CN101652489A - Heat-resistant magnesium alloy - Google Patents
Heat-resistant magnesium alloy Download PDFInfo
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- CN101652489A CN101652489A CN200880011043A CN200880011043A CN101652489A CN 101652489 A CN101652489 A CN 101652489A CN 200880011043 A CN200880011043 A CN 200880011043A CN 200880011043 A CN200880011043 A CN 200880011043A CN 101652489 A CN101652489 A CN 101652489A
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- C22C23/00—Alloys based on magnesium
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Abstract
A heat-resistant magnesium alloy comprising Mg as a main component; at least any one selected from among Al and Ni as a first alloy element (M1); at least any one selected from among Mn, Ba, Cr and Feas a second alloy element (M2); and Ca. This heat-resistant magnesium alloy has a metallographic structure containing Mg crystal grains; platelike precipitates having precipitated within the Mg crystal grains; and grain boundary crystallizates having crystallized at boundaries of the Mg crystal grains and forming a microscopically continuous network. By virtue of the presence of the platelike precipitates within the Mg crystal grains, the transfer of dislocation within the Mg crystal grains is blocked to thereby restrict any deformation. Further, by virtue of the microscopically continuous presence of network forming grain boundary crystallizates at boundaries of the Mg crystal grains, the grain boundary strength is enhanced. This magnesium alloy having its Mg crystal grain interiors andboundaries simultaneously strengthened retains high mechanical properties even in high temperature region.
Description
Technical field
The present invention relates to sustain the heat-resistant magnesium alloy that high loading uses under the high temperature.
Background technology
, be extensive use of from light-weighted viewpoint than the lighter magnesium alloy of aluminium alloy quality as aircraft material or vehicle material etc.But magnesium alloy because intensity or thermotolerance are insufficient, therefore requires further to improve characteristic according to purposes.
Therefore, the spy opens the 2004-162090 communique and Te Kai 2004-232060 communique discloses the magnesium alloy that contains calcium (Ca) and aluminium (Al) in right amount.In these documents, because therefore Ca-Al compound or Mg-Ca compound crystal or separate out to the crystal boundary of the Mg crystal grain of magnesium alloy suppressed the motion of dislocation.As a result, the thermotolerance that magnesium alloy is few in the creep strain of high-temperature area place, demonstration is excellent.And then above-mentioned magnesium alloy is by making the Mn solid solution in Mg crystal grain, with the magnesium alloy solution strengthening.
Summary of the invention
The metal structure of alloy can influence its characteristic greatly.Therefore, in order to obtain to have the magnesium alloy that uses full intensity or creep resistant for high temperature down, be necessary to make the kind of adding element or amount etc. to be fit to the control metal structure.
The objective of the invention is to provides intragranular and crystal grain boundary all to be reinforced, to show the magnesium alloy of excellent heat resistance by using the metal structure of suitable alloying element, control magnesium alloy.
Promptly, heat-resistant magnesium alloy of the present invention, it is characterized in that containing: the magnesium of principal constituent (Mg), be selected from any first above alloying element M1 of aluminium (Al) and nickel (Ni), be selected from any second above alloying element M2 of manganese (Mn), barium (Ba), chromium (Cr) and iron (Fe), calcium (Ca); Have contain Mg crystal grain, separate out tabular precipitate to the particle of this Mg crystal grain, in the crystal boundary crystallization of this Mg crystal grain and form the metal structure of the crystal boundary crystallisate of successive network on the microcosmic.
Illustrated, among the present invention " successive network on the microcosmic " be meant present net structure (three dimensional network structure) on the macroscopic view, at the internal crystallization of the network also state of continued presence (with reference to Fig. 2).Therefore, do not present net structure but discrete state (with reference to Fig. 3) that its inside is made of the brief summary crystalline substance even if do not comprise.
