US20150376755A1 - Copper alloy material for continuous casting mold and process for producing same - Google Patents

Copper alloy material for continuous casting mold and process for producing same Download PDF

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Publication number
US20150376755A1
US20150376755A1 US14/238,173 US201114238173A US2015376755A1 US 20150376755 A1 US20150376755 A1 US 20150376755A1 US 201114238173 A US201114238173 A US 201114238173A US 2015376755 A1 US2015376755 A1 US 2015376755A1
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copper alloy
alloy material
continuous casting
product
casting mold
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Dae Hyun Kim
Bo Min Jeon
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Poongsan Corp
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Poongsan Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

Definitions

  • the present invention relates to a copper alloy material for continuous casting mold and a process for producing the same.
  • the present invention relates to a copper alloy material for continuous casting mold consisting of 0.05 wt % to 0.6 wt % of Cr, 0.01 wt % to 0.5 wt % of Ag, 0.005 wt % to 0.10 wt % of P, and a balance of Cu and a trace of unavoidable impurities; and a process for producing the same.
  • a mold used for continuous casting (or also referred to as a continuous casting mold) has an inside surface with molten steel of about 1600° C. flowing therethrough and an outside surface being quenched by cooling water at the same time, it is very important to select a material which can withstand thermal shock and thermal strain applied thereto as a material of the mold during the continuous casting process. Accordingly, the continuous casting mold material should show soundness of ingot, high strength and high thermal conductivity (electric conductivity), and further should have softening resistance, in which the mold can be used for a long time period when the temperature of the mold is elevated up to about 300° C.
  • a copper alloy material for continuous casting mold used in steel and non-steel industries is needed to have excellent heat resistance, high electric conductivity, high creep properties, excellent abrasion resistance, excellent high-temperature fatigue strength, high tensile strength, high ductility, and excellent processability.
  • a copper alloy material for continuous casting mold should be produced under an air atmosphere to improve work convenience and reduce the production cost.
  • a copper alloy material contains a large amount (>0.6%) of Cr or Zr and the copper alloy material is casted under an air atmosphere; the probability of inclusion of oxides thereto becomes very high. Accordingly, in case that the copper alloy material contains a large amount (>0.6%) of Cr or Zr, the casting process is not easy since the copper alloy material should be cast under a vacuum atmosphere or a completely controlled atmosphere.
  • a copper with silver (silver bearing copper) or chrome based copper alloy material has been widely used as the copper alloy material for continuous casting mold.
  • a well-known chrome-zirconium-copper (CuCrZr, or chrome based copper alloy material) has excellent mechanical properties, it has also a drawback of poor thermal properties including its poor thermal conductivity (electric conductivity) and has poor castability due to a large amount (>0.6%) of Cr and Zr included therein.
  • a copper with silver (a silver bearing copper) has good thermal properties owing to its excellent heat dissipation capability and such properties make melting and casting of the copper with silver very easy, but the copper with silver has poor mechanical properties due to the same reason.
  • Japanese laid open patent application No. 1992-198460 has described a copper alloy material consisting of 0.8 wt % of Cr, 0.2 wt % of Zr, and a balance of Cu, and it has also disclosed that the copper alloy material must include Cr and Zr to meet the requirements of primary mechanical properties, such as tensile strength and hardness.
  • Japanese laid open patent application No. 2003-089832 has disclosed a copper alloy material consisting of 0.01 wt % to 0.3 wt % of Zn, 0.01 wt % to 0.25 wt % of Zr or 0.02 wt % to 0.4 wt % of Cr, 0.005 wt % to 1.0 wt % of at least one of Ti, Ni, Fe, Sn, Si, Mn, P, Mg, Co, Al, B, In and Ag, and a balance of Cu.
  • the above patent publication has disclosed that a copper alloy material has inadequate tensile strength while having high conductivity and that there is no description on an elongation ratio and hardness which are required for sufficient processability.
