Patent Grant
8636853
This application is a national phase application of International Application No. PCT/JP2008/056536, filed Mar. 26, 2008, and claims the priority of Japanese Application No. 2007-080224, filed Mar. 26, 2007, the contents of both of which are incorporated herein by reference.
The present invention relates to an Mg alloy and a method of production thereof, more particularly relates to an Mg alloy improved in isotropy of deformation, and a method of production thereof.
An Mg alloy is light weight, gives strength at room temperature and high temperature, and is improved in corrosion resistance as well, so is being increasingly used for various applications. However, to improve the toughness as a structure and the plastic workability, the ductility has to be improved.
For example, Japanese Patent Publication (A) No. 2002-256370 proposes Mg100-a-bLnaMb, where Ln is at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Tb, Lu, and a misch metal, M is at least one of Al and Zn, 0.5≦a≦5, 0.2≦b≦4, and 1.5≦a+b≦7, where the crystal grain size is less than 2000 nm (=2 μm) so as to obtain high strength and high ductility. However, with a Zn content larger than 1 at %, the solid solubility limit in the Mg is exceeded, so Mg—Zn-based intermetallic compounds are produced and a high ductility is liable not to be realizable.
Further, Japanese Patent Publication (A) No. 5-306929 proposes Mgba1XaLnb, where X is at least one of Zn, Ni, and Cu, Ln is at least one of Y, La, Ce, and a misch metal, 1≦a≦10, and 1≦b≦20, where the average size of the crystal grains is 5 μm or less and the average grain size of the intermetallic compounds is 5 μm or less to provide strength, toughness, and secondary workability.
Japanese Patent Publication (A) No. 7-3375 proposes MgaZnbXc, where X is at least one element of Y, Ce, La, Nd, Pr, Sm, and a misch metal, 87 at %≦a≦98 at %, b and c are in the ranges shown in
International Patent Publication WO2004/085689 proposes including Zn in an amount of a at %, including at least one rare earth element selected from the group of La, Ce, and misch metals in a total of b at %, having a balance of Mg, with a and b satisfying the following expressions (1) to (3): (1) 0.2≦a≦3.0, (2) 0.3≦b≦1.8, and (3) −0.2a+0.55≦b≦−0.2a+1.95 so as to obtain a high strength and high toughness.
Japanese Patent Publication (A) No. 2005-113235 proposes Mg100-a-bZnaYb, where a/12≦b≦a/3 and 1.5≦a≦10, where the microstructure is an aged precipitated phase of Mg3Zn6Y1 quasi-crystals and their similar crystals dispersed in the state of microparticles so as to improve the high temperature strength.
Japanese Patent Publication (A) No. 2006-2184 proposes an Mg-based alloy containing 1 to 8 wt % of rare earth elements and 1 to 6 wt % of Ca and having a microstructure in which the maximum crystal grain size of Mg is 30 μm or less, the maximum grain size of intermetallic compounds is 20 μm or less, and the Mg is dispersed in the crystal grains and at the crystal grain boundaries so as to improve the strength and ductility at room temperature and the high temperature strength and fatigue strength near 200° C.
However, in each of the above, the difference in strength between the tensile deformation and the compressive deformation and ductility was not considered at all.
The present invention has as its object the provision of an Mg alloy provided with both high strength and high ductility by making the strength and ductility in tensile deformation and compressive deformation equal levels and a method of production of the same.
To achieve the above object, according to the first aspect, the Mg alloy of the present invention is characterized by having a chemical composition consisting of Y: 0.1 to 1.5 at % and a balance of Mg and unavoidable impurities and having a microstructure with high Y regions with Y concentrations higher than an average concentration distributed at nanometer order sizes and intervals.
The method of production of the Mg alloy of the present invention is characterized by forming the above microstructure by but working an alloy having the above chemical composition, then isothermally heat treating it.
The Mg alloy of the present invention can be deformed in directions other than along the bottom face of the Mg hexagonal crystal due to the above prescribed chemical composition and microstructure and can realize high ductility due to the match of the yield strengths in tensile deformation and compressive deformation.
The method of the present invention can produce the above Mg alloy of the present invention by hot working and isothermally heat treating an Mg alloy of the above chemical composition to form the above microstructure.