Heat-resistant magnesium alloy of the present invention describes in detail in the back, by containing the second alloying element M2, has in the particle of Mg crystal grain and has the crystal boundary crystallisate that forms successive network on the microcosmic in tabular precipitate, the crystal boundary.Therefore tabular precipitate has hindered the intragranular dislocation moving at Mg owing to be present in the Mg intragranular, is difficult to distortion.In addition, owing to be present in the crystal boundary of Mg crystal grain on the crystal boundary crystallisate microcosmic of formation network continuously, so the intensity of crystal boundary improves.As a result, even if Mg alloy of the present invention also shows high mechanical characteristics in the high temperature field.That is, heat-resistant magnesium alloy of the present invention is by in the particle of strengthening Mg crystal grain simultaneously and crystal boundary, so the mechanical characteristics in the high temperature field improves greatly.
The Laves' phases compound that above-mentioned precipitate comprises C15 type crystal structure is an ideal.In addition, above-mentioned precipitate is parallel to the Mg crystalline { it is ideal that the 001} face is separated out.
Forming on the microcosmic the above-mentioned crystal boundary crystallisate of successive network, to comprise the Mg-M1-Ca based compound be ideal.In addition, the mixed crystal that above-mentioned crystal boundary crystallisate comprises the C14 type crystal structure and the Laves' phases compound of C36 type crystal structure is ideal mutually, and at this moment, above-mentioned mixed crystal structure is compared to C36 type crystal structure and can contains C14 type crystal structure more.
When precipitate is parallel to Mg crystalline { 001} face and when separating out, suppressed the dislocation moving of hexagonal crystal Mg crystallization on slipping plane.The mixed crystal phase time that comprises the Laves' phases compound of C14 type crystal structure and C36 type crystal structure when the crystal boundary crystallisate, the compound that constitutes network can not be separated, be almost monocrystalline (with reference to Fig. 4) outwardly, the area or the number of die that constitute the crystal grain boundary of network reach minimum.
Illustrated that above-mentioned " C14 type ", " C15 type ", " C36 type " are meant the symbol of Strukturberichte magazine, represent the MgZn in the Laves' phases respectively
2, MgCu
2, MgNi
23 similarly basic crystal structures of representative.
And then it is ideal that above-mentioned Mg intragranular has the micropartical that contains the above-mentioned second alloying element M2.
When making heat-resistant magnesium alloy of the present invention all be 100 quality %, preferably contain the following Ca of the above 4 quality % of 2 quality %, make the above-mentioned first alloying element M1 be 0.9 or more 1.1 below, contain the above-mentioned second alloying element M2 below the 0.6 quality % more than the 0.3 quality %, remain and be Mg and unavoidable impurities with respect to the mass ratio (M1/Ca) of Ca.
Perhaps, when making heat-resistant magnesium alloy of the present invention all be 100 atom %, preferably contain the following Ca of the above 2.470 atom % of 1.235 atom %, make the above-mentioned first alloying element M1 be 1.34 or more 1.63 below, contain the above-mentioned second alloying element M2 below the 0.27 atom % more than the 0.13 atom %, remain and be Mg and unavoidable impurities with respect to the atomic ratio (M1/Ca) of Ca.
First alloying element, second alloying element and Ca by heat-resistant magnesium alloy of the present invention is contained contains the proportional proper range that is, can obtain to have the heat-resistant magnesium alloy of the metal structure of mechanical characteristics viewpoint ideal under the high temperature.
Illustrated that " thermotolerance " estimated with the mechanical properties of the magnesium alloy in the hot environment (for example utilizing stress to relax test or axle the try hard to keep creep properties of holding experiment or hot strength etc.) in this specification sheets.
Description of drawings
Fig. 1 is the metal structure photo with metal microstructure sem observation #01 test film cross section.
Fig. 2 is for observing the metal structure photo that #01 observes sample with transmission microscopy (TEM).
Fig. 3 is for observing the metal structure photo of sample with tem observation #C1.
Fig. 4 observes sample for #01 dark-field scanning transmission electron microscope (DF-STEM) as.
Fig. 5 observes the DF-STEM picture of sample for #C1.
Fig. 6 observes the TEM picture and the electron diffraction (incident direction＜110) of sample for #01.
Fig. 7 observes the TEM picture and the electron diffraction (incident direction＜111) of sample for #01.
Fig. 8 observes the TEM picture and the electron diffraction (incident direction＜111) of sample for #C1.
Fig. 9 is for observing the intragranular DF-STEM picture of Mg that #01 observes sample.
Illustrated that #01 is to be used to distinguish the symbol of forming different magnesium alloy with #C1 in aftermentioned embodiment.