  • PCT publication WO 04/074526 has disclosed a copper alloy material consisting of less than 0.2 wt % of Ag, 0.1 wt % to 0.4 wt % of Cr, and 0.03 wt % to 0.1 wt % of Zr.
  • the above copper alloy material can not be cast under an air atmosphere but should be only used in a vacuum furnace due to the total content of highly oxidative Cr and Zr.
  • it also requires Zr as a necessary component.
  • Japanese laid open patent application No. 1995-054079 has disclosed a copper alloy material for mold consisting of 0.5 wt % to 1.0 wt % of Ti, 0.05 wt % to 2.0 wt % of Cr, and 0.05 wt % to 0.7 wt % of Zr.
  • the above patent application has also disclosed that the copper alloy material for mold should include Ti, Cr and Zr, which are highly oxidative, as principal elements.
  • Japanese laid open patent application No. 2009-191337 has disclosed a copper alloy material consisting of 0.01 wt % to 2 wt % of Cr, and 0.005 wt % to 1 wt % of Zr as principal elements.
  • the copper alloy material disclosed in the above patent application can include either or both of Cr and Zr, and requires a high frequency induction furnace for forming a vacuum atmosphere or a controlled reaction atmosphere for producing it.
  • any copper alloy material for continuous casting mold which has mechanical properties and heat resistance properties better than a copper with silver generally used currently, has excellent heat dissipation capability better than a chrome zirconium based copper alloy material, and enables easy casting under an air atmosphere, should be required.
  • an object of the present invention is to provide a copper alloy material for continuous casting mold which enables easy casting under an air atmosphere and has excellent mechanical properties and excellent heat resistance properties, and a process for producing the same.
  • a copper alloy material for continuous casting mold consists of 0.05 wt % to 0.6 wt % of Cr, 0.01 wt % to 0.5 wt % of Ag, 0.005 wt % to 0.10 wt % of P, and a balance of Cu and a trace of unavoidable impurities, and has Brinell hardness of higher than 120 HB, and electric conductivity of higher than 85% IACS.
  • the copper alloy material can further include less than 0.1 wt % of at least one of elements selected from a group consisting of Sn, Ti, Mg, Mn, Fe, Co, Al, Si, Mo, Zr and W.
  • a process for producing a copper alloy material for continuous casting mold includes the steps of casting an ingot consisting of 0.05 wt % to 0.6 wt % of Cr, 0.01 wt % to 0.5 wt % of Ag, 0.005 wt % to 0.10 wt % of P, and a balance of Cu under an air atmosphere, homogenizing the obtained ingot at 700° C. to 950° C. for 30 minutes to 6 hours, hot working the homogenized product at 10% to 90%, cold working the hot worked product at 10% to 80%, precipitating the obtained cold worked product at 400° C. to 600° C.
  • the ingot can further include less than 0.1 wt % of at least one of elements selected from a group consisting of Sn, Ti, Mg, Mn, Fe, Co, Al, Si, Mo, Zr and W.
  • a process for producing a copper alloy material for continuous casting mold includes the steps of casting an ingot consisting of 0.05 wt % to 0.6 wt % of Cr, 0.01 wt % to 0.5 wt % of Ag, 0.005 wt % to 0.10 wt % of P, and a balance of Cu under an air atmosphere, homogenizing the obtained ingot at 700° C. to 950° C. for 30 minutes to 6 hours, cold working the homogenized product at 10% to 80%, precipitating the cold worked product at 400° C. to 600° C. for 1 hour to 8 hours, and cold working the precipitated product at 10% to 80% after cooling the product down to a room temperature.
  • the ingot can further include less than 0.1 wt % of at least one of elements selected from a group consisting of Sn, Ti, Mg, Mn, Fe, Co, Al, Si, Mo, Zr and W.
  • a process for producing a copper alloy material for continuous casting mold includes the steps of casting an ingot consisting of 0.05 wt % to 0.6 wt % of Cr, 0.01 wt % to 0.5 wt % of Ag, 0.005 wt % to 0.10 wt % of P, and a balance of Cu under an air atmosphere, cold working the obtained ingot at 10% to 80%, precipitating the cold worked product at 400° C. to 600° C. for 1 hour to 8 hours, and cold working the precipitated product at 10% to 80% after cooling the product down to a room temperature.
  • the ingot can further include less than 0.1 wt % of at least one of elements selected from a group consisting of Sn, Ti, Mg, Mn, Fe, Co, Al, Si, Mo, Zr and W.
  • the present invention has following advantageous effects.
