CN103502494A - Mg-al-ca-based master alloy for mg alloys, and a production method therefor - Google Patents
Mg-al-ca-based master alloy for mg alloys, and a production method therefor Download PDFInfo
- Publication number
- CN103502494A CN103502494A CN201280021220.1A CN201280021220A CN103502494A CN 103502494 A CN103502494 A CN 103502494A CN 201280021220 A CN201280021220 A CN 201280021220A CN 103502494 A CN103502494 A CN 103502494A
- Authority
- CN
- China
- Prior art keywords
- alloy
- melting
- ratio
- mother alloy
- weight percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
Abstract
The present invention relates to an Mg-Al-Ca-based master alloy for Mg alloys and to a production method therefor, and concerns an alloying master alloy used for magnesium or magnesium alloys. To this end, a feature of the invention is that, while the Ca:Al ratio in the composition is maintained at between 7:3 and 1:9, based on percentages by weight in the alloy, a balance of Mg is added in an amount of up to 85% of the entire weight of the master alloy, based on percentage by weight. The production method comprises the steps of: preparing the components of the master alloy by selecting a composition in which, while the Ca:Al ratio in the composition is maintained at between 7:3 and 1:9, based on percentages by weight in the alloy, there is a balance of Mg in an amount of up to 85% of the entire weight of the master alloy, based on percentage by weight; sequentially melting Mg, Al and Ca; completely melting the above constituents by applying an adequate amount of heat; and rapidly cooling the molten pool.
Description
Technical field
The present invention relates to Mg-Al-Ca base mother alloy and manufacture method thereof for the Mg alloy.
Background technology
The density of Mg alloy is about 1.8g/cm
3, this is the minimum density level of commercially available up to now various alloys, and demonstrates higher specific tenacity and Young's modulus.Especially, the Mg alloy has excellent vibration or shock absorption ability, conduction and thermal conductivity, workability, fatigue strength at high temperature, impact property etc.Particularly, the Mg alloy has the various favourable character met in many fields lightweight requirement, and these fields comprise transportation equipment (as automobile, aircraft etc.), for the equipment of national defense industry, universal machine etc.
One of the most favourable advantage of Mg alloy is lightweight.At present the weight/power ratio scope of commercially available Mg alloy is 1.79 to 1.81, and it is lighter by approximately 35% or lighter than Al alloy, and demonstrates excellent mechanical property.That is to say, although the Mg alloy is compared with Al alloy or plastic material being similar to Al or stainless steel aspect Young's modulus and density, it demonstrates the effect that significantly reduces weight.
In the lower melting of relatively low temperature (temperature range is 650 ℃ to 680 ℃), although because the kind of used alloying element makes melt temperature slightly different, only consume a small amount of energy due to the Mg alloy when reclaiming the Mg alloy.Especially, can be only to manufacture first 1/4th energy recovery Mg alloy of Mg alloy pig institute energy requirement, thereby demonstrate very high energy-saving effect.The Mg alloy reclaimed from the situ production process can be melted to reclaim, and removes afterwards impurity reduction components, and the Mg alloy of recovery can be repeated with the new essentially identical state of Mg alloy to utilize.In addition, the molded life-span of Mg alloy is grown to few twice than the Al alloy, and its manufacturability is also high than Al alloy.Therefore, can reduce the required manufacturing cost of each single part.
If add a group element in the manufacture of alloy, they may not be properly mixed.Therefore, for the amount with unified adds the alloying element used, common situation is, the alloy that contains relatively large institute addition element is as alloy stream (flux) preparation separately, and will a small amount of alloy stream join as after in the molten metal of mother metal use of the desired alloy that is diluted.Herein, the alloy that contains a large amount of institutes addition element is called as mother alloy (master alloy).This mother alloy is also referred to as master alloy.
When being used as the alloying element of Mg, Al has best effect.The intensity that the adding of Al makes the Mg alloy and hardness increase, and improved the mobility in the castingprocesses and solidification range increased, thereby having improved castability.When with 6wt% or amount still less, adding Al, it can change the sosoloid in the Mg matrix into.On the other hand, when the amount with higher than 6wt% adds Al, it can be because thermal treatment precipitation occurs and solidifies.Usually, in the alloy of most commercial, the content of Al is 10wt% or still less, wherein from intensity and unit elongation aspect, opens, and the Al alloy has excellent physical properties.Yet, when Al and Mg react, can form Mg
17al
12phase, thus creep resistance at high temperature reduced.
Ca makes hot strength and the creep resistance of Mg-Al base Mg alloy significantly improve.In solidification process, in the Mg alloy that contains Al, add trace (<0.5%) calcium to form Al
2the Ca intermetallic compound, it is at high temperature stable, thereby has increased intensity and thermotolerance.In addition, Ca prevents that alloy from being also known at the effective element of casting or during Heat Treatment generation oxidation.And Ca can play the effect that makes crystalline particle form microstructure.Yet Ca can reduce the mobility of molten metal, thereby make the castability variation, hot tearing easily occurs, and make the viscosity with respect to mould during die casting increase, thereby finally reduce manufacturability.If add Ca with 0.3wt% or higher amount, at weld period, there will be crackle.
