US20080175744A1 - Magnesium alloys - Google Patents

Magnesium alloys Download PDF

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Publication number
US20080175744A1
US20080175744A1 US11/787,426 US78742607A US2008175744A1 US 20080175744 A1 US20080175744 A1 US 20080175744A1 US 78742607 A US78742607 A US 78742607A US 2008175744 A1 US2008175744 A1 US 2008175744A1
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weight
alloys
alloy
sample
added
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US11/787,426
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Tetsuichi Motegi
Yosuke Tamura
Yukio Sanpei
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Sanyu Seiki Co Ltd
Adco Koki Co Ltd
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Sanyu Seiki Co Ltd
Adco Koki Co Ltd
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Assigned to ADCO KOKI CO., LTD., SANYU SEIKI CO., LTD., MOTEGI, TETSUICHI, SAITO, KAZUYOSHI reassignment ADCO KOKI CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SANPEI, YUKIO, MOTEGI, TETSUICHI, TAMURA, YOSUKE
Publication of US20080175744A1 publication Critical patent/US20080175744A1/en
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    • 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

Definitions

  • the present invention relates to magnesium alloys, and more particularly to magnesium alloys for use in casting.
  • Magnesium (Mg) has the specific gravity of 1.74, which is approximately two seconds of the specific gravity of aluminum (Al) and approximate one fourth of the specific gravity of iron (Fe).
  • Magnesium is most lightweight among practical metals, and has various favorable properties such as excellent specific tensile strength, specific rigidity, shielding of electromagnetic waves, heat conduction, size invariance and cutting facility, as well as availability for recycle. Because of these properties, magnesium is used in bodies of cell phones, note-type personal computers and mobile electronic devices that require weight saving. Also for weight saving of vehicles, which is the most effective way for improving the fuel consumption rate, the car industry is promoting development and practical use of automotive parts made of magnesium alloys (hereafter called Mg alloys as well).
  • Ma-Al—Zn based AZ91D alloys and Mg—Al based AM60B alloys are known as typical magnesium alloys for use in casting. Names of the magnesium alloys are determined in accordance with the ASTM standards.
  • the JIS standards Japanese Industrial Standards
  • the notation system according to these standards assigns specific alphabetical letters to respective elements contained in alloys.
  • the notation system uses A for aluminum (Al), Z for zinc (Zn), M for manganese (Mn), K for zirconium (Zr), E for rare earth elements, S for silicon (Si), Q for silver (Ag), L for lithium (Li), C for copper (Cu), W for yttrium (Y), H for terbium (Tb), for example.
  • Numerals following the atomic symbols represent quantities of the components, and alphabetical letters suffixed at the ends indicate the sequential order of establishment of the alloys.
  • the AZ91D alloy is not only excellent in balance between its castability, such as flow, hot cracking resistance and shrinkage property, and its mechanical properties, but it is also economical. Therefore, applications of the AZ91D alloy widely range from vehicle parts to electronic devices. On the other hand, the AM60B alloy is used mostly in vehicle parts because of its better ductility than the AZ91D alloy.
  • Exemplary applications of the AZ91D alloy are key lock housings, sunroofs, retractable roofs, glove boxes, ashtrays, and so on.
  • Exemplary applications of the AM60B alloy are beams of instrument panels, pedal brackets, sheet frames, airbag housings, steering columns, pedal brackets, ABS mount brackets, road wheels, and so on.
  • magnesium alloys for weight saving of vehicles, the use of magnesium alloys in transmissions, engine-peripherals and other parts, which are subject to severe environments, is under research.
  • existing magnesium alloys including AZ91D and AM60B involve the issue of creep strain or deformation under the temperature of 100° C. or more, and the creep deformation degrades the dimensional accuracy of the bolt-tightening portions and degrades the tightening strength.
  • Mg—Al—Si based alloys such as AS21 and AS41 are liable to seize up to the mold in the course of casting, and their heat resistance is still insufficient for use in engine parts.
  • Mg-RE based alloys, WE54, ZE41 and QE22 are good in heat resistance, but they are expensive and will increase the cost of the products.
