diagram just as shown in Figure 9 is desired, on the contrary, it has kept strengthening phase.And, can assert, under the situation that reclaims sharp alumite, if use above-mentioned characteristic, above-mentioned heat-resisting aluminium alloy can be used for selecting energetically and reclaiming aluminium as matrix metal effectively, and Fe and Ni reach the initial level of ecological friendly type as alloying element.
Preparation example 15
Comprise that except using comparing of Fe-Ni is 50wt.%: 50wt.%, the Fe-Ni master alloy by plasma arc melting (PAM) preparation, by preparing the sample of heat-resisting aluminium alloy with the same program described in the preparation example 4.
Figure 46 illustrates in the preparation example 15 figure according to the mean sizes of the homogeneous sosoloid of each sample of the alloying element preparation of adding.After the microstructural image by each sample of preparation in the opticmicroscope analyte preparation example 15, with the mean sizes of image analyzer homogeneous sosoloid of the alloying element of definite different content from the image of analyzing.
Results verification, if add the Fe-Ni master alloy of 0.5wt.%, the amount of the homogeneous sosoloid of formation descends, and its size is also little of about 3 μ m or following.On the other hand, when the amount of adding is 10wt.% or when above, homogeneous sosoloid be of a size of about 280 μ m or more than, therefore coarse a lot.Therefore, the content of each alloying element in adding aluminium to is under the situation of 0.5wt.% to 10wt.%, and Fe-Ni homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention can be included in the capacity homogeneous sosoloid that wherein forms, thereby represents good alloy effect.And, can prevent because the problem that roughen causes such as liquate.
[embodiment 8] Cu-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy
Preparation example 16
Except the amount of using Cu and each 1.5wt.% of Mn as the alloying element, by with preparation example 1 in the same program preparation described have the sample (calling " Cu-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy " in the following text) of the heat-resisting aluminium alloy of Cu-Mn homogeneous sosoloid strengthening phase.
Figure 47 is the optical microscopy map that the observations of the microtexture of the sample of preparation in the preparation example 16 is shown, wherein sample grinds with SiC emery paper #200, #400, #600, #800, #1000, #1500 and #2400, use 1 μ m Al2O3 powder fine grainding then, then by the observation by light microscope structures of samples.Find that from Figure 47 the heat-resisting aluminium alloy sample of preparation has the strengthening phase of the crystal interface shape of size 1 to 10 μ m in the preparation example 12.
Figure 48 is the drawing result's of sample that preparation is shown in the preparation example 16 microtexture of using EPMA a photograph.Can confirm that the crystal interface shape strengthening phase shown in Figure 47 is a Cu-Mn homogeneous sosoloid.
In addition,, the sample elder generation of preparation in the preparation example 16 was heated 200 hours at 300 ℃, follow microtexture by this heated sample of observation by light microscope in order to analyze the high-temperature stability of Cu-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention.Observations as shown in figure 49.
As shown in figure 49, with under the high temperature in aluminum matrix roughen or the existing intermetallic compound that stands phase decomposition compare, the strengthening phase of being made up of Cu-Mn homogeneous sosoloid shows as the strengthening phase of the crystal interface shape identical with the microtexture shown in Figure 47.And, owing to do not observe the roughen or the phase decomposition of strengthening phase, can think, even the Cu-Mn homogeneous sosoloid strengthening phase of Cu-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention also is stable at 300 ℃.Therefore, Cu-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy can improve the heat-resisting limit of motor car engine, improves fuel efficiency thus.
Figure 50 is the optical microscopy map that shows the microtexture observations of the sample that obtains after the sample refuse for preparing in the preparation example 16 is cast again.Herein, the cast samples that obtains after the refuse be basically by will be in the preparation example 16 the sample refuse of preparation to the fusing point of aluminium, cast the sample of this processing then and obtain.
As shown in figure 50, as can be seen, even homogeneous sosoloid also not roughen or the decomposition during refuse that forms in the Cu-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention, binary alloy phase diagram just as shown in Figure 10 is desired, on the contrary, it has kept strengthening phase.And, can assert that reclaiming under the situation of alumite, if use above-mentioned characteristic, above-mentioned heat-resisting aluminium alloy can be used for selecting energetically and reclaiming aluminium as matrix metal effectively, and Cu and Mn reach the initial level of ecological friendly type as alloying element.
Preparation example 17
Comprise Cu except using: the comparing of Mn be 50wt.%: 50wt.%, the Cu-Mn master alloy by plasma arc melting (PAM) preparation, by preparing the sample of heat-resisting aluminium alloy with the same program described in the preparation example 4.