  • a copper alloy material for continuous casting mold and the process for producing the same of the present invention can provide a copper alloy material for continuous casting mold which has high tensile strength and hardness, and excellent electric conductivity, and can be cast in the atmosphere.
  • FIG. 1 illustrates a flow chart showing the steps of a process for producing a copper alloy material in accordance with a preferred embodiment of the present invention.
  • FIG. 2 illustrates a graph showing softening resistance of a copper alloy material for continuous casting mold in accordance with a preferred embodiment of the present invention, showing Brinell hardness (unit: HB) of a test piece of the copper alloy material held for 30 minutes in each temperature section and measured after cooling down to a room temperature to show variation of the hardness with time.
  • Brinell hardness unit: HB
  • the copper alloy material for continuous casting mold is required to have minimum thermal deformation and excellent resistance to stress, as well as a good heat dissipation performance through the mold.
  • the copper alloy material for continuous casting mold consists of 0.05 wt % to 0.6 wt % of Cr, 0.01 wt % to 0.5 wt % of Ag, 0.005 wt % to 0.10 wt % of P, and a balance of Cu.
  • the copper alloy material for continuous casting mold of the present invention includes 0.05 wt % to 0.6 wt % of Cr with reference to the total weight of the copper alloy material.
  • the copper alloy material of the present invention has Cr phases finely scattered in a copper matrix, and thus, improves mechanical properties of the copper alloy material owing to the said Cr precipitates in the copper matrix, and heat resistance properties owing to the Cr precipitates in the matrix by suppressing the grain boundary migration of the copper alloy material upon heat treatment.
  • the copper alloy material for continuous casting mold of the present invention includes 0.01 wt % to 0.5 wt % of Ag with reference to the total weight of the copper alloy material. Since Ag is melted during the casting and becomes solid solution throughout the Cu matrix uniformly so as to be distributed on the copper alloy material matrix uniformly, Ag has a solid solution enhancing effect without a falling-off in electric conductivity, to serve improving the mechanical properties, accordingly.
  • the content of Ag is less than 0.01 wt %, the improvement of strength and electric conductivity due to the addition of Ag is not satisfactory, and when the content of Ag is more than 0.5 wt %, economic efficiency of the addition of Ag becomes falling off significantly due to excessive cost caused by high cost of raw materials.
  • the copper alloy material for continuous casting mold of the present invention includes 0.005 wt % to 0.10 wt % of P with reference to the total weight of the copper alloy material.
  • P is a principal element which improves de-acidification in the production of the copper alloy material, and improves strength and heat resistance, additionally.
  • the element P influences electric conductivity which is required for the copper alloy material for continuous casting mold, significantly. If the content of P is less than 0.005 wt %, a residual oxygen quantity in the molten metal becomes excessive to affect castability and makes to fail to obtain a sound ingot. However, if the content of P is more than 0.1 wt %, problems take place, in which the electric conductivity, which is a principal property required for a mold material, drops sharply and accordingly the brittleness of the obtained copper alloy material increases.
  • Copper (Cu) is a principal component, of course. Copper is included as a balance amount in the aforementioned copper alloy material composition in order to make up 100 wt % in total.
  • the copper alloy material for continuous casting mold can further include less than 0.1 wt % of at least one of elements selected from a group consisting of Sn, Ti, Mg, Mn, Fe, Co, Al, Si, Mo, Zr and W.
  • a content of copper included to the copper alloy material for continuous casting mold as a balance is reduced as much as the element included thereto thus. If the element is added, the obtained copper alloy material provides an equivalent or similar effect with the copper alloy material without such element, and the element does not affect the strength (Hardness and/or tensile strength) and electric conductivity of the copper alloy material significantly.
  • the copper alloy material of the present invention can include a trace of impurities within a range which does not affect necessary properties of the copper alloy material.