When conventional Ca alloying element directly being put into to Mg or Mg alloy with for the manufacture of the Mg alloy time, there is the sosoloid of a certain amount of Ca in the Mg alloy, so that conventional Ca alloying element changes the sosoloid in the Mg alloy substrate into, rather than form phase in the Mg alloy substrate.In addition, when in the Mg molten metal, adding conventional Ca alloying element, it is highly brittle, and adds the productive rate of Ca not high, but can form the oxide compound derived from Ca.For example, when the amount of 1.3wt% or higher (being 0.8wt% under nonequilibrium state) of take adds Ca, Ca can further not be dissolved in the Mg matrix, and forms intermetallic compound.The conventional example of intermetallic compound that affects the physical properties of Mg or other alloying elements comprises Al
2ca.
Summary of the invention
Technical problem
In order to overcome above-mentioned shortcoming, the invention provides a kind of novel Mg-Al-Ca base mother alloy for the Mg alloy and preparation method thereof, it is different from the alloy in order to form Mg or Mg alloy or conventional mother alloy and the alloying element that adds.With conventional Mg alloy phase ratio, utilize and show excellent physical properties according to the Mg alloy of mother alloy manufacture of the present invention.In the present invention, when the Ca:Al ratio of components remains on the weight percent of 7:3 to 1:9(based on alloy) between the time, the amount up to 85% that can the mother alloy gross weight adds the Mg(of surplus based on weight percent).
Purpose of the present invention is not limited to above-mentioned purpose, those of ordinary skills according to the following description of preferred implementation can understand above other purposes of not describing.
Technical scheme
According to an aspect of the present invention, Mg-Al-Ca base mother alloy for the Mg alloy is provided, wherein remain on the weight percent of 7:3 to 1:9(based on alloy when the Ca:Al ratio of components) between the time, the amount up to 85% that can the mother alloy gross weight adds the Mg(of surplus based on weight percent).
Particularly, the Ca:Al ratio of components can be remained between 6:4 to 2:8, based on weight percent.
Contained Al content can be 15% or higher (based on weight percent) of Mg-Al-Ca base mother alloy gross weight.
When the Ca:Al ratio of components remains on 4.3:5.7, the content of Mg can be for the 65%(of mother alloy gross weight based on weight percent).
According to an aspect of the present invention, manufacture method for the Mg-Al-Ca base mother alloy of Mg alloy is provided, this manufacture method comprises by selecting wherein to remain on the weight percent of 7:3 to 1:9(based on alloy when the Ca:Al ratio of components) between the time surplus the Mg composition up to 85% amount (based on weight percent) that is the mother alloy gross weight prepare the component of mother alloy, melting Mg, Al and Ca afterwards, make the complete melting of component by the heat that applies q.s, and solidify this molten metal.
Solidifying of molten metal can comprise cooling this molten metal fast.
The Ca:Al ratio of components can be remained between 6:4 to 2:8, based on weight percent.
The content of contained Al can for Mg-Al-Ca base mother alloy gross weight 15% or higher, based on weight percent.
In melting, can be at first by the Mg melting, then by the Al melting, finally by the Ca melting.
In melting, can be at first by the Al melting, then by the Mg melting, finally by the Ca melting.
In melting, can be by Mg melting together with Al, then by the Ca melting.
In melting, can be by Mg melting together with Ca, then by the Al melting.
Beneficial effect
As described above, the component of the alloying element by the commercially available Mg alloy of the production by added is controlled in compositing range so that form Al
2the Ca phase, mother alloy according to the present invention is used to manufacture the Mg alloy with excellent physical properties.That is to say, keep the Al formed by mother alloy in final Mg alloy
2the Ca phase, thus make the Mg alloy there is microstructure and the yield strength of Mg alloy and tensile strength are increased.In addition, suppressed heat-labile β-Mg
17al
12the formation of phase, and can significantly reduce casting flaw.
The accompanying drawing explanation
The calculating phasor that Fig. 1 is the Al-Ca binary alloy;
The calculating phasor that Fig. 2 is the Mg-Al binary alloy;
The calculating phasor that Fig. 3 is the Mg-Ca binary alloy;
Fig. 4 is the diagram that shows the compositing range according to one embodiment of the present invention (zone 1) on the liquid projection view of the Mg-Al-Ca ternary phase diagrams meaned with weight ratio; And
Fig. 5 is the diagram that shows the compositing range according to another embodiment of the present invention (zone 2) on the liquid projection view of the Mg-Al-Ca ternary phase diagrams meaned with weight ratio.
Embodiment
Below with reference to accompanying drawing, the preferred embodiment of the present invention is described in further detail.In the situation that each is possible, in specification sheets and accompanying drawing, similar label is used in reference to same or analogous element/element of generation.And subject matter of the present invention is hard to understand for fear of making, omitted known function and structure.