Figure 51 illustrates the figure of preparation example 17 according to the mean sizes of the homogeneous sosoloid of each sample of the alloying element preparation of adding.After the microstructural image by each sample of preparation in the opticmicroscope analyte preparation example 17, with the mean sizes of image analyzer homogeneous sosoloid of the alloying element of definite different content from the image of analyzing.
Results verification, if add the Cu-Mn master alloy of 0.5wt.%, the amount of the homogeneous sosoloid of formation descends, and its size is also little of about 2 μ m or following.On the other hand, when the amount of adding is 10wt.% or when above, homogeneous sosoloid be of a size of about 250 μ m or more than, therefore coarse a lot.Therefore, the content of each alloying element in adding aluminium to is under the situation of 0.5wt.% to 10wt.%, and Cu-Mn homogeneous sosoloid intensified type heat-resisting aluminium alloy of the present invention can be included in the capacity homogeneous sosoloid that wherein forms, thereby represents good alloy effect.And, can prevent because the problem that roughen causes such as liquate.
Can obviously find out from foregoing, heat-resisting aluminium alloy of the present invention is characterised in that the homogeneous sosoloid strengthening phase of being made up of two types alloying element, it is with respect to do not have solvus as the aluminium of matrix metal, the homogeneous sosoloid strengthening phase of Xing Chenging simultaneously, even under 300 ℃ or higher high temperature also not with reactive aluminum, conversely, do not produce coarse or stand phase decomposition.Therefore, can significantly improve thermotolerance.And, when reclaiming used alloying element and aluminium, can screen, but therefore be used for to environmental friendliness various field based on their fusing point or the difference of proportion after the refuse.Because the restriction of alumite, although aluminium can not use under 200 ℃ or higher temperature in some fields, for example automobile, diesel motor, aircraft parts etc., but the present invention also can be applicable to above-mentioned field, particularly, improve the stable on heating limit of existing motor car engine, thereby improved fuel efficiency.
And, can use the homogeneous sosoloid strengthening phase of the alloying element formation of appropriate amount to prevent their roughening or liquate.
Be used to explain though the present invention discloses preferred implementation, yet one with ordinary skill in the art would appreciate that under the prerequisite of the scope and spirit that do not deviate from the appended claim of the present invention that various distortion, interpolation and replacement can be arranged.

Claims (29)

1. a heat-resisting aluminium alloy comprises aluminium and two kinds of alloying elements, and described alloying element forms homogeneous sosoloid and combines to form homogeneous sosoloid strengthening phase.
2. heat-resisting aluminium alloy as claimed in claim 1, wherein said alloying element are in being included in the amount with respect to aluminium 0.5-10wt.%.
3. heat-resisting aluminium alloy as claimed in claim 2, a kind of alloying element of wherein said two kinds of alloying elements are in the amount with 10-90wt.% is included in, and another kind of alloying element is a amount with 90-10wt.% be included in.
4. heat-resisting aluminium alloy as claimed in claim 3, wherein said two kinds of alloying elements are chromium (Cr) and tungsten (W).
5. heat-resisting aluminium alloy as claimed in claim 4, wherein under the situation that homogeneous sosoloid strengthening phase is made up of Cr and W, it keeps stable single phase under up to 1800 ℃ temperature, and has the size of 1-200 μ m.
6. heat-resisting aluminium alloy as claimed in claim 3, wherein said two kinds of alloying elements are copper (Cu) and nickel (Ni).
7. heat-resisting aluminium alloy as claimed in claim 6, wherein under the situation that homogeneous sosoloid strengthening phase is made up of Cu and Ni, it keeps stable under up to 873 ℃ temperature, and has the crystal interface shape of size 1-50 μ m.
8. heat-resisting aluminium alloy as claimed in claim 3, wherein said two kinds of alloying elements are iron (Fe) and chromium (Cr).
9. heat-resisting aluminium alloy as claimed in claim 8, wherein under the situation that homogeneous sosoloid strengthening phase is made up of Fe and Cr, it keeps stable single phase under up to 1500 ℃ temperature, and has the small flat surface shape of size 1-60 μ m.
10. heat-resisting aluminium alloy as claimed in claim 3, wherein said two kinds of alloying elements are iron (Fe) and manganese (Mn).