According to the second aspect, the Mg alloy of the present invention is characterized by having a chemical composition consisting of Y: more than 0.1 at % and a balance of Mg and unavoidable impurities, having a microstructure with high Y regions with Y concentrations higher than an average Y concentration distributed at nanometer order sizes and intervals and having an average recrystallized grain size within the range satisfying the following formula 1:
−0.87c+1.10<log d<1.14c+1.48 formula 1:
Preferably, according to the second aspect, the Mg alloy has a Y content of more than 0.6 at % and an average recrystallized grain size within the range satisfying the following formula 2:
−0.55c+15.9<log d<1.13c+0.93. formula 2:
More preferably, according to the second aspect, the Mg alloy has an average recrystallized grain size within the range satisfying the following formula 3:
log d>−0.31c+0.92. formula 3:
Most preferably, the Mg alloy has an average recrystallized grain size within the range satisfying the following formula 4:
−0.31c+1.22<log d<−2.60c+6.14. formula 4:
The inventors newly discovered that in the first aspect of the present invention, by adding 0.1 to 1.5 at % of Y to Mg and hot working and isothermally heat treating it to form a microstructure with high Y regions with Y concentrations higher than an average concentration dispersed at nanometer order sizes and intervals, it is possible to match the yield strengths in tensile deformation and compressive deformation and possible to achieve high deformation isotropy and thereby completed the present invention.
In the method of the present invention, the temperature and amount of strain of the hot working and the temperature of the heat treatment do not particularly have to be limited so long as they are temperatures giving the above microstructures as a result. In general, the hot working temperature is preferably 300° C. or more so as to form uniform fine recrystallized grains over the entire material, but to build up strain along with working, it is preferably 450° C. or less. The amount of strain of the hot working is preferably an equivalent plastic strain of 3 or more so as to make the initial structure uniformly finer. The temperature of the heat treatment is preferably the hot working temperature or more so as to grow equiaxed crystal grains, but to form regions with different Y concentrations, the temperature is preferably 450° C. or less.
In a conventional wrought Mg alloy such as AZ31, the plastic deformation near normal temperature is performed by slip deformation due to the motion of dislocations in the close packed crystal plane, that is, the so-called basal plane of an Mg hexagonal crystal. If slip deformation other than the direction along the basal plane is hard to occur in this way, in particular in compressive deformation, deformation by twinning easily occurs. That is, in compressive deformation, deformation by twinning occurs with priority over slip deformation due to dislocations. Specifically, in a stress-strain diagram, the phenomenon occurs where the yield strength and the work hardening rate after yielding fall in compressive deformation compared with tensile deformation.
If the deformation behavior differs between tensile deformation and compressive deformation in this way, that is, so-called deformation anisotropy occurs, when an external force acts on a 3D structure made of the Mg alloy, twinning deformation will occur at the locations acted on by the compressive stress, so deformation will start by a lower stress than the locations acted on by tensile stress and, further, the work hardening rate will be small, deformation twinning occurs forming fracture origins at a low stress and small strain and deformation concentrates at part of the deformation twinning, so the stress rapidly increases, then fracture occurs at a small strain.
Therefore, in the past, the strength characteristics of an Mg alloy in the final analysis ended up having a deformation degree limited by the deformation characteristics in compression.
In the Mg alloy of the present invention, to achieve the deformation behavior in tensile deformation and compressive deformation, in particular matched yield strengths and isotropy of deformation, a chemical composition consisting of Y: 0.1 to 1.5 at % and a balance of Mg and unavoidable impurities and a microstructure where high Y regions with Y concentrations higher than an average concentration are dispersed at nanometer order sizes and intervals are prescribed.
In the present invention, as indicators of the isotropy of deformation, the two characteristic values of the following (1) and (2) are used. When these simultaneously satisfy their prescribed conditions, the deformation isotropy is judged good.
1) Yield Stress Ratio≧0.6
The ratio between the yield stress in compressive deformation and the yield stress in tensile deformation, that is, the “yield stress ratio”, is used. The value should be 0.6 or more.
2) Nominal Compressive Strain≧0.4
As an indicator of ductility in compressive deformation, the “nominal compressive strain” is used. The value should be 0.4 or more.
To simultaneously satisfy these conditions, the Y content must be within the range of 0.1 to 1.5 at %.
Below, specific examples will be used to explain in further detail the present invention including the mechanism of achieving deformation isotropy.
Examples of the first aspect of the present invention will be described.
<Preparation of Alloy>
Yttrium (Y) and pure magnesium (Mg) (purity 99.95 wt %) were completely melted in an argon atmosphere and cast into iron molds to prepare seven Mg—Y alloys with Y contents of 0.1 at %, 0.3 at %, 0.6 at %, 1.0 at %, 1.2 at %, 1.5 at %, and 2.2 at %. The Y contents 0.1 at % to 1.5 at % are invention examples in the range of the present invention, while the Y content 2.2 at % is a comparative example outside the range of the present invention, which are shown in Table 1 as Examples 1 to 6 and Comparative Example 1. Note that Table 1 also shows alloys with Al, Zn, and Li as elements other than Y as Comparative Examples 2 to 6. The alloys of Comparative Examples 1 to 6 were also prepared by the procedure and conditions shown below in the same way as the alloys of Examples 1 to 6.