  • the impurities can be, for an example, As, S, Nb, and Sb, or a combination thereof.
  • the impurities can be included as a trace less than 0.01 wt % of the total weight of the copper alloy material.
  • the impurities can be one that can be added unintentionally during general production of the copper alloy material, and since the impurities are added in trace, the impurities do not affect the properties of the copper alloy material of the present invention, significantly.
  • the thermal properties and the conductivity of the copper alloy material of the present invention can be measured by hardness and electric conductivity after high temperature heat treatment.
  • the hardness of the copper alloy material is dependent on an extent of processing after the heat treatment in the production. It is required that the copper alloy material of the present invention has over 120 HB, and, preferably in the range of 130 HB to 150 HB in Brinell hardness (2.5/62.5 kg), right after a precipitation regardless of an additional cold processing.
  • the electric conductivity of the copper alloy material is greater than 85% IACS, and, preferably in the range of 85% IACS to 95% IACS. That is, the copper alloy material of the present invention meets the conditions of hardness of higher than 90 HB and electric conductivity of higher than 80% IACS, which are reference values for a copper alloy material for continuous casting mold, adequately, and is excellent over the references.
  • the tensile strength of the copper alloy material for continuous casting mold of the present invention can be guessed from measurement of the hardness because the tensile strength is proportional to the hardness, or can also be measured directly according to KS B0802.
  • the tensile strength of Cu—Ag—P based copper alloy material used in the related art was around at a level of 380 MPa, while that of the copper alloy material for continuous casting mold of the present invention is higher than 400 MPa, more specifically, in a range of 450 MPa to 550 MPa. This is because the copper alloy material of the present invention has transgranular and intergranular Cr precipitation phases formed by addition of Cr to serve as a factor for improving the hardness and the tensile strength of the matrix.
  • the copper alloy material for continuous casting mold of the present invention is produced by a process including the following steps of:
  • the copper alloy material for continuous casting mold of the present invention can be produced by a process without the step of hot working the homogenized product, including the following steps of:
  • the ingot can further include less than 0.1 wt % of at least one of elements selected from a group consisting of Sn, Ti, Mg, Mn, Fe, Co, Al, Si, Mo, Zr and W. If the aforementioned elements are further included, the content of copper is reduced as much.
  • the obtained ingot is homogenized at 700° C. to 950° C. for 30 minutes to 6 hours.
  • the solution heat treatment of Cr in the matrix is not made properly due to failure of adequate heating, and accordingly, the obtained product fails to obtain an adequate precipitation during the precipitating, whereas when the ingot is homogenized at a higher temperature than 950° C., intensive surface oxidation takes place on the obtained product due to a high temperature.
  • the ingot is homogenized shorter than 30 minutes, hot workability becomes poor due to heavy working load caused by shortage of a homogenization time period. Further, if the ingot is homogenized longer than 6 hours, excessive surface oxidation is liable to take place.
  • the temperature and the time period of the precipitation can be selected appropriately and combined within the above ranges.
  • the step of homogenization the obtained ingot can be omitted, as necessary. If omitted, the following step of hot working the obtained homogenized product is also omitted.
  • the obtained product is hot worked at the working rate of 10% to 90%.
  • the step of hot working the obtained product can be omitted, as necessary.
  • the obtained product is cooled down to a room temperature (about 20° C. to 30° C.), and cold worked at the working rate of 10% to 80%. If the working rate is lower than 10%, the cold working effect is not adequately provided, and, if the working rate exceeds 80%, excessive cold working causes work hardening, and thus, makes further processing difficult.