The invention provides a kind of Mg-Al-Ca base mother alloy and manufacture method thereof, this mother alloy is different from and joins conventional alloying element or the conventional mother alloy that is used to form alloy in Mg or Mg alloy, to attempt utilizing mother alloy according to the present invention to develop the Mg alloy that the conventional Mg alloy of a kind of ratio has better physical properties.
When conventional Ca alloying element directly being put in Mg or Mg alloy with for the manufacture of the Mg alloy time, the sosoloid of a certain amount of Ca appears in the Mg alloy, so that this routine Ca alloying element changes the sosoloid in the Mg alloy substrate into, rather than form phase in the Mg alloy substrate.In addition, in the time of in the Mg molten metal that conventional Ca alloying element is joined to be highly brittle (or frangible), along with Ca add productive rate not high, and can produce the oxide compound derivative from Ca.For example, when take 1.3wt% or higher amount (being 0.8wt%) while adding Ca under nonequilibrium state, Ca can further not dissolve in the Mg matrix, and can form intermetallic compound.The common example that affects the intermetallic compound (intermetallic compound) of the physical properties of Mg or other alloying elements comprises Al
2ca.
In the present invention, utilizing mother alloy input (or input) alloying element is to realize by such input, and described input comprises that the prepared Mg-Al-Ca mother alloy of input is so that Al
2ca is formed at Mg or Mg alloy mutually.Therefore, the conventional Mg alloy that the Mg alloy ratio obtained obtains by the alloying element that adds same composition has better physical properties.Herein, in order to obtain the composition of expectation, except mother alloy, can also add Ca or Al.
The calculating phasor that Fig. 1 is the Al-Ca binary alloy.Can confirm to form intermetallic compound in different compositing ranges.The example of intermetallic compound can comprise Al
4ca, Al
2ca, Al
14ca
13and Al
3ca
8.Particularly, Al
2ca has quite high fusing point.Should be appreciated that, observe in the present invention Al for the purpose of improving physical properties
2ca is a kind of dystectic intermetallic compound that has.The method of calculating and obtain phasor is that correlative technology field is known.Especially, commercially available program, for example the CALPHAD method also can be used in and calculate and obtain in phasor.
The calculating phasor that Fig. 2 is the Mg-Al binary alloy.As shown in Figure 2, Mg or Al all have high solid solubility with respect to each relative element.When Mg and Al being mixed and during melting, its melting point depression.
The calculating phasor that Fig. 3 is the Mg-Ca binary alloy.Mg
2ca exists as the intermetallic compound between the Mg-Ca binary alloy.Mg
2the fusing point of Ca is between the fusing point of pure Mg and pure Ca.That is to say Mg
2the fusing point of Ca is higher than the fusing point of pure Mg, but lower than the fusing point of pure Ca.
The liquid projection view that Fig. 4 and Fig. 5 are the Mg-Al-Ca ternary phase diagrams that means with weight ratio.In Fig. 4 and Fig. 5, illustrate according to the present invention and the compositing range of the mother alloy of illustrative embodiments exploitation.In this ternary phase diagrams, the mark that vertex of a triangle is illustrated in the component Mg of this some place, Ca and Al is respectively 100%, and leg-of-mutton limit means the binary system of two kinds of components on each limit.
As shown in Figure 4 and Figure 5, along with temperature reduces, Al
2ca is present in wider compositing range.Comparatively speaking, along with temperature reduces, Al
4ca, Al
14ca
13, Mg
2ca and Al
3ca
8be present in narrower compositing range.In institute's drawings attached (Fig. 1 to Fig. 5), can be simply by the temperature value from meaning with Fahrenheit temperature (K) deduct 273 calculate centigradetemperature (℃).
The mother alloy of the base of the Mg-Al-Ca for the Mg alloy of producing in the present invention has kept the Ca:Al ratio of components between 7:3 to 1:9, based on weight percent.
As shown in Figure 4, along line 1. the line that the Ca:Al ratio of components is 7:3 keeps, and along line 2. the line that the Ca:Al ratio of components is 1:9 keeps.In the present invention, the implication of statement " keep Ca:Al ratio of components between 7:3 to 1:9, based on weight percent " be under 1. the scope of this mother alloy component is confirmed as online and line 2. on.In addition, according to the present invention, when Ca:Al ratio of components (based on weight percent) is maintained between 7:3 to 1:9, further add the Mg(up to 85% amount based on the mother alloy gross weight based on weight percent), on 3. it be confirmed as online.
In the present invention, the composition of mother alloy is determined to be in by line 1., 2. and 3. in definite zone (being meaned by zone 1).That is to say, 1., 2. and 3. this mother alloy is being produced in the compositing range in definite zone 1 by line.
More preferably, the Ca:Al ratio of components is remained between 6:4 to 2:8, this compositing range by line 4., 5. and 3. form, as shown in Figure 5.That is to say, in the situation that the Ca:Al ratio of components remains between 6:4 to 2:8, the composition of mother alloy is defined in by line 4., 5. and 3. in definite scope.