Embodiment
Below explanation is used to implement the best mode of heat-resistant magnesium alloy of the present invention (hereinafter to be referred as " magnesium alloy ").
Magnesium alloy of the present invention contains magnesium (Mg), the first alloying element M1, the second alloying element M2, the calcium (Ca) of principal constituent, have contain Mg crystal grain, separate out tabular precipitate to the particle of Mg crystal grain, in the crystal boundary crystallization of this Mg crystal grain and form the metal structure of the crystal boundary crystallisate of successive network on the microcosmic.
In the magnesium alloy of the present invention, tabular precipitate is present in the Mg intragranular.Tabular precipitate hinders in the intragranular dislocation moving of Mg.The crystalline distortion is moved on slipping plane by dislocation and is taken place.Therefore, can be parallel to hexagonal crystal Mg crystalline c face, be Mg crystallization { the tabular precipitate of 001} face.Illustrated that the thickness of slab of tabular precipitate is that 2～20nm, thickness of slab are thick more, then mechanical characteristics improves more.
In addition, precipitate can comprise the Laves' phases compound of C15 type crystal structure.Its reason is, can predict Mg crystalline c face and C15 structure { the 111} face is easy to form interface stable mutually on the crystallography, promotes the formation of tabular precipitate.The compound that constitutes the precipitate with this crystal structure can be M1-Ca based compound and/or Mg-M1-Ca based compound.
Magnesium alloy of the present invention also can further have micropartical in the particle of Mg crystal grain.Micropartical is the Mg intragranular, be present in substantially tabular precipitate around.Even if can think that this micropartical is present in the Mg intragranular, also can directly not help to improve the intragranular intensity of Mg.Yet, atomic existence relevant with the generation of precipitate (back narration), micropartical for example contains the micropartical of M2 for M1-M2 based compound etc.Illustrated that micropartical is for roughly sphere, particle diameter are about 10～15nm.
In the magnesium alloy of the present invention, the crystal boundary crystallisate that forms successive network on the microcosmic exists in the crystal boundary crystallization of Mg crystal grain.For example, even if from magnesium alloy of the present invention, remove the composition of the second alloying element M2, also there is macroscopic view to go up the crystal boundary crystallisate in the crystal boundary crystallization of Mg crystal grain, form the situation of network simultaneously.But, in the magnesium alloy that does not contain Mg, in the crystal boundary crystallisate that forms network, do not observe the continuity of microcosmic.On the other hand, in the magnesium alloy of the present invention, by containing M2, the crystal boundary crystallisate forms successive network on the microcosmic.Continuous on microcosmic by network, the area or the number of die of the crystal grain boundary of the compound of the network of reduction formation greatly.As a result, the intensity of crystal boundary improves, is reinforced.At this moment, the network of crystal boundary crystallisate is wished to cover and (will be worth abbreviation " fraction of coverage of network ") more than 70% in the Mg crystal particle crystal boundary that presents wire about the 400 μ m * 600 μ m of magnesium alloy on the regional cross section.
In addition, the crystal boundary crystallisate can comprise the C14 type crystal structure and the Laves' phases compound of C36 type crystal structure mixed crystal mutually.C14 type crystal structure and C36 type crystal structure be hexagonal system each other, is easy to form the mixed crystal phase, is ideal therefore.The Laves' phases compound of mixed crystal phase is unqualified, because near monocrystalline, so the crystal boundary crystallisate is continuous on microcosmic, the area of the crystal grain boundary of the compound of formation network or number of die reach minimum.
In addition, to comprise the Mg-M1-Ca based compound be ideal to the crystal boundary crystallisate.Mg
2Ca is a C14 type crystal structure, infers by the M1 solid solution in Mg
2Among the Ca, the mixed crystal of formation C14 type crystal structure and C36 type crystal structure mutually.At this moment, mixed crystal is compared to C36 type crystal structure in mutually, can contains C14 type crystal structure more.
Have the as above magnesium alloy of the present invention of metal structure and contain magnesium (Mg), the first alloying element M1, the second alloying element M2 and the calcium (Ca) of principal constituent.