  • the obtained cold worked product is precipitated at 400° C. to 600° C. for 1 hour to 8 hours in an annealing furnace. If the precipitation is performed at a temperature lower than 400° C., the effect of the heat treatment can not be obtained adequately, and if the precipitation is performed at a temperature higher than 600° C., the electric conductivity increases but the strength becomes poor due to the over-aging phenomenon.
  • the product can be anisotropic since precipitation of Cr granules as well as re-crystallization of a metallic microstructure from a prior processing is not adequate. Meanwhile, if the precipitation is performed for a time period longer than 8 hour, through increase of the electric conductivity can be expected by over aging, the microstructure becomes coarse to make a quality of the copper alloy material (the final product) poor, and the heat treatment for a long time period makes productivity poor.
  • the copper alloy material for continuous casting mold of the present invention can be produced, omitting the step of homogenization the obtained ingot together with the step of hot working the obtained product, or the step of hot working the obtained product alone.
  • the obtained product from the prior step can be cold worked at a working rate of 10% to 80%, and the steps thereafter including the step of first cold working, i.e., the first cold working step, the precipitation step and the second cold working step, can be progressed in the same way.
  • the step of homogenization the ingot and the successive cold working step can be performed, repeatedly.
  • the process for producing a copper alloy material of the present invention permits not only to cast even under an air atmosphere, but also obtain a final product of a copper alloy material for continuous casting mold, having excellent tensile strength and electric conductivity.
  • each of the ingots are cold worked at 60%, and precipitated at 480° C. for 3 hours.
  • Each obtained product is cold worked at 50% after cooling the product down to the room temperature, to obtain a final sample.
  • Test pieces having the composition shown in table 1 are cut from each of the products by the aforementioned production process. Then, their surface defects, tensile strength (TS), elongation (El), Vickers hardness (Hv), Brinell hardness (BH) and electric conductivity are tested, and the result of the above tests are shown in table 2.
  • the tensile strength and the elongation are measured according to KS B0802, and the electric conductivity, which is related to both of thermal and electric conductivity, is measured according to KS D0240.
  • the Vickers hardness is measured according to KS B0811 and the Brinell hardness is measured according to KS B0805.
  • Example 1 50.3 137 150.3 92.0
  • Example 2 52.0 140 158.4 88.4
  • Example 3 53.6 142 162.9 85.5
  • Example 4 52.4 139 156.5 89.0
  • Example 5 52.0 140 157.1 92.0
  • Example 6 53.7 141 160.1 83.7
  • Example 7 50.2 137 150.6 93.2
  • Example 8 51.5 138 153.1 90.6 C.
  • Example 1 120 — 90 C.
  • Example 3 — — 140 70 C.
  • Example 6 40.8 90 — 92.0
  • the specifications required for a copper alloy material for continuous casting mold used in steel industries are over 80% IACS electric conductivity and over 90 HB.
  • the copper alloy material of the present invention has the Brinell hardness (2.5/62.5 kg) of over 120 HB, and more particularly in the range of 130 HB to 150 HB, measured after processing the copper alloy material at 10% to 80% right after final heat treatment, and the electric conductivity of over 85% IACS, and more specifically, in the range of 85% IACS to 95% IACS.
  • test pieces of Examples 1 to 8 show similar electric conductivity to that of CuAgP material in comparative example 6, which is commercially available, while the test pieces show the tensile strength and the hardness better than the comparative example 6, and thus, these test pieces of Examples 1 to 8 meet all of specifications required for the copper alloy material for continuous casting mold.
  • FIG. 2 illustrates a graph showing softening resistance of a copper alloy material for continuous casting mold in accordance with a preferred Example of the present invention.
  • Brinell hardness (HB) of a test piece of the copper alloy material held for 30 minutes in each temperature section is measured, and their heat resistance properties are better than that of CuAgP in comparative example 6.
  • the softening resistance of the copper alloy material of this present invention is similar to CuCrZr in comparative example 2.
  • the present invention provides a copper alloy material for continuous casting mold which permits casting even in the atmosphere, and has high electric conductivity and excellent hardness; and a process for producing the same.