11. heat-resisting aluminium alloy as claimed in claim 10 wherein has thermotolerance at homogeneous sosoloid strengthening phase under up to 1245 ℃ temperature, and forms the small flat surface shape with size 1-50 μ m.
12. heat-resisting aluminium alloy as claimed in claim 3, wherein said two kinds of alloying elements are manganese (Mn) and vanadium (V).
13. heat-resisting aluminium alloy as claimed in claim 12, wherein homogeneous sosoloid strengthening phase keeps stable single phase under up to 1245 ℃ temperature, and has the small flat surface shape of size 1-100 μ m.
14. heat-resisting aluminium alloy as claimed in claim 3, wherein said two kinds of alloying elements are cobalt (Co) and nickel (Ni).
15. heat-resisting aluminium alloy as claimed in claim 14, wherein homogeneous sosoloid strengthening phase has thermotolerance under up to 1490 ℃ temperature, and forms the needle-like shape with size 1-70 μ m.
16. heat-resisting aluminium alloy as claimed in claim 3, wherein said two kinds of alloying elements are iron (Fe) and nickel (Ni).
17. heat-resisting aluminium alloy as claimed in claim 16, wherein homogeneous sosoloid strengthening phase keeps stable single phase under up to 1245 ℃ temperature, and has the particle shape of size 1-30 μ m.
18. heat-resisting aluminium alloy as claimed in claim 3, wherein said two kinds of alloying elements are copper (Cu) and manganese (Mn).
19. heat-resisting aluminium alloy as claimed in claim 18, wherein homogeneous sosoloid strengthening phase keeps stable single phase under up to 873 ℃ temperature, and has the size of 1-10 μ m.
20. a method of making heat-resisting aluminium alloy comprises: multiple alloying element is added in the aluminium melts of being made up of molten aluminum; And after being fused, casts described alloying element this metal.
21. method as claimed in claim 20, wherein said alloying element are Cr and W, it directly adds in the melts, perhaps adds as the Cr-W master alloy, perhaps adds in the melts as Al-Cr master alloy and Al-W master alloy.
22. method as claimed in claim 20, wherein said alloying element are Cu and Ni, it directly adds in the melts, perhaps adds as the Cu-Ni master alloy, perhaps adds in the melts as Al-Cu master alloy and Al-Ni master alloy.
23. method as claimed in claim 20, wherein said alloying element are Fe and Cr, it directly adds in the melts, perhaps adds as the Fe-Cr master alloy, perhaps adds in the melts as Al-Fe master alloy and Al-Cr master alloy.
24. method as claimed in claim 20, wherein said alloying element are Fe and Mn, it directly adds in the melts, perhaps adds as the Fe-Mn master alloy, perhaps adds in the melts as Al-Fe master alloy and Al-Mn master alloy.
25. method as claimed in claim 20, wherein said alloying element are Mn and V, it directly adds in the melts, perhaps adds as the Mn-V master alloy, perhaps adds in the melts as Al-Mn master alloy and Al-V master alloy.
26. method as claimed in claim 20, wherein said alloying element are Co and Ni, it directly adds in the melts, perhaps adds as the Co-Ni master alloy, perhaps adds in the melts as Al-Co master alloy and Al-Ni master alloy.
27. method as claimed in claim 20, wherein said alloying element are Fe and Ni, it directly adds in the melts, perhaps adds as the Fe-Ni master alloy, perhaps adds in the melts as Al-Fe master alloy and Al-Ni master alloy.
28. method as claimed in claim 20, wherein said alloying element are Cu and Mn, it directly adds in the melts, perhaps adds as the Cu-Mn master alloy, perhaps adds in the melts as Al-Cu master alloy and Al-Mn master alloy.
29. as each described method in the claim 20 to 28, wherein said alloying element is to add with the amount with respect to the 0.5-10wt.% of aluminium.
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KR1020090006694A KR101254569B1 (en) 2009-01-28 2009-01-28 Fe-Mn solid solution strengthened high temperature aluminum alloys and Manufacturing Method Thereof
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KR1020090006688A KR101164898B1 (en) 2009-01-28 2009-01-28 Cr-W solid solution strengthened high temperature aluminum alloys and Manufacturing Method Thereof
KR1020090006689A KR20100087583A (en) 2009-01-28 2009-01-28 Cu-mn solid solution strengthened high temperature aluminum alloys and manufacturing method thereof
KR1020090006693A KR101205792B1 (en) 2009-01-28 2009-01-28 Mn-V solid solution strengthened high temperature aluminum alloys and Manufacturing Method Thereof
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