The first alloy M1 can use at least a kind that is selected from aluminium (Al) and the nickel (Ni).Al and Ni all form compound with the Ca reaction, are the elements that presents this structure of C15 type pressgang, at the Mg that presents this structure of C14 type pressgang
2Under the condition of Ca for domination, by Al and/or Ni solid solution in Mg
2Among the Ca, the mixed crystal of formation C14 type this structure of pressgang and this structure of C36 type pressgang mutually.
The second alloying element M2 can use at least a kind that is selected from manganese (Mn), barium (Ba), chromium (Cr) and iron (Fe).Can use the reason of these elements to change by the tissue of magnesium alloy of the present invention in process of cooling as M2 describes.
Common when casting comprises the castings of magnesium alloy of the present invention solidifies visible 3 temperature stagnation points the cooling curve of operation (air cooling), and (making each temperature is T1, T2 and T3, T1＞T3, T2＞T3).When temperature of melt metal reaches liquidus temperature (solidify more than the temperature of beginning: T1=600 ℃ below 620 ℃), primary crystal Mg crystallization.In addition, during measurable arrival T2, M1 and M2 react, and produce the micropartical that generates the M1-M2 based compound of compound as high temperature.Then, when reaching eutectic temperature T3, along with the crystal boundary crystallisate crystallization of eutectic Mg, formation network.When the micropartical of castings was carried out ultimate analysis, the result was compared to theoretical value as can be known and contains more M2.That is, can predict and be compared in the more cryogenic zone of T3, M1 discharges from micropartical (M1-M2 based compound), and the M1 of discharge is along with the aggegation that is dissolved in the intragranular Ca of Mg, forms compound with Ca and separates out.
Therefore, the second alloying element M2 be necessary under being higher than the high temperature of T3 with first alloying element M1 reaction in, be difficult to be dissolved in Mg.From this reason,, in transition element, can use at least a kind that is selected from manganese (Mn), barium (Ba), chromium (Cr) and iron (Fe) as second alloying element.These elements have equal extent atomic radius, adopt similar crystal structure, and then in the zone of higher temperatures, only between T1 and T3, generate compound particularly with M1.
Illustrated that magnesium alloy of the present invention contains above-mentioned first alloying element and second alloying element at least a kind separately.A kind of in the 1st element and the 2nd element can be contained respectively, several any one or both wherein can also be contained.
Magnesium alloy of the present invention is when inciting somebody to action all as 100 quality %, preferably contain the following Ca of the above 4 quality % of 2 quality %, make the above-mentioned first alloying element M1 be 0.9 or more 1.1 below, contain the above-mentioned second alloying element M2 below the 0.6 quality % more than the 0.3 quality %, remain and be Mg and unavoidable impurities with respect to the mass ratio (M1/Ca) of Ca.Perhaps, magnesium alloy of the present invention will be in the time will all being 100 atom %, preferably contain the following Ca of the above 2.470 atom % of 1.235 atom %, make the above-mentioned first alloying element M1 be 1.34 or more 1.63 below, contain the above-mentioned second alloying element M2 below the 0.27 atom % more than the 0.13 atom %, remain and be Mg and unavoidable impurities with respect to the atomic ratio (M1/Ca) of Ca.
Is less than 0.9 when (promptly with atomic ratio measuring less than 1.34) at M1/Ca with mass ratio, and the content of Ca is many, castibility worsens, and is therefore not preferred.On the other hand, when M1/Ca surpassed for 1.1 (promptly surpassing 1.63 with atomic ratio measuring) with mass ratio, the crystal boundary crystallisate is difficult to become the mixed crystal phase, is easy to form the crystal grain that only is made of this structure of C36 type pressgang, is separated, and was therefore not preferred.And then C36 type crystal structure is exposed to high temperature following time, is easy to the phase transition of C15 type crystal structure (ScriptaMaterialia 51 (204) 1005-1010).C15 type crystal structure is easy to take place block aggegation in high-temperature area, can not form successive crystallisate network on the microcosmic, so the pyritous mechanical characteristics reduces significantly.And then preferred L 1/Ca value is (that is being 1.42～1.56 with atomic ratio measuring) below 1.05 more than 0.95.