  • rare earth elements RE are too expensive to use as additive elements. Furthermore, alloys containing RE involve the problems that their melts degrade in fluidity and are liable to seize up to the mold, which lead to degrading castability and strength at room temperature.
  • Mg-RE based alloys tends to incline toward alloys adjusted in amount of additive Zn or Ag to improve the castability and alloys added with Ca or Si to enhance the heat resistance.
  • alloys based on the Mg—Al system has become active in recent years and, for enhancing heat resistance, various trials have been made to add combinations of RE, Ca, Si and Sr to Mg—Al based alloys such as AZ91D and AM60B, for example, as basic alloys.
  • these additive elements if added excessively, not only degrade the castability, but also deteriorate the room temperature strength and the corrosion resistance.
  • a further object of the invention is to provide a heat-resistant casting Mg alloy well balanced in heat-resistance and room temperature strength.
  • a still further object of the invention is to provide a heat-resistant casting Mg alloy that can be inhibited from deterioration of corrosion resistance while keeping well balanced in heat resistance and room temperature strength.
  • a casting Mg alloy comprising an Mg—Al based alloy containing approximately 5.0-9.0 weight % Al and added with Cu.
  • the Mg—Al based alloy preferably contains approximately 8.0 weight % aluminum (Al). If the amount of Cu added to the alloy is in the range approximately from 1.0 to 5.0 weight %, heat resistance and room temperature strength will be well balanced. However, it is preferable to limit the amount of Cu to the range approximately from 1.0 to 1.5 weight % and add manganese (Mn) to prevent deterioration of the corrosion resistance. Preferable amount of Mn added here is approximately 0.5-1.0 weight %.
  • FIG. 1 shows creep curves of sample Mg alloys added with 1.0-5.0 weight % Cu and comparative alloys.
  • FIG. 2 is a diagram plotting creep rate of sample Mg alloys added with 1.0-5.0 weight % Cu together with that of comparative alloys.
  • FIG. 3 is a graph showing 0 . 2 % proof strength of sample Mg alloys added with 1.0-5.0 weight % Cu at 23° C. (room temperature) and 150° C. (high temperature), together with that of comparative alloys.
  • FIG. 4 is a graph showing maximum tensile stress of sample Mg alloys added with 1.0-5.0 weight % Cu at 23° C. (room temperature) and 150° C. (high temperature), together with that of comparative alloys.
  • FIG. 5 is a graph showing tensile elongation of sample Mg alloys added with 1.0-5.0 weight % Cu at 23° C. (room temperature) and 150° C. (high temperature), together with that of comparative alloys.
  • FIG. 6 is a graph showing corrosion rate of sample Mg alloys added with 1.0-5.0 weight % Cu, together with that of comparative alloys.
  • FIG. 7 is a graph showing corrosion rate of sample Mg alloys containing 1 . 5 weight % Cu and 0.25-1.0 weight % Mn, together with that of comparative alloys.
  • FIG. 8 shows creep curves of sample Mg alloys containing 1.5 weight % Cu and 0.25-1.0 weight % Mn, together with those of comparative alloys.
  • FIG. 9 is a diagram plotting creep rate of sample Mg alloys containing 1 . 5 weight % Cu and 0.25-1.0 weight % Mn, together with that of comparative alloys.
  • FIG. 10 is a graph showing 0.2% proof strength of sample Mg alloys containing 1.5 weight % Cu and 0.25-1.0 weight % Mn at 23° C. (room temperature) and 150° C. (high temperature), together with that of comparative alloys.
  • FIG. 11 is a graph showing maximum tensile stress of sample Mg alloys containing 1.5 weight % Cu and 0.25-1.0 weight % Mn at 23° C. (room temperature) and 150° C. (high temperature), together with that of comparative alloys.
  • FIG. 12 is a graph showing maximum tensile elongation of sample Mg alloys containing 1.5 weight % Cu and 0.25-1.0 weight % Mn at 23° C. (room temperature) and 150° C. (high temperature), together with that of comparative alloys.