In the Ca:Al ratio of components, due to following reason, than 7:3, more preferably 6:4.That is to say, when compositing range from by Mg
2ca, Al
14ca
13and Al
2the definite zone of Ca is towards Al
2when Ca moves, guarantee to form Al more surely
2ca.That is to say, due at Mg
2ca, Al
14ca
13and Al
2there is the 7:3 ratio of components around boundary line between Ca, thereby also have formation Mg
2ca and Al
14ca
13, rather than Al
2the possibility of Ca.Yet the 6:4 ratio of components can make confirms to form Al more surely
2ca.
In the Ca:Al ratio of components, due to following reason, than 1:9, more preferably 2:8.That is to say, when compositing range from by Al
2ca and Al
4the definite zone of Ca is towards Al
2when Ca moves, guarantee to form Al more surely
2ca.That is to say, due at Al
2ca and Al
4there is the 1:9 ratio of components around boundary line between Ca, thereby also have formation Al
4ca, rather than Al
2the possibility of Ca.Yet the 2:8 ratio of components can make confirms to form Al more surely
2ca.
In addition, the invention is characterized in, based on weight percent, contained Al content be Mg-Al-Ca base mother alloy gross weight 15% or higher.If Al content is less than 15%, formed Al
2the amount of Ca reduces.In this case, as the Al of mother alloy
2it is unimportant that the effect of Ca can become.
According to the manufacture method of the base of the Mg-Al-Ca for the Mg alloy mother alloy of one embodiment of the present invention, comprise by selecting such composition to prepare the component of mother alloy, wherein when the Ca:Al ratio of components remains between 7:3 to 1:9 based on weight percent, exist the mother alloy gross weight up to 85%(based on weight percent) the Mg of surplus of amount, melting Mg, Al and Ca subsequently, make the complete melting of component by the heat that applies q.s, and the metal that solidifies this melting.Preferably, in the solidifying of molten metal, can this molten metal is cooling fast.Herein, rapidly cooling referring to forced coolingly, and it is faster than the spontaneous curing in general casting technique.Force cooling comprise water cooling (comprising brine quenching) or by blow air quench carry out cooling fast.
Herein, select to be defined in the scope in the zone 1 shown in Fig. 4 for the manufacture of the composition of Mg-Al-C base mother alloy.Reason has briefly been described above.That is to say, by liquidus line temperature is increased to higher than zone 1 corresponding composition, make the complete melting of alloy compositions, then that the metal of melting is cooling fast, thus farthest produce the desired Al of mother alloy of the present invention
2ca.
More preferably, the Ca:Al ratio of components can be remained between 6:4 to 2:8, based on weight percent.Selection for the manufacture of the composition of Mg-Al-Ca base mother alloy be determined to be in shown in Fig. 5 by line 4., 5. and 3. in the scope in definite zone 2.As described above, in the Ca:Al ratio of components, than 7:3, more preferably 6:4 because when compositing range from by Mg
2ca, Al
14ca
13and Al
2the definite zone of Ca is towards Al
2when Ca moves, guarantee to form Al more surely
2ca.In other words, due at Mg
2ca, Al
14ca
13and Al
2there is the 7:3 ratio of components around boundary line between Ca, thereby also have formation Mg
2ca and Al
14ca
13, rather than Al
2the possibility of Ca.Yet the 6:4 ratio of components can make confirms to form Al more surely
2ca.
In the Ca:Al ratio of components, due to following reason, than 1:9, more preferably 2:8.That is to say, when compositing range from by Al
2ca and Al
4the definite zone of Ca is towards Al
2when Ca moves, guarantee to form Al more surely
2ca.That is to say, due at Al
2ca and Al
4there is the 1:9 ratio of components around boundary line between Ca, thereby also have formation Al
4ca, rather than Al
2the possibility of Ca.Yet the 2:8 ratio of components can make confirms to form Al more surely
2ca.More preferably, when the Ca:Al ratio of components remains on 4.3:5.7, the amount of contained Mg is 65% of mother alloy gross weight, based on weight percent.When the Ca:Al ratio of components is 4.3:5.7(wt%) time, remain on 1:2 by the mol ratio by Ca:Al and can expect maximum Al
2ca forms mutually.As Fig. 5 (Al
2the Ca line) confirm in, when the amount of the Mg contained is 65% or still less the time, can guarantee to form Al more surely
2the Ca phase.
As shown in Figure 5, at Al
2on the Ca line, Al and Ca keep Al
2the Ca ratio of components.By ratio of components is being remained on to Al
2in the time of on the Ca line, add Mg to form the Al of desired quantity
2ca.In this case, more preferably the amount up to (up to) 65% with the mother alloy gross weight adds Mg, based on weight percent.
the melting method of each component
For the preparation of each component formed according to Mg-Al-Ca base mother alloy of the present invention, subsequently by Mg, Al and Ca melting one by one.For example, by the heat that applies q.s, carry out melting Mg, then melting Al, finally melting Ca.