Proportional during when containing of the second alloying element M2 less than 0.3 quality % (i.e. 0.13 atom %), the M1 that constitutes precipitate in process of cooling (process of setting) is kept as compound, precipitate can not be separated out fully, and is therefore not preferred.In addition, residual because a lot of M1 does not combine with M2, be easy to form the crystal grain that only has this structure of C36 type pressgang that does not adopt the mixed crystal structure as the crystal boundary crystallisate, be separated, therefore not preferred.On the other hand, containing of M2 is proportional when surpassing 0.6 quality % (i.e. 0.27 atom %), and the compound that contains M2 is separated out to the crystal boundary crystallisate, cuts off network, and is therefore not preferred.Preferred M2 contains proportional following being limited to more than the 0.34 quality % (i.e. 0.15 atom %).Be limited on the preferred M2 below the 0.55 quality % (i.e. 0.25 atom %), more preferably below the 0.5 quality % (i.e. 0.23 atom %).
Ca is the element that forms C14 and this structure of C36 type pressgang with Mg.Containing of Ca is proportional during less than 2 quality % (i.e. 1.235 atom %), can't generate precipitate or crystal boundary crystallisate fully, and the raising effect of heat-resistant quality is insufficient, and be therefore not preferred.On the other hand, when containing of Ca is proportional when surpassing 4 quality % (i.e. 2.470 atom %), the growing amount of precipitate or crystal boundary crystallisate is too much, can go wrong in post-treatment, and is therefore not preferred.Preferred Ca to contain proportional be the above 3.5 quality % of 2.5 quality % following (promptly below the above 2.16 atom % of 1.54 atom %).
Magnesium alloy of the present invention is not limited to common gravitational casting or compression casting, can also be through the die-cast person.In addition, cast employed mold and also be not limited to sand mo(u)ld, metal pattern etc.The speed of cooling of solidifying operation also is not particularly limited, and can put cold in atmospheric environment.
The purposes of magnesium alloy of the present invention is representative with the field of universe, military affairs, aviation, relates to various fields such as automobile, household appliances.Most preferably the goods that use under its thermotolerance of performance, hot environment for example use magnesium alloy of the present invention in engine, variator, idle call compressor or their the related goods that disposed in the engine cabin of automobile.Can enumerate the cylinder head of oil engine, cylinder body, oil pan, the transmission case that the impeller charger of oil engine uses with compressor, automobile etc. etc. particularly.
The embodiment of heat-resistant magnesium alloy of the present invention more than has been described, the present invention and non-limiting above-mentioned embodiment.Can in the scope that does not break away from purport of the present invention, implement with the change of the carrying out that those skilled in the art were implemented, the variety of way of improvement.
Below enumerate embodiment, specifically describe the present invention.
Making has changed 2 kinds of test films of the Al in the magnesium alloy, Ca and Mn content (addition), when observing these metal structures, carries out stress and relaxes test.
[manufacturing of test film]
The solder flux of the iron crucible inner face of preheating coating chlorination system in electric furnace, to wherein drop into the pure magnesium base metal of weighing, pure Al, as required Mg-Mn alloy dissolves.And then, in remaining in this molten metal of 750 ℃, add Ca (molten metal preparation section).
Stir this molten metal fully, fully behind the dissolving raw material, in the synthermal of short duration down maintenance of leaving standstill.In this dissolving operation, in order to prevent the burning of Mg, brush the mixed gas of carbonic acid gas and SF6 gas to molten metal surface, solder flux is suitably interspersed among molten metal surface.
The various alloy molten metals that so obtain are flowed in the metal pattern of stipulating shape (molten metal injection process), in atmospheric environment, make it solidify (solidifying operation).So, utilize gravitational casting to make the test film of 30mm * 300mm * 40mm.With the gained test film as #01 (embodiment that contains Mn), #C1 (comparative example that does not contain Mn).The chemical constitution of each test film is shown in table 1.Illustrated, during the magnesium alloy of table 1 is formed, remain and be Mg.
Table 1
Illustrated that in the table 1, the unit of the alloy composition of #01 and #C1 uses [quality %] and [atom %].Here, used the input amount of the value of unit [quality %], this value has been scaled " atom % " as the molten metal preparation section.
[observation of metal structure]
Use metalloscope or transmission electron microscope (TEM) viewing test sheet #01 and #C1.