  • the Inventors considered it advantageous to use Mg—Al based alloys as a master and add one or more elements that contribute to enhancement of heat resistance. Consequently, the Inventors selected copper (Cu) as an element that can enhance the heat resistance. Cu not only enhances heat resistance without degrading room temperature strength and castability, but also is available at a lower cost than rare earth elements (RE). Cu enhances heat resistance by accelerating solid solution and generating compounds in the system. Solid-soluble limit of Cu was examined on a Mg—Al—Cu ternary alloy, and it has been confirmed that Cu can be solid-soluble to the maxim, 3.0 weight %, when Al is added to Mg by 8.0 weight %.
  • Cu copper
  • Mg—Al based alloys are added with 5.0-9.0 weight % Al to improve castability and room temperature strength. Therefore, from the viewpoint of heat resistance and other properties, appropriate amount of Al to be added will be 5.0-9.0 weight %, and preferable amount of Al is 8.0 weight %.
  • Zn has a function to improve the mechanical strength of Mg and the fluidity of the melt during casting, room temperature strength and castability similar to those of the most demanded AZ91D alloy by adding Zn. However, if the amount of added Zn reaches 2.0% or more, it disturbs alloying. Therefore, appropriate amount of Zn is 2.0%. Additionally, since the use of SF 6 , etc. for preventing combustion of magnesium will be prohibited for protection of the environment, beryllium (Be) having a combustion-preventing effect was added by 0.1%. Beryllium prevents the surface of the Mg melt from contact with and oxidation by air, and prevents combustion of the melt. Therefore, AZ91D alloys are added with a slight amount of Be as well.
  • Be beryllium
  • creep deformation resistance is one of the most important properties of materials.
  • creep deformation if a metal is exposed to continuous application of a stress of a level even lower than the maximum tensile stress, the metal deforms and breaks down in the long run. This phenomenon of deformation with time under a certain stress is called “creep deformation” or simply “creep”.
  • Tm is the melting point in absolute temperature, which is 461.5 K for pure Mg.
  • creep deformation resistance was examined as an index of heat resistance with the following five Mg alloys prepared as samples different in amount of added Cu.
  • melts for the first to fifth sample alloys were prepared in the following manner. First prepared is a crucible plated with molten alumina (SUS430 stainless steel). The crucible was heated to 750° C. in an electric furnace, and weighed amounts of pure Mg, pure Al, pure Cu, Al-2.98% Be master alloy and Zn of Norsk-Hydro were molten. The melts of the alloys were next poured into a mold, and cooled at room temperature. Thus, the first to fifth sample alloys were obtained. As comparative alloys, AZ91D and AS21B were used. For preparing a melt of As21B, high-purity Si (6N) was used.
  • composition details of the comparative alloys AZ91D and AS21B were as follows.
  • Composition of AZ91D used as the first comparative alloy Al (8.7 weight %), Zn (0.7 weight %), Be (0.0013 weight %), and Mg (the rest).
  • Composition of AS21B used as the second comparative alloy Al (2.5 weight %), Zn (0.2 weight %), Si (1.2 weight %) and Mg (the rest).
  • Creep test is the commonest test for examining heat resistance. It reveals deformation conditions of materials at high temperatures. The examination was conducted by using a single type creep tester. Under the test conditions of test temperature: 150° C., test load: 50 MPa, warm-up time length:24 hours, and test time length: 100 hours, creep elongation and creep rate were measured.
  • FIG. 1 shows creep curves of the first to fifth sample alloys (S 1 through S 5 ) and the first and second comparative alloys (C 1 and C 2 ). It is acknowledged from the creep curves of FIG. 1 that the first to fifth sample alloys exhibit creep strains lower than those of the AS21B and AZ91D alloys as the first and second comparative alloys. In addition, while the sample alloys added with 3.0-5.0 weight % Cu (third to fifth sample alloys) decreased in creep stress as the amount of added Cu increased, the sample alloys added with 1.0-1.5 weight % Cu (first and second alloys) exhibited equivalent values of creep strain. From these results, it has been confirmed that creep deformation resistance is enhanced by addition of 1.0 weight % or more Cu.
  • FIG. 2 shows the relation between creep rates and time of the first to fifth sample alloys (S 1 to S 5 ) as well as the first and second comparative alloys (C 1 and C 2 ) on logarithmic scales. Since any of the first to fifth sample alloys as well as the first and second comparative alloys exhibits a creep rate in form of a straight line having a negative inclination, they are assumed to be in the stage of transient creep.