Herein, melting also can be with from Mg to Al and to Ca, Al to Ca to Mg, or Ca to Mg carrying out to the order of Al.As shown in Figure 1, Figure 2 and Figure 3, when during melting, producing intermetallic compound, due to the high-melting-point of produced intermetallic compound, only can produce this molten metal by applying much more heat, this is disadvantageous.Therefore, when each component of melting, do not wish from starting just by Al melting together with Ca is formed to Al
2ca.Therefore, the order melting with Al-Ca-Mg or Ca-Al-Mg is least desirable method.
Different from above-mentioned melting order, can be by Mg melting together with Al, maybe can be by Ca melting together with Mg, and all the other alloying elements of melting subsequently (Ca or Al).As described above, formed immediately Al in order to prevent before forming mother alloy
2the Ca intermetallic compound, melting Al and Ca are the most unaccommodated simultaneously.With Fig. 3, confirm as shown in Figure 1, Figure 2, except the situation of Al and Ca, for the situation of Al and Mg and Ca and Mg, with melted pure metallographic phase ratio, when two kinds of metals of while melting, melting point depression.Certainly, for the situation of Ca-Mg binary system, when two kinds of metals of while melting, with the Ca of melted pure or the situation of Mg, compare, fusing point descends and increases after passing through eutectic point in the definite composition scope.Yet, also can confirm to form intermetallic compound Mg
2the temperature of Ca is lower than the melt temperature of Ca.
Herein, also can while melting three kinds of component Mg, Al and Ca.In in shielding gas atmosphere, three kinds of component Mg, Al and Ca being put into to crucible and while applying q.s hot, they are melting in crucible, thereby is formed for forming the molten metal of Mg-Al-Ca base mother alloy.In the situation that, because Mg or Ca composition catch fire (burning), can in shielding gas atmosphere, implement melting.
Manufacture
the melt temperature of mother alloy
In the present invention, the melt temperature that forms molten metal and solid metallic be enough to melting for after the temperature of desirable liquid phase of existence equally high.Yet, consider molten metal temperature can along with after drop into adding of component and reduce, be necessary molten metal is remained in the temperature range in having enough allowances.In metallography, common situation is the progress melting point depression according to alloying.
If melt temperature excessively raises, the evaporation of liquid metal can occur, and Mg or Ca cause losing a certain amount of molten metal because its character can easily be evaporated, thereby due to the oxide compound of burning, final physical character is caused to disadvantageous effect.
In order to form the molten metal of mother alloy, preferably stir this molten metal.Can produce electric field by the device that be provided for applying electromagnetic field around the smelting furnace containing this molten metal, thereby cause that the convection current of molten metal implements to stir.Alternately, can implement mechanical stirring to molten metal from outside.
In following table 1, the composition in the compositing range with zone 1 or 2 has confirmed to form Al in mother alloy after producing mother alloy
2ca.In order to make the Al in liquid phase
2ca is present in solid phase, preferably by cooling enforcement casting on molten metal fast.Implementing cooling fast is because can not determine that cooling meeting makes liquid phase Al
2which phase Ca can be converted into.That is to say, implementing cooling purpose fast is to keep the at high temperature Al in liquid phase
2ca exists as much as possible immediately at room temperature in solid phase.
Fig. 4 shows the composition a to j listed in following table 1.
Table 1
| Form | Mg?wt% | Al?wt% | Ca?wt% | Al 2Ca forms |
| a | 10 | 30 | 60 | Confirm |
| b | 10 | 50 | 40 | Confirm |
| c | 20 | 45 | 35 | Confirm |
| d | 30 | 35 | 35 | Confirm |
| e | 30 | 60 | 10 | Confirm |
| f | 40 | 24 | 36 | Confirm |
| g | 40 | 40 | 20 | Confirm |
| h | 50 | 18 | 32 | Confirm |
| i | 60 | 18 | 22 | Confirm |
| j | 70 | 20 | 10 | Confirm |
According to melting method of the present invention, the component of each alloy shown in melting table 1 at sufficiently high temperature.In table 1, by X-ray diffraction, confirm Al
2the existence of Ca.Herein, do not measure Al
2the content of Ca.
Table 2 shows the yield strength that mother alloy by being produced by the present invention according to ratio of components is put into the final Mg alloy obtained in Mg or Mg alloy.Table 3 shows the measuring result of yield strength of Mg alloy that has the comparative example of same composition ratio with embodiments of the invention, wherein in comparative example by Al and/or Ca are directly joined in final Mg alloy, rather than the mother alloy that adds the present invention to produce.Shown in table 2 for the numeral that identifies each embodiment corresponding to shown in table 3 for identifying the numeral of each comparative example.When utilization has the Al formed in the present invention
2when the mother alloy of Ca produces the Mg alloy, this Mg alloy shows than having the general Mg alloy higher yield strength of same composition than (composition ratios).
Aforesaid reason may be owing in the final mother alloy produced of the present invention, comprising a large amount of Al as intermetallic compound
2ca.Therefore, the physical properties of Mg alloy is improved.
In addition, confirmed by adding the mother alloy that the present invention produces to make the Mg alloy by micro-structural.And, confirmed except Al
2mg outside Ca
2ca or (Mg, Al)
2ca also is distributed in the Mg alloy substrate mutually.