Fig. 1 is the metal structure photo that utilizes the cross section of metal microstructure sem observation #01 test film.Observe Mg crystal grain (light) and at the crystal boundary crystallisate (dark part) of the network-like existence of Mg crystal particle crystal boundary.Illustrated that though not shown, the cross section of observation #C1 test film also obtains the metal structure photo identical with Fig. 1.That is, any test film is all observed network-like crystal boundary crystallisate on macroscopic view.
Then, in order to observe the microstructure of metal structure, as laminar observation sample, use TEM to observe each test film.
Fig. 2 and Fig. 3 are respectively the metal structure photo of observing sample with tem observation #01 and #C1.All observe the crystal grain boundary that the crystal grain of 2 above primary crystal Mg adjoins each other.Among Fig. 2 (#01), it is crystalline and continuous that crystal boundary crystallisate (dark part) is grown into sheet.Among Fig. 3 (#C1), the crystal boundary crystallisate is partly blocked and is discontinuous.Illustrated that the network coverage of #01 is about 90%.
In addition, Fig. 4 and Fig. 5 be respectively observe #01 and #C1 observe sample the crystal boundary crystallisate dark-field scanning transmission electron microscope (DF-STEM) as.The test film of #01 does not see as shown in Figure 4 and is separated that as seen the test film of #C1 is separated as shown in Figure 5.When the DF-STEM picture of Fig. 4 and Fig. 5 was utilized the element mapping of energy dispersion type X ray optical spectroscopy (EDX), among Fig. 4 (#01), Mg, Al and Ca distributed equably; But among Fig. 5 (#C1), in aggegation is granular, the crystal grain that is separated, the concentration height of Al.Obtain the electron diffraction of C36 type crystal structure by the high crystal grain of Al concentration.On the other hand, among Fig. 4 and Fig. 5, mainly obtain the electron diffraction pattern of C14 type crystal structure by Mg, Al and the equally distributed respectively crystallization of Ca,, point diffraction also occurred as the C36 type crystal structure of 2 doubling times of C14 type crystal structure even if a part is not separated.That is, Mg, Al and Ca equably fractional crystallisation be that the mixed crystal of C14 type crystal structure and C36 type crystal structure is almost monocrystalline mutually, outwardly.Therefore, continuous on the crystal boundary crystallisate microcosmic of formation network in the test film of #01, be almost monocrystalline outwardly.On the other hand, even if form network on the crystal boundary crystallisate macroscopic view in the test film of #C1, but discontinuous on the microcosmic, only the Laves' phases compound that is made of C36 type crystal structure is separated and exists.
Illustrated that though not shown, Mn content is the magnesium alloy of 0.2 quality % (i.e. 0.09 atom %) among the #01 for making, and also uses tem observation crystal boundary crystallisate.According to gained DF-STEM picture, when Mn amount increased, the block aggegation seen in the #C1 (Fig. 5) reduced, and the banded compound that extends occupies majority, and Mn content is not seen the viewed continuity of #01 (Fig. 4) when being 0.2 quality %.
Fig. 6 and Fig. 7 are that TEM picture, Fig. 8 of test film #01 is the TEM picture of test film #C1.It is＜110 that Fig. 6 makes incident direction 〉, to make incident direction be＜111 for Fig. 7 and Fig. 8 observe the Mg intragranular.Among Fig. 6 (#01), as seen be parallel to { the striated precipitate of 001} face.And, by in the position identical with Fig. 6, Fig. 7 of observing of oblique incidence direction as can be known, precipitate is for being parallel to { 001} face tabular.When carrying out the STEM-EDX analysis, mainly detect Al and Ca for this tabular precipitate.In addition, obtain and Al by tabular precipitate
2The electron diffraction pattern of the corresponding to C15 type of Ca crystal structure.
On the other hand, among Fig. 8 (#C1), do not see clear and definite striated contrast.Illustrated, analyzed, also almost do not detected Al or Ca even if carry out the STEM-EDX identical with #01.Therefore, in the test film of #C1, there is precipitate hardly.
Fig. 9 is for observing the intragranular DF-STEM picture of Mg that #01 observes sample.Visible a plurality of microparticals around tabular precipitate.(B of Fig. 9) when carrying out ultimate analysis, detects Mn to micropartical.Illustrated,, also do not detected Mn even if analyze (A of Fig. 9) tabular precipitate.