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US14/238,173 2011-08-11 2011-09-30 Copper alloy material for continuous casting mold and process for producing same Abandoned US20150376755A1 (en)

Applications Claiming Priority (3)

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KR1020110080180A KR101364542B1 (ko) 2011-08-11 2011-08-11 연속주조 몰드용 동합금재 및 이의 제조 방법
KR10-2011-0080180 2011-08-11
PCT/KR2011/007254 WO2013022144A1 (en) 2011-08-11 2011-09-30 Copper alloy material for continuous casting mold and process for producing same

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US20170292181A1 (en) * 2014-09-25 2017-10-12 Mitsubishi Materials Corporation CASTING MOLD MATERIAL AND Cu-Cr-Zr ALLOY MATERIAL
KR20180078244A (ko) * 2015-11-09 2018-07-09 미쓰비시 마테리알 가부시키가이샤 구리 합금 소재
US20180297109A1 (en) * 2015-10-15 2018-10-18 Mitsubishi Materials Corporation CASTING MOLD MATERIAL AND Cu-Cr-Zr-Al ALLOY MATERIAL
US20190062874A1 (en) * 2015-11-09 2019-02-28 Mitsubishi Materials Corporation Copper alloy material
US20190259966A1 (en) * 2018-02-21 2019-08-22 Samsung Display Co., Ltd. Display device
WO2020052714A1 (de) 2018-09-14 2020-03-19 Kme Germany Gmbh & Co. Kg Verwendung einer kupferlegierung
US11697864B2 (en) * 2017-10-18 2023-07-11 Poongsan Corporation Copper alloy strip having high heat resistance and thermal dissipation properties
CN116555620A (zh) * 2023-04-24 2023-08-08 扬州地标金属制品有限公司 一种多元合金材料及其制备方法

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CN105950902A (zh) * 2016-06-13 2016-09-21 芜湖卓越线束系统有限公司 高强度高导电率线束端子用合金材料及其制备方法

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DE4427939A1 (de) * 1994-08-06 1996-02-08 Kabelmetal Ag Verwendung einer aushärtbaren Kupferlegierung
JP3769695B2 (ja) * 1996-05-23 2006-04-26 同和鉱業株式会社 リードフレーム用銅合金及びその製造法
JP2004107741A (ja) 2002-09-19 2004-04-08 Kobe Steel Ltd 耐通電不良性に優れた銅合金材
JP2008081762A (ja) 2006-09-26 2008-04-10 Nikko Kinzoku Kk 電子材料用Ｃｕ−Ｃｒ系銅合金

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US10544495B2 (en) * 2014-09-25 2020-01-28 Mitsubishi Materials Corporation Casting mold material and Cu—Cr—Zr alloy material
US20170292181A1 (en) * 2014-09-25 2017-10-12 Mitsubishi Materials Corporation CASTING MOLD MATERIAL AND Cu-Cr-Zr ALLOY MATERIAL
US20180297109A1 (en) * 2015-10-15 2018-10-18 Mitsubishi Materials Corporation CASTING MOLD MATERIAL AND Cu-Cr-Zr-Al ALLOY MATERIAL
KR20180078244A (ko) * 2015-11-09 2018-07-09 미쓰비시 마테리알 가부시키가이샤 구리 합금 소재
US20180291490A1 (en) * 2015-11-09 2018-10-11 Mitsubishi Materials Corporation Copper alloy material
US20190062874A1 (en) * 2015-11-09 2019-02-28 Mitsubishi Materials Corporation Copper alloy material
KR102493118B1 (ko) 2015-11-09 2023-01-27 미쓰비시 마테리알 가부시키가이샤 구리 합금 소재
US11697864B2 (en) * 2017-10-18 2023-07-11 Poongsan Corporation Copper alloy strip having high heat resistance and thermal dissipation properties
US11515497B2 (en) * 2018-02-21 2022-11-29 Samsung Display Co., Ltd. Display device
US20190259966A1 (en) * 2018-02-21 2019-08-22 Samsung Display Co., Ltd. Display device
US11005054B2 (en) * 2018-02-21 2021-05-11 Samsung Display Co., Ltd. Display device comprising heat sink comprising metal alloy
US20210257567A1 (en) * 2018-02-21 2021-08-19 Samsung Display Co., Ltd. Display device
DE102018122574A1 (de) * 2018-09-14 2020-03-19 Kme Germany Gmbh & Co. Kg Kupferlegierung
RU2760444C1 (ru) * 2018-09-14 2021-11-25 Кме Спешл Продактс Гмбх Унд Ко. Кг Применение медного сплава
DE102018122574B4 (de) * 2018-09-14 2020-11-26 Kme Special Products Gmbh Verwendung einer Kupferlegierung
WO2020052714A1 (de) 2018-09-14 2020-03-19 Kme Germany Gmbh & Co. Kg Verwendung einer kupferlegierung
US12129538B2 (en) 2018-09-14 2024-10-29 Cunova Gmbh Use of a copper alloy
CN116555620A (zh) * 2023-04-24 2023-08-08 扬州地标金属制品有限公司 一种多元合金材料及其制备方法

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IN2014CN00928A (enrdf_load_stackoverflow) 2015-04-10

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