  • FIGS. 3 , 4 and 5 maximum tensile stress and tensile elongation of respective alloys are shown in FIGS. 3 , 4 and 5 .
  • the comparative alloy, AZ91D exhibited the highest maximum tensile stress both at room temperature and at the high temperature.
  • tensile strength of the first to fifth sample Mg alloys (S 1 to S 5 ) added with Cu was slightly lower than that of the comparative alloy AZ91D at room temperature, but it became approximately equal at the high temperature.
  • the 0.2% proof strength of FIG. 3 although the sample alloys exhibited similar tendency at room temperature, the alloys containing 3.0 weight % or more Cu exhibited higher 0.2% proof strength than AZ91D alloy at the high temperature.
  • the AZ91D alloy largely varied in tensile elongation from 8.0% at room temperature to 24.3% at the high temperature.
  • variance in tensile elongation tended to decrease with increase of the amount of Cu added. From this result, Cu is appreciated to increase its effect of suppressing tensile deformation at high temperatures as its amount of addition increases.
  • 1.0-5.0 weight % Cu added to Mg-8.0% Al alloys enhances heat resistance properties of the alloys, such as creep resistance and hot tensile resistance.
  • electrode potential of Cu is as high as 0.153 V as compared to electrode potential ⁇ 2.363 V of Mg. Because of this large potential difference, Cu may degrade the corrosion resistance.
  • salt water immersion test was also conducted.
  • As the salt water for the test 5.0 weight % NaCl water solution was prepared by dissolving special grade NaCl (sodium chloride) into distilled water.
  • the first to fifth sample alloys as well as the first and second comparative alloys were immersed into the test salt water for 12 hours, and they were washed with distilled water. After that, the alloys were immersed into 10% chromium oxide water solution heated to 100° C., and corrosive products (magnesium hydroxide adhering on the alloys were removed.
  • The, the corrosion rate of each alloy was calculated by introducing its mass loss, pre-test surface area and test time into the following equation to evaluate the corrosion resistance.
  • Corrosion rate (mm/year) ⁇ corrosion amount (mg) ⁇ 365 (day/year) ⁇ 10 (mm/cm) ⁇ / ⁇ density (1810 mg/cm 3 ) ⁇ surface area (cm 2 ) ⁇ lapsed time (day) ⁇
  • FIG. 6 shows corrosion rates of the first to fifth sample alloys and the first and second comparative alloys.
  • the Mg alloys added with Cu (first to fifth sample alloys) exhibited higher corrosion rates than those of the comparative alloys AZ91D and AS21B, and were inferior in corrosion resistance.
  • the first to fifth sample alloys tend to deteriorate in corrosion resistance as the amount of Cu added increases.
  • the Mg alloys containing 1.5% or less Cu (first and second sample alloys) have lower corrosion rates.
  • Mn was added as a trial. Since Mn was considered to separate out as simple substance without forming compounds when added by 1.0% or more, corrosion resistance test and heat resistance test were conducted with alloys added with 0.25-1.0 weight % Mn.
  • Melts of the sixth to eighth sample alloys were prepared in the same manner as the first to fifth sample alloys. To add Mn, an Al—Mn master alloy and high-purity aluminum were molten in a high-frequency melting furnace, and Al—Mn master alloys adjusted in components and having the target compounding ratios were used. Further, Mg melt was heated to 800° C. in an electric furnace and, after adding the Al—Mn master alloy, the melt was stirred for 60 seconds approximately.
  • FIG. 7 shows corrosion rates of the sixth to eighth Mn-added sample alloys (S 6 to S 8 ), first and second comparative alloys (AZ91D and AS21B) and the second sample alloy (1.5% Cu—Mg alloy) as another comparative alloy.
  • the corrosion rate is 40.96 mm/year, which is not so different from 46.23 mm/year of the alloy not containing Mn (second sample alloy).
  • the corrosion rate decreased to 22.80-26.18 mm/year. This demonstrates that addition of 0.5-1.0 weight % Mn contributes to improvement of corrosion resistance.