[stress relaxes test]
To on the basis of #01 of test film shown in the table 1 and #C1, each test film of containing AXE662 shown in the table 2, AE42, AZ91D (being the ASTM specification) carries out stress and relaxes test, the thermotolerance (creep properties) of research magnesium alloy.The process that stress when during stress relaxes between test determination at the trial test film being applied loading to the regulation deflection reduces in time.Specifically, in 150 ℃ of atmospheric environments, to the stress under compression of test film load 100MPa, process in time reduces this stress under compression, makes the displacement of test film at this moment keep necessarily.
Stress after the alloy composition of table 2 and each test film of table 3 expression and stress relax 40 hours that test.Illustrated that residue was Mg during the magnesium alloy of table 2 and table 3 was formed.In addition, " RE " is mish metal.
Table 2
Table 3
Test film #01 compares with other test films, and the minimizing ratio of the stress of being loaded is few especially, even if at high temperature also show high creep resistant.Its reason is, the existence by Mn, form the firm network of successive on the microcosmic at the crystal boundary of Mg crystallization example particle, the intragranular tabular precipitate of Mg suppresses dislocation moving, resistance to deformation increases, the intensity of test film #01 improves.
Claims (12)
1. heat-resistant magnesium alloy, it contains: the magnesium of principal constituent (Mg), be selected from any first above alloying element M1 of aluminium (Al) and nickel (Ni), be selected from any the above second alloying element M2 and calcium (Ca) of manganese (Mn), barium (Ba), chromium (Cr) and iron (Fe); It is characterized in that, have contain Mg crystal grain, separate out tabular precipitate to the particle of this Mg crystal grain, in the crystal boundary crystallization of this Mg crystal grain and form the metal structure of the crystal boundary crystallisate of successive network on the microcosmic.
2. heat-resistant magnesium alloy as claimed in claim 1, wherein said precipitate comprise the Laves' phases compound of C15 type crystal structure.
3. heat-resistant magnesium alloy as claimed in claim 1, wherein said precipitate are parallel to the Mg crystalline, and { the 001} face is separated out.
4. heat-resistant magnesium alloy as claimed in claim 1, wherein said grain boundary precipitate comprises the Mg-M1-Ca based compound.
5. the mixed crystal that heat-resistant magnesium alloy as claimed in claim 1, wherein said grain boundary precipitate comprise the C14 type crystal structure and the Laves' phases compound of C36 type crystal structure mutually.
6. heat-resistant magnesium alloy as claimed in claim 5 is compared to C36 type crystal structure in the wherein said mixed crystal structure and contains C14 type crystal structure more.
7. heat-resistant magnesium alloy as claimed in claim 1, wherein said Mg intragranular has the micropartical that contains M2.
8. heat-resistant magnesium alloy as claimed in claim 1, when making when all being 100 quality %, contain the following Ca of the above 4 quality % of 2 quality %, make the above-mentioned first alloying element M1 be 0.9 or more 1.1 below, contain the above-mentioned second alloying element M2 below the 0.6 quality % more than the 0.3 quality %, remain and be Mg and unavoidable impurities with respect to the mass ratio (M1/Ca) of Ca.
9. heat-resistant magnesium alloy as claimed in claim 8 wherein contains the following above-mentioned second alloying element M2 of the above 0.5 quality % of 0.3 quality %.
10. heat-resistant magnesium alloy as claimed in claim 1, when making when all being 100 atom %, contain the following Ca of the above 2.470 atom % of 1.235 atom %, make the above-mentioned first alloying element M1 be 1.34 or more 1.63 below, contain the above-mentioned second alloying element M2 below the 0.27 atom % more than the 0.13 atom %, remain and be Mg and unavoidable impurities with respect to the atomic ratio (M1/Ca) of Ca.
11. heat-resistant magnesium alloy as claimed in claim 10 wherein contains the following above-mentioned second alloying element M2 of the above 0.25 atom % of 0.15 atom %.
12. heat-resistant magnesium alloy as claimed in claim 1, wherein above-mentioned first alloying element are that Al, above-mentioned second alloying element are Mn.
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| JP2007097760 | 2007-04-03 | ||
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| US (1) | US20100116378A1 (en) |
| EP (1) | EP2135965A4 (en) |
| JP (1) | JPWO2008120497A1 (en) |
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| WO (1) | WO2008120497A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018048A (en) * | 2013-02-28 | 2014-09-03 | 精工爱普生株式会社 | Magnesium-based alloy powder and magnesium-based alloy molded article |
| CN106119646A (en) * | 2016-08-17 | 2016-11-16 | 浙江特富锅炉有限公司 | A kind of boiler tube and processing technology thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5445820B2 (en) * | 2008-10-03 | 2014-03-19 | 株式会社豊田自動織機 | Heat resistant magnesium alloy |
| US8435444B2 (en) | 2009-08-26 | 2013-05-07 | Techmag Ag | Magnesium alloy |
| JP5375482B2 (en) * | 2009-09-24 | 2013-12-25 | 株式会社Ｇｓユアサ | Negative electrode active material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2741642B2 (en) * | 1992-03-25 | 1998-04-22 | 三井金属鉱業株式会社 | High strength magnesium alloy |
| JPH08269609A (en) * | 1995-03-27 | 1996-10-15 | Toyota Central Res & Dev Lab Inc | Mg-al-ca alloy excellent in die castability |
| JP3522963B2 (en) * | 1996-04-04 | 2004-04-26 | 三井金属鉱業株式会社 | Method for producing heat-resistant magnesium alloy member, magnesium alloy used therefor, and magnesium alloy molded member |
| JP3415987B2 (en) * | 1996-04-04 | 2003-06-09 | マツダ株式会社 | Molding method of heat-resistant magnesium alloy molded member |
| JP2000104137A (en) * | 1998-09-30 | 2000-04-11 | Mazda Motor Corp | Magnesium alloy forging stock, forged member and production of the forged member |
| US6264763B1 (en) * | 1999-04-30 | 2001-07-24 | General Motors Corporation | Creep-resistant magnesium alloy die castings |
| JP3611759B2 (en) * | 1999-10-04 | 2005-01-19 | 株式会社日本製鋼所 | Magnesium alloy and magnesium alloy heat-resistant member with excellent heat resistance and castability |
| JP3737440B2 (en) * | 2001-03-02 | 2006-01-18 | 三菱アルミニウム株式会社 | Heat-resistant magnesium alloy casting and manufacturing method thereof |
| JP3592659B2 (en) * | 2001-08-23 | 2004-11-24 | 株式会社日本製鋼所 | Magnesium alloys and magnesium alloy members with excellent corrosion resistance |
| JP2004162090A (en) * | 2002-11-11 | 2004-06-10 | Toyota Industries Corp | Heat resistant magnesium alloy |
| JP4575645B2 (en) * | 2003-01-31 | 2010-11-04 | 株式会社豊田自動織機 | Heat-resistant magnesium alloy for casting and heat-resistant magnesium alloy casting |
-
2008
- 2008-02-01 JP JP2009507427A patent/JPWO2008120497A1/en active Pending
- 2008-02-01 CN CN200880011043A patent/CN101652489A/en active Pending
- 2008-02-01 WO PCT/JP2008/052085 patent/WO2008120497A1/en active Application Filing
- 2008-02-01 EP EP08710964A patent/EP2135965A4/en not_active Withdrawn
- 2008-02-01 US US12/594,508 patent/US20100116378A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018048A (en) * | 2013-02-28 | 2014-09-03 | 精工爱普生株式会社 | Magnesium-based alloy powder and magnesium-based alloy molded article |
| CN104018048B (en) * | 2013-02-28 | 2019-02-15 | 精工爱普生株式会社 | Magnesium base alloy powder and magnesium base alloy formed body |
| CN106119646A (en) * | 2016-08-17 | 2016-11-16 | 浙江特富锅炉有限公司 | A kind of boiler tube and processing technology thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008120497A1 (en) | 2008-10-09 |
| JPWO2008120497A1 (en) | 2010-07-15 |
| EP2135965A1 (en) | 2009-12-23 |
| EP2135965A4 (en) | 2010-03-31 |
| US20100116378A1 (en) | 2010-05-13 |
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