The obtained cast alloys were held in a furnace at a temperature of 500° C. for 24 hours in the atmosphere, then water cooled to solution treat them.
After this, the alloys were machined to prepare cylindrical materials having a diameter of 40 mm and a length of 70 mm.
These cylindrical materials were held in containers held at the extrusion temperatures shown in Table 1 (in the atmosphere) for 30 minutes, then extruded by an extrusion ratio of 25:1 in severe hot working. The average equivalent plastic strain determined from the rate of reduction of cross-section was 3.7.
The extruded materials were isothermally held in a furnace at 400° C. for 24 hours, then air cooled outside the furnace.
<Observation of Microstructure>
If the conventional typical wrought Mg alloy AZ31 is rolled, forged, extruded, or otherwise hot worked, it strongly tends to form a texture with the close packed crystal plane of the crystal lattice (basal plane of hexagonal crystal) oriented parallel to the working direction and aggravates the anisotropy of deformation. As opposed to this, in the alloy of the present invention, even in the state as hot extruded as above, the crystal grain structure becomes an equiaxed grain structure, no texture due to working is observed, and a structure advantageous for achieving isotropy of deformation is obtained. Note that in this example, the hot working was performed by extrusion, but rolling, forging, or other hot working methods may also be used.
Furthermore, the results of atom probe observation of an Mg-0.6 at % alloy are shown in
Further, by further detailed observation, it was learned that in each example, such nanometer order high Y regions are uniformly distributed in the crystal grains, but the density of distribution is also high at the crystal grain boundaries.
<Static Tensile Test and Static Compression Test>
For the prepared Mg alloys of Examples 1 to 6 and Comparative Examples 1 to 6, test pieces taken from the above extruded and heat treated materials were subjected to a static tensile test and compressive test at room temperature at a strain rate of 1×10−3/sec.
From the results of Table 1, Examples 1 to 6 where the Y content is in the range of 0.1 at to 1.5 at % have yield stress ratios (=compressive yield stress/tensile yield stress) of 0.6 or more, have compressive breakage strains of 0.4 or more, and have high isotropy of deformation. Note that in Example 5 and Example 6 of 1.2 at % Y and 1.5 at % Y, a deformation isotropy with a yield stress ratio close to 1.0 is secured.
As opposed to this, in Comparative Example 1 where the Y content is outside the range of the present invention and Comparative Examples 2 to 6 of alloys other than with Y, the yield stress ratio was less than 0.6, the compressive breakage strain was less than 0.4, and the isotropy of deformation was inferior.
<Impact Compression Test>
A test piece was taken from the hot extruded and heat treated material and subjected to an impact compression test at room temperature at a strain rate of 1.3×103/sec. A compressive load was applied until a nominal strain of 27%, but the test piece deformed uniformly without the occurrence of cracks at the side faces.
The high deformation isotropy was believed to have been achieved in the Mg alloy of the present invention as shown in the above examples due to the following mechanism.
The presence of nanometer order high Y regions where the large atom size Y concentrates causes the crystal lattice to be remarkably distorted, so it becomes difficult for the dislocations to pass through the high Y regions when moving through the basal plane of the hexagonal crystal. As a result, slip no longer occurs preferentially at the basal plane and the slip system at the crystal planes other than the basal plane becomes active.
As shown in
The reason why anisotropy of deformation due to compressive deformation and tensile deformation occurred was the occurrence of twinning due to compressive deformation. Therefore, in the alloy of the present invention where the occurrence of twinning is reduced at the time of start of deformation due to the increase in the slip deformation, the difference in deformation behavior in tension and compression is greatly reduced or completely eliminated and the isotropy of the yield stress remarkably rises.
Furthermore, the lattice strain due to the distribution of nanometer order high Y regions preventing the occurrence of twinning in the above way simultaneously functions as resistance to motion of the dislocations responsible for slip deformation, so act extremely effectively as an alloy strengthening mechanism. The strengthening mechanism in action here is not just strengthening in the grains due to lattice strain in the crystal grains. It also effectively acts for strengthening of the crystal grain boundaries at which the high Y regions are distributed at a higher density than in the grains and contributes to improvement of the ductility of the alloy due to the prevention of intergranular fracture. Of course, grain boundary strengthening is also effective for improving the creep strength at high temperatures.
Examples of the second aspect of the present invention will be described.