  • FIGS. 8 and 9 show creep curves and creep rates of the sixth to eighth sample alloys and the first, second comparative examples and the second sample alloy. All of the alloys added with Mn exhibited creep strain equivalent to those of alloys not containing Mn. Creep rates appeared in form of similar straight lines as well. It is assumed from this result that addition of Mn does not adversely affect the creep deformation resistance.
  • FIGS. 10 through 12 show 0.2% proof strength, maximum tensile stress and tensile elongation of the sixth to eighth sample alloys, first and second comparative alloys, and the second sample alloy.
  • alloys containing 0.5% and 1.0% Mn exhibited equivalent tensile properties to those of the alloy not containing Mn (second sample) both at the high temperature (150° C.) and at room temperature (23° C.).
  • maximum tensile stress and tensile elongation were significantly low at the high temperature (150° C.).
  • increase of temperature activates dislocations and increases tensile deformation of a material.
  • the 0.25% Mn alloy (sixth sample) exhibited the low tensile property probably because some defects such as inclusions existed in the sample piece and functioned to start the fracture.

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US20090288911A1 (en) * 2008-05-23 2009-11-26 Foxconn Technology Co., Ltd. Sound box structure
US20140190705A1 (en) * 2012-06-08 2014-07-10 Halliburton Energy Services, Inc. Methods of removing a wellbore isolation device using galvanic corrossion of a metal alloy in solid solution
US9169542B2 (en) 2009-06-17 2015-10-27 Kabushiki Kaisha Toyota Chuo Kenkyusho Recycled magnesium alloy, process for producing the same, and magnesium alloy
US9357996B2 (en) * 2010-09-08 2016-06-07 DePuy Synthes Products, Inc. Fixation device with magnesium core
US20160230494A1 (en) * 2014-08-28 2016-08-11 Halliburton Energy Services, Inc. Degradable downhole tools comprising magnesium alloys
US9689227B2 (en) 2012-06-08 2017-06-27 Halliburton Energy Services, Inc. Methods of adjusting the rate of galvanic corrosion of a wellbore isolation device
US9689231B2 (en) 2012-06-08 2017-06-27 Halliburton Energy Services, Inc. Isolation devices having an anode matrix and a fiber cathode
US9777549B2 (en) 2012-06-08 2017-10-03 Halliburton Energy Services, Inc. Isolation device containing a dissolvable anode and electrolytic compound
US10329653B2 (en) 2014-04-18 2019-06-25 Terves Inc. Galvanically-active in situ formed particles for controlled rate dissolving tools
US10329643B2 (en) 2014-07-28 2019-06-25 Magnesium Elektron Limited Corrodible downhole article
US10625336B2 (en) 2014-02-21 2020-04-21 Terves, Llc Manufacture of controlled rate dissolving materials
US10689740B2 (en) 2014-04-18 2020-06-23 Terves, LLCq Galvanically-active in situ formed particles for controlled rate dissolving tools
US10758974B2 (en) 2014-02-21 2020-09-01 Terves, Llc Self-actuating device for centralizing an object
US10865465B2 (en) 2017-07-27 2020-12-15 Terves, Llc Degradable metal matrix composite
US11167343B2 (en) 2014-02-21 2021-11-09 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
US11365164B2 (en) 2014-02-21 2022-06-21 Terves, Llc Fluid activated disintegrating metal system
EP4047106A4 (en) * 2019-10-18 2023-01-11 Kurimoto, Ltd. DEGRADABLE MAGNESIUM ALLOY
US11674208B2 (en) 2014-02-21 2023-06-13 Terves, Llc High conductivity magnesium alloy

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CN104561713A (zh) * 2014-12-15 2015-04-29 镁联科技（芜湖）有限公司 耐腐蚀镁合金及其制备方法和应用
PL3438303T3 (pl) * 2016-03-31 2020-09-21 Kurimoto, Ltd. Ulegający degradacji stop Mg
CN106756362A (zh) * 2016-12-14 2017-05-31 宁波翔博机械有限公司 一种耐热的镁合金及制备方法
JP7078839B2 (ja) * 2017-12-12 2022-06-01 富士通株式会社 マグネシウム合金、及びその製造方法、並びに電子機器
CN115287514B (zh) * 2018-04-23 2023-11-03 佳能株式会社 镁-锂系合金