Table 2
| Embodiment | Ratio of components (wt%) | Yield strength [MPa] |
| 1 | Mg-4Al-0.5Ca | 127 |
| 2 | Mg-5Al-0.5Ca | 139 |
| 3 | Mg-6Al-0.5Ca | 151 |
| 4 | Mg-4Al-1.0Ca | 135 |
| 5 | Mg-5Al-1.0Ca | 149 |
| 6 | Mg-6Al-1.0Ca | 158 |
Notice, the ratio of components of listing in table 2 and table 3 has been indicated the composition that utilizes the final Mg alloy produced according to mother alloy of the present invention.
Table 3
| Comparative example | Ratio of components (wt%) | Yield strength [MPa] |
| 1 | Mg-4Al-0.5Ca | 109 |
| 2 | Mg-5Al-0.5Ca | 115 |
| 3 | Mg-6Al-0.5Ca | 126 |
| 4 | Mg-4Al-1.0Ca | 112 |
| 5 | Mg-5Al-1.0Ca | 128 |
| 6 | Mg-6Al-1.0Ca | 135 |
Following table 4 shows by 10Mg-50Al-40Ca is added in Mg as the mother alloy (wt%) of invention, and directly joins in Mg or Mg alloy the comparative result of Ca productive rate while producing Mg-5Al-2Ca using Ca as alloying element.In addition, when in case of necessity, further add Al to be adjusted to Mg-5Al-2Ca finally forming.Herein, productive rate means to be used in the per-cent (percentile) of the amount of the Ca of final alloying in the Mg alloy divided by total Ca input amount acquisition.
As following table 4 confirms, when the Ca that adds by mother alloy as alloying element, the situation that the rate of recovery of Ca will directly add as alloying element higher than Ca.Aforesaid reason is can not carry out well alloying when directly adding Ca.
Table 4
| ? | Ratio of components (wt%) | Add the productive rate after Ca |
| Embodiment | Add the 10Mg-50Al-40Ca mother alloy | 95% |
| Comparative example | Directly add Ca | 72% |
As described above, can confirm that the mother alloy by adding the present invention to produce can make the Mg alloy microstructure, wherein add in the present invention mother alloy and Mg
2ca, Al
2ca or (Mg, Al)
2ca is evenly distributed in the Mg alloy mutually.In addition, can suppress heat-labile β-Mg
17al
12the formation of phase, and can significantly reduce casting flaw.Therefore, the tensile strength of the increase of the yield strength of Mg alloy and Mg alloy also increases.
The Mg-Al-Ca base mother alloy that can produce according to the present invention joins in the material in the choosing group that freely pure Mg, Mg alloy and equivalent thereof form as alloying means (alloying means).In addition, the available example of Mg alloy can comprise AZ91D, AM20, AM30, AM50, AM60, AZ31, AS41, AS31, AS21X, AE42, AE44, AX51, AX52, AJ50X, AJ52X, AJ62X, MRI153, MRI230, AM-HP2, Mg-Al, Mg-Al-Re, Mg-Al-Sn, Mg-Zn-Sn, Mg-Si and Mg-Zn-Y, but aspect of the present invention is not limited to this.Can use industrial normally used any Mg alloy.
Although above described illustrative embodiments of the present invention in detail, but should be appreciated that, many variations of basic inventive concept as herein described and modification are apparent for those skilled in the art, and be also included within the spirit and scope of illustrative embodiments of the present invention, the spirit and scope of the present invention are defined by the following claims.
Claims (12)
1. the base of the Mg-Al-Ca for a Mg alloy mother alloy, wherein, when the weight percent of Ca:Al ratio of components based in described alloy remains between 7:3 to 1:9, add the Mg of surplus with the amount up to 85% of described mother alloy gross weight based on weight percent.
2. Mg-Al-Ca base mother alloy according to claim 1, wherein, described Ca:Al ratio of components remains between 6:4 to 2:8 based on weight percent.
3. Mg-Al-Ca base mother alloy according to claim 1 and 2, wherein, the gross weight that contained Al content is described Mg-Al-Ca base mother alloy 15% or higher, based on weight percent.
4. Mg-Al-Ca base mother alloy according to claim 1 and 2, wherein, when the Ca:Al ratio of components remains on 4.3:5.7, the amount of contained Mg is 65% of described mother alloy gross weight, based on weight percent.
5. the manufacture method of the base of the Mg-Al-Ca for a Mg alloy mother alloy, described manufacture method comprises:
, wherein when the weight percent of Ca:Al ratio of components based in described alloy remains between 7:3 to 1:9, there is the Mg of the surplus up to 85% amount of described mother alloy gross weight in the component that forms to prepare mother alloy by selection, based on weight percent;
Order melting Mg, Al and Ca;
Make the complete melting of described component by the heat that applies q.s; And
Solidify described molten metal.
6. manufacture method according to claim 5, wherein, the curing cooling described molten metal fast that comprises of described molten metal.