Mg—Y alloys having the chemical compositions shown in Table 2 were prepared in the same procedure and conditions as in Example I. The extrusion temperatures shown in Table 2 were used. Average recrystallized grain size (μm), tensile yield stress (A), compressive yield stress (B), yield stress ratio (B/A), and compressive breakage strain were measured in the same way as in Example I. The results are summarized in Table 2.
In
In the region (1) of
−0.87c+1.10<log d<1.14c+1.48, formula 1:
where c: Y content (at %) and
In the region (2) of
−0.55c+1.20<log d<1.13c+0.93, formula 2:
where c: Y content (at %) and
In the region (1) of
log d>−0.31c+0.92, formula 3:
where c: Y content (at %) and
In the region (2) of
−0.31c+1.22<log d<−2.60c+6.14, formula 4:
where c: Y content (at %) and
As shown in Example II, an extremely high yield stress ratio and compressive breakage strain can be achieved by appropriate combination of the Y concentration (c) and average recrystallized grain size (d).
According to the present invention, there are provided an Mg alloy provided with a high strength and high ductility due to the strength and ductility at tensile deformation and compressive deformation being matched to equal levels and a method of production of the same.
The Mg alloy of the present invention achieves an increase in the freedom of deformation in the crystal grains and randomization of the crystal orientation distribution. Therefore, the isotropy of deformation which could not be achieved in conventional magnesium alloys, that is, closer yield stresses in compressive and tensile deformations, becomes possible.
Therefore, when an external force acts on a 3D structure formed using a wrought material (plates, bars, or pipes) comprised of the Mg alloy of the present invention, the deformation of the material becomes close to isotropic, whereby equal strength is exhibited with respect to locally acting compressive load and tensile load. In conventional Mg wrought material, in general the compressive yield stress is lower than the tensile yield stress, so there is the drawback that the strength of the structure against load is governed by the yield stress on the compression side, but the Mg alloy of the present invention overcomes this weak point.
Due to the above-mentioned isotropy of deformation, in the Mg alloy of the present invention, a high deformation ability is also exhibited with respect to both high speed deformation and impact loads. Therefore, the alloy can be used as a shock absorbing material or structural material for automobiles where impact loads act.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2007-080224 | Mar 2007 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2008/056536 | 3/26/2008 | WO | 00 | 3/18/2010 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2008/117890 | 10/2/2008 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3391034 | London et al. | Jul 1968 | A |
| 20020197181 | Osawa et al. | Dec 2002 | A1 |
| 20050279427 | Park et al. | Dec 2005 | A1 |
| 20080017285 | Mukai et al. | Jan 2008 | A1 |
| Number | Date | Country |
|---|---|---|
| 1 688 509 | Aug 2006 | EP |
| 5-306424 | Nov 1993 | JP |
| 7-3375 | Jan 1995 | JP |
| 9-125172 | May 1997 | JP |
| 2002-256370 | Sep 2002 | JP |
| 2005-113235 | Apr 2005 | JP |
| 2006-2184 | Jan 2006 | JP |
| 2006-16658 | Jan 2006 | JP |
| WO 2004085689 | Oct 2004 | WO |
| Entry |
|---|
| Suzuki et al. “Creep behavior and deformation microstructures of Mg—Y alloys at 550 K.” Materials Science and Engineering A252, pp. 248-255. 1998. |
| M. Nishijima et al., “Characterization of β′ Precipitate Phase in Mg-2 at %Y Alloy Aged to Peak Hardness Condition by High-Angle Annular Detector Dark-Field Scanning Transmission Electron Microscopy (HAADF-STEM),” Materials Transactions, vol. 48, No. 1, pp. 84-87 (2007). |
| S. Agnew et al., “Mg Sheet Metal Forming: Lessons Learned from Deep Drawing Li and Y Solid-Solution Alloys,” JOM, pp. 62-69 (May 2006). |
| T. Mukai et al., “Magnesium no Shitsuon Henkei Oto ni Oyobosu Biryo Yoshitsu Genso Tenka no Eikyo,” Abstracts of the Japan Institute of Metals 2006 Nen Shunki (Dai 138 Kai) Taikai, p. 126 (Mar. 21, 2006). |
| H. Somekawa et al., “Yttrium Bunsan ni yoru Magnesium Tenshinzai no Henkei Ihosei Teigen,” Abstracts of the Japan Institute of Metals 2007 Nen Shunki (Dai 140 Kai ) Taikai, p. 451 (Mar. 27, 2007). |
| Extended European Search Report for EP Appl. No. 08739647.9 dated Dec. 12, 2011. |
| Number | Date | Country | |
|---|---|---|---|
| 20100163141 A1 | Jul 2010 | US |