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Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090288911A1 (en) * 2008-05-23 2009-11-26 Foxconn Technology Co., Ltd. Sound box structure
US9169542B2 (en) 2009-06-17 2015-10-27 Kabushiki Kaisha Toyota Chuo Kenkyusho Recycled magnesium alloy, process for producing the same, and magnesium alloy
US9357996B2 (en) * 2010-09-08 2016-06-07 DePuy Synthes Products, Inc. Fixation device with magnesium core
US9863201B2 (en) 2012-06-08 2018-01-09 Halliburton Energy Services, Inc. Isolation device containing a dissolvable anode and electrolytic compound
US9777549B2 (en) 2012-06-08 2017-10-03 Halliburton Energy Services, Inc. Isolation device containing a dissolvable anode and electrolytic compound
US9689227B2 (en) 2012-06-08 2017-06-27 Halliburton Energy Services, Inc. Methods of adjusting the rate of galvanic corrosion of a wellbore isolation device
US9689231B2 (en) 2012-06-08 2017-06-27 Halliburton Energy Services, Inc. Isolation devices having an anode matrix and a fiber cathode
US20140190705A1 (en) * 2012-06-08 2014-07-10 Halliburton Energy Services, Inc. Methods of removing a wellbore isolation device using galvanic corrossion of a metal alloy in solid solution
US9759035B2 (en) * 2012-06-08 2017-09-12 Halliburton Energy Services, Inc. Methods of removing a wellbore isolation device using galvanic corrosion of a metal alloy in solid solution
US11097338B2 (en) 2014-02-21 2021-08-24 Terves, Llc Self-actuating device for centralizing an object
US10758974B2 (en) 2014-02-21 2020-09-01 Terves, Llc Self-actuating device for centralizing an object
US11613952B2 (en) 2014-02-21 2023-03-28 Terves, Llc Fluid activated disintegrating metal system
US11685983B2 (en) 2014-02-21 2023-06-27 Terves, Llc High conductivity magnesium alloy
US11365164B2 (en) 2014-02-21 2022-06-21 Terves, Llc Fluid activated disintegrating metal system
US11674208B2 (en) 2014-02-21 2023-06-13 Terves, Llc High conductivity magnesium alloy
US10625336B2 (en) 2014-02-21 2020-04-21 Terves, Llc Manufacture of controlled rate dissolving materials
US11167343B2 (en) 2014-02-21 2021-11-09 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
US10329653B2 (en) 2014-04-18 2019-06-25 Terves Inc. Galvanically-active in situ formed particles for controlled rate dissolving tools
US10724128B2 (en) 2014-04-18 2020-07-28 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
US10760151B2 (en) 2014-04-18 2020-09-01 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
US10689740B2 (en) 2014-04-18 2020-06-23 Terves, LLCq Galvanically-active in situ formed particles for controlled rate dissolving tools
US10337086B2 (en) 2014-07-28 2019-07-02 Magnesium Elektron Limited Corrodible downhole article
US10329643B2 (en) 2014-07-28 2019-06-25 Magnesium Elektron Limited Corrodible downhole article
US10106872B2 (en) * 2014-08-28 2018-10-23 Halliburton Energy Services, Inc. Degradable downhole tools comprising magnesium alloys
US9702029B2 (en) * 2014-08-28 2017-07-11 Halliburton Energy Services, Inc. Degradable downhole tools comprising magnesium alloys
US20160230494A1 (en) * 2014-08-28 2016-08-11 Halliburton Energy Services, Inc. Degradable downhole tools comprising magnesium alloys
US10865465B2 (en) 2017-07-27 2020-12-15 Terves, Llc Degradable metal matrix composite
US11649526B2 (en) 2017-07-27 2023-05-16 Terves, Llc Degradable metal matrix composite
US11898223B2 (en) 2017-07-27 2024-02-13 Terves, Llc Degradable metal matrix composite
EP4047106A4 (en) * 2019-10-18 2023-01-11 Kurimoto, Ltd. DEGRADABLE MAGNESIUM ALLOY

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EP1847626A2 (en) 2007-10-24
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CA2585318A1 (en) 2007-10-17
AU2007201703A1 (en) 2007-11-01
KR20070102952A (ko) 2007-10-22

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