7. according to the described manufacture method of claim 5 or 6, wherein, described Ca:Al ratio of components remains between 6:4 to 2:8 based on weight percent.
8. according to the described manufacture method of claim 5 or 6, wherein, the gross weight that contained Al content is described Mg-Al-Ca base mother alloy 15% or higher, based on weight percent.
9. according to the described manufacture method of claim 5 or 6, wherein, in melting, melting Mg at first, melting Al then, last melting Ca.
10. according to the described manufacture method of claim 5 or 6, wherein, in melting, melting Al at first, melting Mg then, last melting Ca.
11., according to the described manufacture method of claim 5 or 6, wherein, in melting, Mg is melting together with Al, then melting Ca.
12., according to the described manufacture method of claim 5 or 6, wherein, in melting, Mg is melting together with Ca, then melting Al.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110028939A KR101385685B1 (en) | 2011-03-30 | 2011-03-30 | Mg-Al-Ca MASTER ALLOYS FOR Mg ALLOYS AND MANUFACTURING METHOD THEREOF |
| KR10-2011-0028939 | 2011-03-30 | ||
| PCT/KR2012/002426 WO2012134243A2 (en) | 2011-03-30 | 2012-03-30 | Mg-al-ca-based master alloy for mg alloys, and a production method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103502494A true CN103502494A (en) | 2014-01-08 |
| CN103502494B CN103502494B (en) | 2017-05-31 |
Family
ID=46932185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280021220.1A Active CN103502494B (en) | 2011-03-30 | 2012-03-30 | For the Mg Al Ca bases foundry alloys and its manufacture method of Mg alloys |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20140010702A1 (en) |
| EP (1) | EP2692883B1 (en) |
| KR (1) | KR101385685B1 (en) |
| CN (1) | CN103502494B (en) |
| WO (1) | WO2012134243A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245593A (en) * | 2017-06-26 | 2017-10-13 | 重庆文理学院 | Magnesium intermediate alloy grain refiner and its preparation method and application |
| CN111155011A (en) * | 2020-02-21 | 2020-05-15 | 江苏理工学院 | High-performance Mg-Al-Ca magnesium alloy and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE202014001801U1 (en) | 2014-02-26 | 2015-05-27 | Liebherr-Components Biberach Gmbh | crane |
| JP6596236B2 (en) * | 2015-05-27 | 2019-10-23 | 本田技研工業株式会社 | Heat-resistant magnesium alloy and method for producing the same |
| KR101961468B1 (en) * | 2017-09-29 | 2019-04-15 | (주)한국주조산업 | Al-Mg-Ca MASTER ALLOY FOR ALUMINUM ALLOY AND MANUFACTURING METHOD THEREOF |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269609A (en) * | 1995-03-27 | 1996-10-15 | Toyota Central Res & Dev Lab Inc | Mg-al-ca alloy excellent in die castability |
| CN1249355A (en) * | 1998-09-30 | 2000-04-05 | 玛志达株式会社 | Magnesium alloy forged material and member, and method for mfg. forged member |
| CN101033519A (en) * | 2006-01-27 | 2007-09-12 | 爱信精机株式会社 | Magnesium alloy and casting |
| CN101774013A (en) * | 2010-02-26 | 2010-07-14 | 华南理工大学 | Composite grain finer for Mg-Al alloy and preparation method thereof |
| CN101812607A (en) * | 2010-04-22 | 2010-08-25 | 东北轻合金有限责任公司 | Magnesium alloy refiner and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2033456C1 (en) * | 1990-10-08 | 1995-04-20 | Иван Андреевич Баранник | Blend for pig iron working |
| JPH0748646A (en) * | 1993-03-15 | 1995-02-21 | Toyota Motor Corp | High strength magnesium base alloy and production thereof |
| IL125681A (en) | 1998-08-06 | 2001-06-14 | Dead Sea Magnesium Ltd | Magnesium alloy for high temperature applications |
| US6342180B1 (en) | 2000-06-05 | 2002-01-29 | Noranda, Inc. | Magnesium-based casting alloys having improved elevated temperature properties |
| US8123877B2 (en) * | 2003-01-31 | 2012-02-28 | Kabushiki Kaisha Toyota Jidoshokki | Heat-resistant magnesium alloy for casting heat-resistant magnesium alloy cast product, and process for producing heat-resistant magnesium alloy cast product |
| KR100519721B1 (en) * | 2003-03-26 | 2005-10-14 | 주식회사 다이너머트리얼스 | High strength magnesium alloy and its preparation method |
| CN101314803B (en) * | 2008-04-23 | 2012-01-11 | 谢华 | Calloy deoxidizing agent for steel-smelting |
-
2011
- 2011-03-30 KR KR1020110028939A patent/KR101385685B1/en active IP Right Grant
-
2012
- 2012-03-30 US US14/008,081 patent/US20140010702A1/en not_active Abandoned
- 2012-03-30 WO PCT/KR2012/002426 patent/WO2012134243A2/en active Application Filing
- 2012-03-30 EP EP12763216.4A patent/EP2692883B1/en active Active
- 2012-03-30 CN CN201280021220.1A patent/CN103502494B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269609A (en) * | 1995-03-27 | 1996-10-15 | Toyota Central Res & Dev Lab Inc | Mg-al-ca alloy excellent in die castability |
| CN1249355A (en) * | 1998-09-30 | 2000-04-05 | 玛志达株式会社 | Magnesium alloy forged material and member, and method for mfg. forged member |
| CN101033519A (en) * | 2006-01-27 | 2007-09-12 | 爱信精机株式会社 | Magnesium alloy and casting |
| CN101774013A (en) * | 2010-02-26 | 2010-07-14 | 华南理工大学 | Composite grain finer for Mg-Al alloy and preparation method thereof |
| CN101812607A (en) * | 2010-04-22 | 2010-08-25 | 东北轻合金有限责任公司 | Magnesium alloy refiner and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SHAW C ETAL.: "Characteristics of formation of nanoscale αMg dispersions in glassy melt-spun Mg-Al-Ca alloys", 《SCRIPTA MATERIALIA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245593A (en) * | 2017-06-26 | 2017-10-13 | 重庆文理学院 | Magnesium intermediate alloy grain refiner and its preparation method and application |
| CN111155011A (en) * | 2020-02-21 | 2020-05-15 | 江苏理工学院 | High-performance Mg-Al-Ca magnesium alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2692883B1 (en) | 2017-10-04 |
| WO2012134243A3 (en) | 2013-01-03 |
| KR101385685B1 (en) | 2014-04-16 |
| EP2692883A2 (en) | 2014-02-05 |
| KR20120110818A (en) | 2012-10-10 |
| EP2692883A4 (en) | 2014-11-19 |
| US20140010702A1 (en) | 2014-01-09 |
| WO2012134243A2 (en) | 2012-10-04 |
| CN103502494B (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| UA119515C2 (en) | Aluminum alloy | |
| JP5345647B2 (en) | Magnesium-based alloy having excellent melt fluidity and hot cracking resistance and method for producing the same | |
| CN101787472B (en) | Heat-resistant forged magnesium-rare earth alloy and preparation method thereof | |
| CN104372225B (en) | Preparation method of cast-state Mg-Gd-Zn(-Zr) alloy with LPSO structure | |
| CN100390313C (en) | High strength magnesium alloy and its preparation method | |
| Yang et al. | Effects of Sn addition on as-cast microstructure, mechanical properties and casting fluidity of ZA84 magnesium alloy | |
| CN104694805A (en) | Low-cost multi-component heat-resistant magnesium alloy and preparation method of magnesium alloy | |
| JP2011206847A (en) | Magnesium alloy for high temperature and method for manufacturing the same | |
| CN101440450A (en) | Preparation of lanthanum-containing AE heat resisting die-casting magnesium alloy | |
| CN101353747A (en) | Die-casting heat resisting magnesium alloy and preparation thereof | |
| CN103502494A (en) | Mg-al-ca-based master alloy for mg alloys, and a production method therefor | |
| CN1962914A (en) | Cast magnesium alloy containing rare-earth and preparation method thereof | |
| CN104032195A (en) | Efficiently-extrudable low-cost high-performance heat-conducting magnesium alloy and preparation method thereof | |
| CN102337437A (en) | High-plasticity casting Mg-Sn-Zn-Al series magnesium alloy | |
| JP5595891B2 (en) | Method for producing heat-resistant magnesium alloy, heat-resistant magnesium alloy casting and method for producing the same | |
| CN108300884A (en) | A kind of hypoeutectic Al-Mg2The rotten and thinning method of Si alloys | |
| Yang et al. | As-cast microstructures and mechanical properties of Mg–4Zn–xY–1Ca (x= 1.0, 1.5, 2.0, 3.0) magnesium alloys | |
| Mingbo et al. | Microstructure, tensile and creep properties of as-cast Mg-3.8 Zn-2.2 Ca-xCe (x= 0, 0.5, 1 and 2 wt.%) magnesium alloys | |
| CN103882273A (en) | Mg-Mn wrought magnesium alloy and preparation method thereof | |
| JP4433916B2 (en) | Magnesium alloy and magnesium alloy member for plastic working | |
| CN105220046A (en) | A kind of Mg-Al-Zn alloy of Sn, Mn composite strengthening | |
| CN104928549A (en) | High-strength and high-elasticity-modulus casting Mg-RE alloy and preparation method thereof | |
| CN105603281B (en) | Low-cost and high-performance Mg Al Mn magnesium alloys | |
| JP2001316787A (en) | METHOD FOR PRODUCING HALF-MELTED BILLET OF Al ALLOY FOR TRANSPORTING MACHINE | |
| CN105154733A (en) | Novel non-rare earth cast magnesium alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160921 Address after: Chungnam, South Korea Applicant after: Korea Ind Tech Inst Applicant after: EMK Corporation Address before: Chungnam, South Korea Applicant before: Korea Ind Tech Inst |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |