WO2004040042A1 - Matiere de cuivre a nanocristaux dotee d'une resistance et d'une conductivite tres elevees et son procede de fabrication - Google Patents

Matiere de cuivre a nanocristaux dotee d'une resistance et d'une conductivite tres elevees et son procede de fabrication Download PDF

Info

Publication number
WO2004040042A1
WO2004040042A1 PCT/CN2003/000867 CN0300867W WO2004040042A1 WO 2004040042 A1 WO2004040042 A1 WO 2004040042A1 CN 0300867 W CN0300867 W CN 0300867W WO 2004040042 A1 WO2004040042 A1 WO 2004040042A1
Authority
WO
WIPO (PCT)
Prior art keywords
strength
twin
nano
ultra
copper
Prior art date
Application number
PCT/CN2003/000867
Other languages
English (en)
French (fr)
Inventor
Lei Lu
Xiao Si
Yongfeng Shen
Ke Lu
Original Assignee
Institute Of Metal Research Chinese Academy Of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute Of Metal Research Chinese Academy Of Sciences filed Critical Institute Of Metal Research Chinese Academy Of Sciences
Priority to JP2004547350A priority Critical patent/JP4476812B2/ja
Priority to AU2003275517A priority patent/AU2003275517A1/en
Priority to EP03757640A priority patent/EP1567691B1/en
Priority to US10/532,674 priority patent/US7736448B2/en
Publication of WO2004040042A1 publication Critical patent/WO2004040042A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys

Definitions

  • the invention relates to a nano-crystalline metal material, in particular to an ultra-high-strength, ultra-high-conductivity nano-twin copper material and a preparation method thereof.
  • Copper and its alloys are one of the earliest and most widely used non-ferrous metals. China is one of the earliest countries to use copper alloys. In the Yin and Zhou dynasties more than 3,700 years ago, bronzes were used to manufacture bell jars and weapons. Until now, copper and its alloys are still the most widely used metal materials. The main characteristics of copper and its alloys are electrical conductivity, good thermal conductivity, good corrosion resistance in the atmosphere, sea water and many media, and good plasticity and wear resistance. It is suitable for various plastic processing and casting methods. This product is an indispensable metal material for industrial sectors such as electricity, electrical engineering, thermal engineering, chemical industry, instrumentation, shipbuilding and machinery manufacturing.
  • Fe and Ni has an influence on the magnetic properties of Cu, which is not good for the manufacture of compasses and aviation instruments; Cd, Zn, Sn, Pb, etc. It is volatile in vacuum, and it is restricted in the manufacture of tube parts.
  • Nanocrystalline materials refer to a class of single-phase or multi-phase solid materials composed of extremely fine grains with a characteristic dimension ranging from 1 to 100 nanometers. Due to its extremely fine grains and a large number of interface densities, and a large number of grain boundaries and grains In terms of physical and chemical properties, nano-materials exhibit huge differences in physical and chemical properties from ordinary micron-sized polycrystalline materials, and have peculiar mechanical, electrical, magnetic, optical, thermal, and chemical properties.
  • the strengthening method using solid solution strengthening and adding a second phase is also effective in blocking the movement of lattice dislocations, thereby strengthening the material.
  • the cold working method (or plastic deformation method) is also used to hinder the further movement of dislocations through a large number of dislocations generated during the deformation process. Therefore, all strengthening methods are based on introducing a large number of defects (such as grain boundaries, dislocations, point defects, second phases, etc.) to hinder the movement of dislocations. These defects, while hindering the movement of dislocations, also increase the scattering effect on the electrons, thus leading to a decrease in the conductive properties of the material.
  • the tensile strength (o y ) of ordinary coarse crystalline pure copper at room temperature is only 0.035 GPa, which is about two orders of magnitude lower than the theoretical prediction and the elongation is about 60%. After cold working (cold-rolled), the strength of the Cu material increased, and ⁇ ⁇ was about 250 GPa.
  • the yield strength of nano-copper materials has been greatly improved compared to coarse crystalline copper.
  • American scientist JR Weertman et al. Document 1: Sanders, PG, Eastman, JA & Weertman, JR, Elastic and tensile behavior of nanocrystalline copper and palladium, Acta Mater.
  • the nanocrystalline copper material with a grain size of about 30 nm prepared by an inert gas condensation method has a yield strength of 365 MPa when stretched at room temperature.
  • Professor R. Suryanarayana et al. Reference 2: Suryanarayana, R. et al., Mechanical properties of nanocrystalline copper produced by solution-phase synthesis, J. Mater. Res. 11, 439-448 (1996)
  • Heij was prepared by ball milling After the nano-copper powder is purified and cold-pressed, the yield strength of nano-copper with a grain size of about 26 nm is about 400 MPa, and the elongation of these two samples is very small about 1 ⁇ 2. %.
  • the grain size prepared by the severe plastic deformation method is about Room temperature compression experiments of a copper material at 109 nm show that its yield strength is about 400 MPa, and its room temperature (293K) resistivity is as high as 2.46 ⁇ 1 ( ⁇ 8 ⁇ ⁇ ⁇ (only 68% IACS)) [Reference 5: RK Islamgaliev, K. Pekala , M. Pekala and RZ Valiev., Phys. Stat. Sol "(a). 559-566, 162 (1997).] Summary of the Invention
  • the object of the present invention is to provide a nano-twin copper material with ultra-high strength and ultra-high conductivity and a preparation method thereof.
  • the technical solution of the present invention is as follows-ultra-high-strength ultra-high-conductivity nano-twin copper material, the microstructure of which is composed of sub-micron grains that are nearly equiaxed, and there are high-density different orientations inside the grains
  • the structure of the twin layer, the twin layers with the same orientation are parallel to each other, the thickness of the twin layer ranges from a few nanometers to 100 nm, and the length is 100 ⁇ 500 nm ;
  • the electrolyte is selected from electronic pure high-purity copper CuS0 4 solution, plus high-purity ion-exchanged water or high-purity distilled water, PH value is 0.5 1.5, 99.99% pure copper plate is used as the anode, and the surface of the cathode is plated with Iron plate or low carbon steel plate with Ni-P amorphous layer;
  • Electrolysis process parameters pulse current density is 40 ⁇ 100A / cm 2 , pulse plating is used; on time (t. N ) is 0.01 ⁇ 0.05s, off time (t. Ff ) is l ⁇ 3s, cathode anode distance 50 150 nun, anode-cathode area ratio 30 ⁇ 50: 1, electrolyte temperature 15 ⁇ 30 ° C; electrolyte adopts electromagnetic stirring method; additives: 0.02 ⁇ 0.2ml / l 5 ⁇ 25% strength gelatin aqueous solution and 0.2 ⁇ 1.0 ml / 1 5 ⁇ 25% high purity NaCl aqueous solution.
  • the invention uses the reasonable process and process parameters in the electrolytic deposition technology to prepare a copper material with a nano-scale twin wafer layer structure under the action of pulse current.
  • the thickness of the twin wafer layer ranges from a few nanometers to 100 nm. Its length is about 100 ⁇ 500 nm, and it has a unique microstructure;
  • the material of the present invention has a very high yield strength at room temperature, which can reach 900 MPa, which is much higher than the yield strength of nano-copper samples of comparable grain size prepared by other traditional methods. And this sample has very good conductivity, and the conductivity at room temperature (293K) can reach 96% ICAS.
  • the copper material in the present invention has a special nano-scale twin wafer layer structure, the material has very high strength, and also has very high electrical conductivity (because the twin boundary is a very stable interface structure) and Thermal stability. Therefore, this ultra-high-strength and ultra- ⁇ conducting nano-twin copper material is of great value to the rapid development of the computer industry, the wireless communication industry, and the printing industry.
  • the preparation method is simple.
  • the present invention utilizes the traditional electrolytic deposition technology, and it is only necessary to improve the process conditions and control the appropriate deposition parameters to obtain such a nano twin copper material with ultra-high strength and high conductivity with a nano twin structure.
  • Figure 1-1 is a bright-field observation image of a TEM image of the twins of the electrolytically deposited nano-twin copper material of the present invention.
  • Figure 1-2 is a statistical distribution of the grain size of the TEM photograph of the twins of the electrolytically deposited nanotwinned copper material of the present invention.
  • Figure 1-3 is the statistical distribution of the thickness of the twin layer of the TEM photograph of the twins of the electrolytically deposited nano-twin copper material of the present invention.
  • Figure 2 -1 is an HRTEM photograph of the twins of the electrolytically deposited nanocrystalline copper material of the present invention
  • Figure 2-2 is an electron diffraction pattern of an HRTEM photograph of the twins of electrolytically deposited nanocrystalline copper material of the present invention.
  • T is twin
  • A is matrix
  • a and T are twins.
  • FIG. 3 is a tensile curve of the nano-twin copper material and the coarse-grained copper material according to the present invention at room temperature.
  • Figure 4 is a comparison of the low-temperature resistance (4K-296K) of the nano-twin copper material and the ordinary coarse-grain copper material of the present invention. detailed description
  • Electrolytic deposition equipment single pulse electrolytic deposition equipment
  • the anode is a pure copper plate with a purity higher than 99.99%, and the cathode is an iron plate with an Ni-P amorphous layer on the surface.
  • Electrolysis process parameters pulse current density is 50 A / cm 2 , pulse plating; on-time (t. N ) is 0.02s, off-time (t. Ff ) is 2s, cathode-anode pole distance is 100 mm, The anode and cathode area ratio is 50:
  • the electrolysis temperature is 20 ⁇ , and the electrolyte is electromagnetically stirred.
  • Gelatin 0.1 ml / 1 (15% strength gelatin water solution);
  • FIG. 3 shows the true stress-strain curve of the electrolytically deposited nano-crystalline Cu sample at room temperature.
  • Figure 4 shows the nano twin of the present invention.
  • the low-temperature resistance (4K ⁇ 296K) of crystalline copper material and ordinary coarse-grained copper material is compared. It can be seen that the room temperature resistivity of Cu material with nano-twin structure is only 1.75 ⁇ 0.02 ⁇ 10 ⁇ 8 ⁇ ⁇ ⁇ , which is similar to ordinary coarse crystal
  • the room temperature resistivity of Cu materials is comparable.
  • Embodiment 1 The difference from Embodiment 1 lies in:
  • Electrolytic process parameters Pulse current density is 80 A / cm 2 , and the conduction time (t. N ) is 0.05s, turn-off time (t. Ff ) is 3s ; cathode and anode pole distance is 50mm, electrolyte temperature is 15 ° C;
  • high-purity, high-density, lamellar twin nanocrystalline Cu materials can also be prepared. It is observed by transmission electron microscope that the nanocrystalline Cu materials are also composed of sub-micron grains that are nearly equiaxed, and are inside the grains. There are high-density twin wafer layers with different orientations. The average thickness of the twin wafer layers is about 30 nm, and the dislocation density in the sample is also very small. The yield strength of the nanocrystalline Cu material at room temperature is 810 MPa, and the room temperature resistivity is 1.927 ⁇ 0 ⁇ 02 ⁇ 10 -8 ⁇ ⁇ ⁇ .
  • Embodiment 1 It differs from Embodiment 1 in that-
  • cathode and anode electrode pitch is 150mm, electrolysis temperature is 25 ° C ;
  • high-purity, high-density, flaky twin nanocrystalline Cu materials can also be prepared.
  • the transmission electron microscope observed that the nanocrystalline Cu material also consists of sub-micron grains that are nearly equiaxed. There are high-density twin wafer layers with different orientations inside the grains. The average thickness of the twin wafer layers is about 43 nm. The dislocation density in the sample was also small.
  • the yield strength of the nanocrystalline Cu material at room temperature is 650 MPa, and the room temperature resistivity is
  • the yield strength reaches the highest value (360 MPa), the grain size continues to decrease, and the yield strength also decreases.
  • the resistivity of the samples prepared by this method will be greatly improved, and the conductivity will be poor.
  • Comparative Example 4 American scientist J. Weertman et al. Used inert gas condensation method to prepare nano powder, and the powder was pressure-molded at 150 ° C (pressure is usually 1.4 GPa) to prepare a solid nanocrystalline copper material with an average grain size of 26 nm. The density of the sample was 99% of the theoretical density.
  • the tensile properties in a very small sample (the entire length of the sample is about 3 mm, and the cross-sectional area of the tensile section is 200 ⁇ 200 ⁇ m) show that the sample has a high yield strength, which can reach 535 MPa.
  • the mechanical property results obtained in small samples are difficult to represent the mechanical property results of macro samples.
  • Plys. Stat. Sol. (A) 162, 559 (1997)) used a severe plastic deformation method to obtain a sub-micron grade pure copper material with an average grain size of 210 nm.
  • the sample has good compactness but high residual stress. . Stretched at room temperature, the ultimate breaking strength can reach 500MPa and the elongation is about 5%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Conductive Materials (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)

Description

技术领域
本发明涉及纳米晶体金属材料，具体地说是一种超高强度、超高导电性纳米孪晶 铜材料及制备方法。 背景 ¾术
铜及其合金是人类应用最早和最广的一种有色金属。我国是应用铜合金最早的国 家之一， 远在 3700多年前的殷周时代就幵始使用青铜制造钟鼎和武器， 直到现在， 铜及其合金仍是应用最广的金属材料。铜及其合金的主要特点是导电， 导热性好，在 大气， 海水和许多介质中抗腐蚀性好， 并有很好的塑性和耐磨性， 适用于各种塑性加 工和铸造方法生产的各种产品， 是电力， 电工， 热工， 化工， 仪表， 造船和机械制造 等工业部门不可缺少的金属材料。
对于纯铜， 虽然它具有非常好的导电性能， 但其强度非常低。 因此， 为了改善铜 材料的力学性能，往往需要采取一些特殊的处理方法来提高材料的强度，如细化晶粒 法，添加合金元素法，冷加工法等。无论是哪种强化方法，在提高铜材料强度的同时， 都会损失其导电性能，例如， 通常情况下， 工业生产中可在铜中添加一些危害较小的 合金元素（如 Al， Fe, Ni, Sn， Cd, Zn， Ag， Sb等） 以提高其强度和硬度。 但是， 这些合金元素的加入往往会使铜的导电性大幅度下降； 另外， 少量 Fe和 Ni对 Cu 的磁性有影响， 对制造罗盘和航空仪器不利； Cd， Zn， Sn, Pb等在高温高真空中易 挥发， 制造电子管零件时受到限制。
在当今的现代科学领域中， 机械设备， 工具器械和仪器仪表装置都在向高速度、 高效率、 高灵敏度、低能耗、微型化方向发展， 因而无论是从精度、可靠性还是高综 合性能方面都对铜材料提出了更高的综合要求。例如， 在迅速发展的计算机行业，汽 车工业领域、 无线通讯业（如手提电话的插塞连接器及锂电池阳极等）、 印刷业（如 多层印制电路板和高密度印制电路板的制做等）等等高技术产品中，对新型高性能铜 材料的需求也越来越高，因此如何解决在大幅度提高铜材料强度的同时又能保持其优 异的导电性能这一问题越来越具有挑战性。
纳米晶体材料是指由极细晶粒组成，特征维度尺寸在 1~100纳米范围内的一类单 相或多相固体材料。由于其极细小的晶粒和大量的界面密度及大量处于晶界和晶粒内 的缺陷原子， 纳米材料在物理化学性能上表现出与普通微米级多晶体材料巨大的差 异， 具有奇特的力学， 电学， 磁学， 光学， 热学及化学等诸多方面的性能。
在工程应用上， 为了强化材料， 常采用细化晶粒法，这是一种利用大量存在的晶 界在限制或钉轧位错运动来提高材料的强度， 可由著名的 Hall-Petoh 关系 ( σ = σ。 + kd-112 )来描述。 然而这种强化效果并不是随着晶粒尺寸的减少而无限制 单调递增的， 当晶粒尺寸减少到一定程度， 尤其是达到纳米量级后，这种强化效应将 不存在了。事实上， 实验观察和计算机模拟工作都已经表明， 当材料的晶粒细化到纳 米量级或晶粒具有足够小的尺寸时， 强化效果减弱或者消失， 继而会出现软化效应。 这实际是由于当晶粒尺寸足够小的时候， 即已经接近点阵中位错间的平衡距离，也就 是说晶粒内部仅可容纳少量（甚至没有）位错。这时候晶界运动的能力会大幅度提高 (如晶界转动， 滑动等)， 晶界运动会使导致材料的强度降低。 因此， 对于纳米材料 来讲， 为了进一步提高强度必须要同时限制阻碍位错运动和晶界运动。
采用固溶强化和添加第二相的强化方法同样是有效地阻碍点阵位错的运动，从而 使材料得到强化。而采用冷加工法（或塑性变形法）强化也是通过变形过程中产生的 大量位错来阻碍位错的进一步运动。因此，所有的强化方法都是基于引入大量缺陷（如 晶界、位错、 点缺陷及第二相等等）来阻碍位错的运动。这些缺陷在阻碍位错运动的 同时也增加了对电子的散射效果， 因此也就导致了材料的导电性能下降。
例如， 普通粗晶体纯铜在室温下拉伸的屈服强度 （oy)仅为 0.035 GPa， 这要比 理论预测值低大约二个数量级， 延伸率约为 60%。 冷加工处理（冷轧态）后 Cu材料 的强度有所提高， σγ约为 250 GPa。纳米铜材料的屈服强度较粗晶体铜有了大幅度的 提高， 美国科学家 J. R. Weertman等人 （文献 1 : Sanders, P.G. , Eastman, J. A. & Weertman, J.R., Elastic and tensile behavior of nanocrystalline copper and palladium, Acta Mater. 45 , 4019-4025 ( 1997 ) )利用惰性气体冷凝法制备的晶粒尺寸约为 30nm 的纳米晶体铜材料， 在室温拉伸时， 其屈服强度可达 365 MPa。 R. Suryanarayana教 授等 (文献 2: Suryanarayana, R. et al. , Mechanical properties of nanocrystalline copper produced by solution-phase synthesis, J. Mater. Res. 11 , 439-448 ( 1996) )禾 ij用球磨法 制备的纳米铜粉， 再将该纳米铜粉提纯冷压成型出后， 得到晶粒尺寸约为 26nm的纳 米铜的屈服强度约为 400 MPa， 这两种样品的延伸率都非常小约 1~2%。 国内卢磊， 卢柯等人（专利申请号： 01114026.7)利用电解沉积技术同样制备出晶粒尺寸为 30 nm 的块体纳米铜材料，表明该沉积态纳米铜样品具有小角晶界（这同传统的纳米材料所 具有的大角晶界有所不同）其室温屈服强度为 119 MPa， 延伸率为 30%。如果将此沉 积态纳米晶体铜样品在室温下轧制，其样品的平均晶粒尺寸不变，但晶粒与晶粒之间 取向差增加，且样品中位错密度增加，这种具有相同晶粒尺寸不同微观结构的轧制态 纳米晶体铜材料的屈服强度大幅度提高， 可达 425 MPa， 但延伸度下降， 仅为 1.4%。 J. R. eertman等人（文献 3 : Legros, Μ·， Elliott, B.R., Rittner, Μ·Ν·， Weertman, J.R. & Hemker, K.J., Microsample tensile testing of nanocrystalline metals, Philos. Mag. A. 80, 1017-1026 (2000) )利用微型纳米晶体铜试样 〈l mm〉拉伸时获得了高达 535 MPa的屈服强度。利用表面纳米化制备纳米铜样品（文献 4: Y.M. Wang, D. Pan, K. Lu, K.J. Hemker and E. Ma" Microsample tensile testing of nanocrystalline Cu, Scripta Mater. , 48,1581-1586 (2003)), 微小样品 （样品厚度约为 11~14μπι， 标距长为 1.7mm， 标距 截面为 0.5x0.015mm2)的室温拉伸结果表明， 其屈服强度可达 760MPa， 但几乎没有 延伸率。从以上分析可以看出， 目前无论是采用加工硬化法还是细化晶粒法（纳米材 料)， 所得到的纯 Cu材料的屈服强度都是有限的。 同时利用严重塑性变形法制备的 晶粒尺寸约为 109nm的铜材料室温压缩实验表明其屈服强度约为 400MPa，而其室温 (293K) 电阻率高达 2.46χ1(Γ8Ω·πι (仅为 68%IACS) [文献 5: R.K. Islamgaliev, K. Pekala, M. Pekala and R.Z. Valiev., Phys. Stat. Sol" (a) . 559-566, 162(1997).] 发明内容
本发明的目的是提供一种具有超高强度超高导电性的纳米孪晶铜材料及制备方 法。
为了实现上述目的， 本发明的技术方案如下- 超高强度超高导电性纳米孪晶铜材料， 其微观结构由近于等轴的亚微米晶粒组 成，在晶粒内部存在高密度的不同取向的孪晶片层结构，取向相同的孪晶片层之间相 互平行， 孪晶片层的厚度从几个纳米到 100 nm不等， 其长度为 100~500 nm;
另外， 具有如下性质： 密度为 8.93±0.03 g/cm3， 纯度为 99.997±0.02 at%， 在室温 条件下拉伸速率为 6xl0"3/s, 其屈服强度可达 900±10MPa， 延伸率为 13.5±0.5%; 所 述亚微米晶粒尺寸为 300-1000 nm;在室温（293K)时的电阻率为 1.75±0.02χ10·8Ω·ιη (相当于电导率 g = 96% IACS其中 IACS为 International annealed copper standard缩 写）。 电阻温度系数为
Figure imgf000005_0001
超髙强度超高导电性纳米孪晶铜材料的制备方法： 利用电解沉积制备技术， 电解液选用电子纯级高纯铜 CuS04溶液， 加配高纯度 离子交换水或高纯度级蒸馏水， PH值为 0.5 1.5， 阳极选用 99.99%的纯铜板， 阴极 为表面镀有 Ni-P非晶层的铁板或低碳钢板；
电解工艺参数：脉冲电流密度为 40~100A/cm2，采用脉冲方式电镀；导通时间（t。n) 为 0.01~0.05s， 关闭时间（t。ff)为 l~3s， 阴极阳极极距为 50 150 nun, 阳极阴极面积 比为 30~50： 1， 电解液温度为 15~30°C ; 电解液采用电磁搅拌方式； 添加剂： 0.02 ~0.2ml/l 5~25%浓度的明胶水溶液及 0.2~1.0 ml/1 5~25%浓度的高纯 NaCl水溶液。
本发明具有如下优点-
1. 具有优良的性质。 本发明利用电解沉积技术中合理的工艺过程和工艺参数在 脉冲电流的作用下，制备出具有纳米级孪晶片层结构的铜材料，该孪晶片层的厚度从 几个纳米到 100 nm不等， 其长度大约为 100~500 nm， 具有独特的微观结构；
本发明材料具有非常高的室温屈服强度， 可达到 900 MPa，该强度已远高于用其 它传统方法制备的相当晶粒尺寸的纳米铜样品的屈服强度。并且该样品具有非常好的 导电性， 室温下 (293K)导电率可达 96% ICAS。
2. 应用性极强。 由于本发明中这种铜材料具有特殊的纳米量级孪晶片层结构， 使得材料具有非常高的强度， 同时也具有非常高的导电性能（因为孪晶界是一种非常 稳定的界面结构）和热稳定性。因此，这种超高强度超髙导电性的纳米孪晶铜材料对 迅速发展的计算机行业及无线通讯业及印刷业的发展具有重要价值。
3. 制备方法简单。 本发明利用传统的电解沉积技术， 只需改进工艺条件， 控制 适当的沉积参数即可获得这种具有纳米孪晶组织的超高强度超高导电性的纳米孪晶 铜材料。 附图说明
图 1-1 为本发明电解沉积纳米孪晶铜材料孪晶的 TEM照片明场观察像。
图 1-2 为本发明电解沉积纳米孪晶铜材料孪晶的 TEM照片的晶粒尺寸的统计分 布图。
图 1-3 为本发明电解沉积纳米孪晶铜材料孪晶的 TEM照片的孪晶片层厚度的统 计分布图。
图 2 -1为本发明电解沉积纳米晶体铜材料孪晶的 HRTEM照片
图 2-2为本发明电解沉积纳米晶体铜材料孪晶的 HRTEM照片的电子衍射花样， 其中 T为孪晶， Α为基体， A和 T互为孪晶。
图 3 为室温条件下， 本发明纳米孪晶铜材料和粗晶铜材料的拉伸曲线。
图 4为本发明纳米孪晶铜材料和普通粗晶铜材料的低温电阻 (4K-296K) 比较。 具体实施方式
下面结构附图和实施例详述本发明。
实施例 1
1. 利用电解沉积技术制备薄片状纳米孪晶晶体 Cu材料
电解沉积设备： 单脉冲电解沉积设备
电解沉积所用电解液要求： 电子纯级 CuS04溶液， 严格控制电解液中重金属杂 质含量， 配电解液所用水应为高纯度去离子水， 电解液酸度为： PH=1。
阴， 阳极要求： 阳极为纯度高于 99.99%的纯铜板， 阴极为表面镀有 Ni-P非晶层 的铁板。
2. 电解工艺参数： 脉冲电流密度为 50 A/cm2， 脉冲方式电镀； 导通时间 （t。n) 为 0.02s， 关闭时间 （t。ff) 为 2s， 阴极阳极极距为 100 mm， 阳极、 阴极面积比为 50:
1； 电解温度为 20Ό , 电解液采用电磁搅拌方式。
添加剂： 明胶： 0.1 ml/1 ( 15%浓度的明胶水溶液）；
高纯 NaCl： 0.6 ml/1 ( 15%浓度的 NaCl水溶液）。
制备出超高纯度、 高致密度、 具有纳米尺度孪晶薄片状 Cu材料（l nm=l(T9m)， 该纳米孪晶 Cu材料在室温（仅为 0.22 Tm， Tm为材料的熔点温度）的屈服强度为 900 ±10MPa, 电阻率为 1.75±0.02χ10·8Ω·ηι (相当于 96% IACS)。
化学分析结果表明， 沉积态纳米 Cu样品的纯度为 99.998 at%。 微量杂质化学成 分含量如下表所示：
元素 微含量（％) 元素 微含量（％)
Bi <0.00003 Sn <0.0001
Sb 0.00005 Ag 0.0002
As 0.0001 Co 0.00003
Pb 0.00005 Zn 0.00005
Fe 0.001 Ni 0.00005 用 Archimedes原理测量样品密度为 8.93±0.03 g/cm3,相当于多晶体纯 Cu理论密 度（8.96 g/cm3)的 99.7%。高分辨电子显微镜观察纳米晶体 Cu材料由近于等轴的亚 微米（300~1000 nm)晶粒组成，在晶粒内部存在高密度的不同取向的孪晶片层结构， 相同取向的孪晶片层之间相互平行（图 1-1、 1-2、 1-3所示）。孪晶片层的厚度从几个 纳米到 100 nm不等， 平均孪晶片层厚度约为 15 nm， 其长度大约为 100~500 nm。 样 品中的位错密度很小。大多数孪晶界面属于完整界面， 也有一部分不全位错存在（图 1-1、 1-2、 1-3， 图 2-1、 2-2所示）。
电解沉积纳米孪晶晶体铜的室温拉伸： 图 3所示为电解沉积纳米晶体 Cu样品室 温下的真应力 -应变曲线， 为了比较， 图中同时给出了粗晶铜材料的拉伸曲线。 从图 中可以看出， 当拉伸速率为 6χ10·3 S"1时， 电解沉积孪晶纳米晶体 Cu 的屈服强度 CTy=900±10 MPa, 延伸率为 13.5%。 图 4为本发明纳米孪晶铜材料和普通粗晶铜材料 的低温电阻（4K~296K) 比较。 可以看出具有纳米孪晶结构的 Cu材料的室温电阻率 仅为 1.75±0.02χ10·8Ω·ηι， 与普通粗晶体 Cu材料的室温电阻率相当。
实施例 2
与实施例 1不同之处在于：
1 )利用电解沉积技术制备薄片状纳米晶体 Cu材料： 电解液用电子纯级高纯度 硫酸铜 CuS04溶液， 加配高纯度蒸溜水， 酸度为 PH=0.5; 阴、 阳极： 阳极为纯度高 于 99.99%的纯铜板， 阴极为表面镀有 Ni-P非晶层的铁板， 阳极阴极面积比为 30: 1。
2)添加剂： 5 %浓度的明胶水溶液 0.02 ml/1, 5%浓度的高纯 NaCl水溶液 0.2ml/l; 电解工艺参数： 脉冲电流密度为 80A/cm2， 导通时间 （t。n)为 0.05s, 关闭时间 （t。ff) 为 3s; 阴、 阳极极距为 50mm， 电解液温度为 15 °C ;
该工艺条件下同样可制备出高纯度、 高致密度、 薄片状孪晶纳米晶体 Cu材料， 透射电子显微镜观察该纳米晶体 Cu材料也由近于等轴的亚微米晶粒组成， 在晶粒内 部存在高密度的不同取向的孪晶片层结构， 孪晶片层的平均厚度约为 30 nm， 样品中 的位错密度也很小。 该纳米晶体 Cu材料在室温的屈服强度为 810 MPa， 室温电阻率 为 1.927±0·02χ10-8Ω·ιη。
实施例 3
与实施例 1不同之处在于-
1 ) 利用电解沉积技术制备薄片状纳米晶体 Cu材料： 电解液用电子纯级硫酸铜 CuS04溶液，加配高纯度蒸熘水，酸度为 PH=1.5; 阴、阳极：阳极为纯度高于 99.99% 的纯铜板， 阴极为表面镀有 Ni-P非晶层的低碳钢板， 阳极阴极面积比为 40: 1。
2)添加剂 : 25%浓度的明胶水溶液 0.15 ml/l，25%浓度的高纯 NaCl水溶液 l.Oml/1; 电解工艺参数： 脉冲电流密度为 40A/cm2， 导通时间（ton)为 0.01s， 关闭时间（t。ff)为
Is; 阴、 阳极极距为 150mm， 电解温度为 25°C ;
该工艺条件下也可制备出高纯度、 高致密度、 薄片状孪晶纳米晶体 Cu材料。 透 射电子显微镜观察该纳米晶体 Cu材料也由近于等轴的亚微米晶粒组成， 在晶粒内部 存在高密度的不同取向的孪晶片层结构， 孪晶片层的平均厚度约为 43 nm。样品中的 位错密度也很小。 该纳米晶体 Cu材料在室温的屈服强度为 650 MPa， 室温电阻率为
2.151±0. 2χ10-8Ω·πι。
比较例 1
普通退火态粗晶体纯铜 （晶粒尺寸约为 100 μη )在室温下拉伸， 其断裂极限强 度 ≤200 MPa， 屈服强度 ≤35 MPa， 延伸率 ≤60 %。 冷轧后的普通粗晶体 纯铜的断裂强度和屈服强度分别可提高到 290MPa和 250MPa，其延伸率约为 8%。因 此， 对于普通粗晶体纯铜 (无论是退火态还是冷轧态)其极限屈服强度往往小于 250 MPa。
比较例 2
美国科学家 R. Suryanarayana等人利用机械合金化技术制备的纳米晶体 Cu粉末， 经提纯后加压成型， 制备成块体的纳米晶体 Cu样品 （晶粒尺寸为 26 nm) o 拉伸状 态下该样品的屈服强度可以达到 400 MPa。
比较例 3
美国科学家 j. Weertman等人利用惰性气体冷凝法以及高真空（10—5 ~10—6Pa)原 位加压技术 （压力通常为 1~5 GPa)， 制备出平均晶粒尺寸在 22~110 nm 的固体纳米 晶体铜材料，样品的密度约为理论密度的 96%，且样品中微观应变较大。室温静态拉 伸实验结果表明， 该纳米晶体铜材料的强度较普通粗晶体铜材料有较大幅度的提高， 其断裂强度可高达 415Mpa -480 MPa, 屈服强度可达到 300 Mpa~360 MPa。 样品的 强度与样品的制备工艺及平均晶粒尺寸有关系， 如晶粒尺寸越细小，其强度越高， 晶 粒尺寸越粗大， 其强度较低， 并且塑性随晶粒尺寸的减小而减小。当晶粒尺寸减小到 22 nm 时， 屈服强度达到最高值（360 MPa) , 晶粒尺寸继续减小， 屈服强度也降低 了。 但利用此方法制备的样品其电阻率会大幅度提高， 导电性能差。
比较例 4 美国科学家 J. Weertman等人利用惰性气体冷凝法制备出纳米粉末， 将该粉末在 150°C加压成型（压力通常为 1.4GPa)，制备出平均晶粒尺寸在 26nm的固体纳米晶体 铜材料， 样品的密度为理论密度的 99%。在非常小的样品（样品整个长度约为 3mm, 拉伸段的横截面积为 200χ200μιη) 中拉伸性能结果表明该样品具有较高的屈服强度， 可达 535 MPa。但是这种在小样品中得到的力学性能结果很难代表宏观样品的力学性 能结果。
比较例 5
国内卢磊，卢柯等人利用电解沉积技术制备出晶粒尺寸为 30nm的块体纳米铜材 料，表明该沉积态纳米铜样品具有小角晶界（这同传统的纳米材料所具有的大角晶界 有所不同）其室温屈服强度为 119 MPa， 延伸率为 30%。如果将此沉积态纳米晶体铜 样品在室温下轧制，其样品的平均晶粒尺寸不变， 但晶粒与晶粒之间取向差增加， 且 样品中位错密度增加，这种具有相同晶粒尺寸不同微观结构的轧制态纳米晶体铜材料 的屈服强度大幅度提高， 可达 425 MPa， 但延伸度下降仅为 1.4%。
比较例 6
俄罗斯科学家 R.Z. Valiev (R.K. Islamgaliev, P. Pekala, M. Pekala and R. E. Valiev,
Plys. Stat. Sol. (a) 162, 559(1997))利用严重塑性变形法获得了亚微米级的纯铜材料， 其平均晶粒尺寸为 210nm， 样品致密性较好， 但残余应力很大。在室温下拉伸， 其极 限断裂强度可达 500MPa， 延伸率约为 5%， 这种材料室温下的电阻较大， 电阻率为 p = 2.24x 1 (Τ8 Ωιη (相当于电导率 g = 70% IACS )。

Claims

叔 利 要 求 书
1. 一种超高强度超高导电性纳米孪晶铜材料， 其特征在于： 其微观结构由近于 等轴的亚微米晶粒组成，在晶粒内部存在高密度的不同取向的孪晶片层结构，取向相 同的孪晶片层之间相互平行， 孪晶片层的厚度从几个纳米到 100 nm, 其长度为 100~500 nm。
2.按照权利要求 1所述超高强度、 超高导电性纳米孪晶铜材料， 其特征在于具有 如下性质： 密度为 8.93±0.03 g/cm3， 纯度为 99.997±0.02 at%， 在室温条件下拉伸速率 为 6xl0—3/s， 其屈服强度可达 900±10MPa， 延伸率为 13.5±0.5%； 在室温 （293K) 时 的电阻率为 1.75±0.02χ10·8Ω·πι， 电阻温度系数为
Figure imgf000011_0001
3.按照权利要求 1所述超髙强度、 超高导电性纳米孪晶体铜材料， 其特征在于： 所述亚微米晶粒尺寸为 300~1000nm。
4. 一种按照权利要求 1所述超高强度超高导电性纳米孪晶铜材料的制备方法， 其特征在于： 利用电解沉积制备技术， 电解液选用电子纯级高纯铜 CuS04溶液， 加 配高纯度离子交换水或高纯度级蒸馏水， PH值为 0.5~1.5, 阳极选用 99.99%的纯铜 板， 阴极为表面镀有 Ni-P非晶层的铁板或低碳钢板；
电解工艺参数：脉冲电流密度为 40~100A/cm2，采用脉冲方式电镀；导通时间（t。n) 为 0.01~0.05s， 关闭时间 （t。ff)为 l~3s， 阴极阳极极距为 50~150mm， 阳极阴极面积 比为 30 50: 1， 电解液温度为 15~30°C ; 电解液采用电磁搅拌方式；
添加剂： 0.02 ~0.2ml/l 5~25%浓度的明胶水溶液及 0.2〜1.0 ml/1 5~25%浓度的 高纯 NaCl水溶液。
PCT/CN2003/000867 2002-11-01 2003-10-16 Matiere de cuivre a nanocristaux dotee d'une resistance et d'une conductivite tres elevees et son procede de fabrication WO2004040042A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2004547350A JP4476812B2 (ja) 2002-11-01 2003-10-16 超高強度及び導電率を有するナノ結晶銅材料ならびにその製造方法
AU2003275517A AU2003275517A1 (en) 2002-11-01 2003-10-16 A nano icrystals copper material with super high strength and conductivity and method of preparing thereof
EP03757640A EP1567691B1 (en) 2002-11-01 2003-10-16 A nano crystals copper material with super high strength and conductivity and method of preparing thereof
US10/532,674 US7736448B2 (en) 2002-11-01 2003-10-16 Nano icrystals copper material with super high strength and conductivity and method of preparing thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN02144519 2002-11-01
CN02144519.2 2002-11-01

Publications (1)

Publication Number Publication Date
WO2004040042A1 true WO2004040042A1 (fr) 2004-05-13

Family

ID=32182023

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2003/000867 WO2004040042A1 (fr) 2002-11-01 2003-10-16 Matiere de cuivre a nanocristaux dotee d'une resistance et d'une conductivite tres elevees et son procede de fabrication

Country Status (5)

Country Link
US (1) US7736448B2 (zh)
EP (1) EP1567691B1 (zh)
JP (1) JP4476812B2 (zh)
AU (1) AU2003275517A1 (zh)
WO (1) WO2004040042A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102534703A (zh) * 2012-01-05 2012-07-04 北京工业大学 一种制备纳米/微米晶复合结构纯铜的方法

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007044959A1 (en) * 2005-10-13 2007-04-19 Inframat Corporation Patterned magnetic inductors
EP3336707A1 (en) 2006-05-05 2018-06-20 Hybir Inc. Group based complete and incremental computer file backup system, process and apparatus
US9005420B2 (en) * 2007-12-20 2015-04-14 Integran Technologies Inc. Variable property electrodepositing of metallic structures
US20090250352A1 (en) * 2008-04-04 2009-10-08 Emat Technology, Llc Methods for electroplating copper
WO2010033873A1 (en) * 2008-09-19 2010-03-25 Fort Wayne Metals Research Products Corporation Fatigue damage resistant wire and method of production thereof
JP4505545B1 (ja) * 2009-11-30 2010-07-21 有限会社ナプラ 回路基板及び電子デバイス
JP2012038823A (ja) * 2010-08-04 2012-02-23 Nitto Denko Corp 配線回路基板
KR101255548B1 (ko) * 2011-02-24 2013-04-17 한양대학교 에리카산학협력단 나노쌍정 구조가 형성된 구리재료의 형성방법
ES2503566T3 (es) 2011-09-29 2014-10-07 Sandvik Intellectual Property Ab Acero inoxidable austenítico TWIP y nano-duplicado y método para producirlo
TWI432613B (zh) 2011-11-16 2014-04-01 Univ Nat Chiao Tung 電鍍沉積之奈米雙晶銅金屬層及其製備方法
US9822430B2 (en) 2012-02-29 2017-11-21 The United States Of America As Represented By The Secretary Of The Army High-density thermodynamically stable nanostructured copper-based bulk metallic systems, and methods of making the same
WO2014030779A1 (ko) * 2012-08-22 2014-02-27 한양대학교 에리카산학협력단 나노쌍정 구조가 형성된 구리재료의 형성방법 및 이에 의해 제조된 구리재료
US20140271336A1 (en) 2013-03-15 2014-09-18 Crs Holdings Inc. Nanostructured Titanium Alloy And Method For Thermomechanically Processing The Same
US10233934B2 (en) * 2013-08-03 2019-03-19 Schlumberger Technology Corporation Fracture-resistant self-lubricating wear surfaces
CN105177645B (zh) * 2015-07-27 2017-05-31 昆明理工大学 一种多层复合梯度纳米纯铜材料的制备方法
CN107619963B (zh) * 2016-07-15 2020-01-03 中国科学院金属研究所 具备超低摩擦系数的金属或合金以及能够大幅降低金属或合金摩擦系数的方法
CN108326069B (zh) * 2017-12-26 2019-08-20 湖南中大冶金设计有限公司 一种高强度微米、纳米级孪晶铜合金丝材的制备方法
EP3814551A4 (en) 2018-06-26 2022-01-19 Purdue Research Foundation HIGH STRENGTH SINGLE-CRYSTAL-LIKE NANOTWIN NICKEL COATINGS AND PROCESS FOR THE PRODUCTION THEREOF
SG11202104479WA (en) * 2018-10-31 2021-05-28 Lam Res Corp Electrodeposition of nanotwinned copper structures
TWI731293B (zh) 2019-01-18 2021-06-21 元智大學 奈米雙晶結構
TWI686518B (zh) * 2019-07-19 2020-03-01 國立交通大學 具有奈米雙晶銅之電連接結構及其形成方法
TWI709667B (zh) 2019-12-06 2020-11-11 添鴻科技股份有限公司 奈米雙晶銅金屬層及其製備方法及包含其的基板
CN112719692B (zh) * 2021-04-01 2021-07-09 四川西冶新材料股份有限公司 一种900MPa级高强钢气保护实心焊丝及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1105398A (zh) * 1993-10-22 1995-07-19 古尔德电子有限公司 电解淀积铜箔及其制作方法
CN1337475A (zh) * 2000-08-04 2002-02-27 三井金属鉱业株式会社 电沉积铜箔的制造方法和电沉积铜箔
CN1389597A (zh) * 2001-06-01 2003-01-08 中国科学院金属研究所 一种高强度高导电性纳米晶体铜材料及制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6126806A (en) * 1998-12-02 2000-10-03 International Business Machines Corporation Enhancing copper electromigration resistance with indium and oxygen lamination
US20020015833A1 (en) 2000-06-29 2002-02-07 Naotomi Takahashi Manufacturing method of electrodeposited copper foil and electrodeposited copper foil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1105398A (zh) * 1993-10-22 1995-07-19 古尔德电子有限公司 电解淀积铜箔及其制作方法
CN1337475A (zh) * 2000-08-04 2002-02-27 三井金属鉱业株式会社 电沉积铜箔的制造方法和电沉积铜箔
CN1389597A (zh) * 2001-06-01 2003-01-08 中国科学院金属研究所 一种高强度高导电性纳米晶体铜材料及制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102534703A (zh) * 2012-01-05 2012-07-04 北京工业大学 一种制备纳米/微米晶复合结构纯铜的方法

Also Published As

Publication number Publication date
JP2006505101A (ja) 2006-02-09
AU2003275517A1 (en) 2004-05-25
EP1567691A1 (en) 2005-08-31
EP1567691B1 (en) 2012-08-22
US7736448B2 (en) 2010-06-15
JP4476812B2 (ja) 2010-06-09
US20060021878A1 (en) 2006-02-02
EP1567691A4 (en) 2010-02-03

Similar Documents

Publication Publication Date Title
WO2004040042A1 (fr) Matiere de cuivre a nanocristaux dotee d&#39;une resistance et d&#39;une conductivite tres elevees et son procede de fabrication
CN1234914C (zh) 一种超高强度超高导电性纳米孪晶铜材料及制备方法
CN102400188B (zh) 一种&lt;111&gt;织构纳米孪晶Cu块体材料及制备方法
Lin et al. Excellent anti-arc erosion performance and corresponding mechanisms of a nickel-belt-reinforced silver-based electrical contact material
CN108149046B (zh) 一种高强、高导石墨烯/铜纳米复合材料及其制备方法和应用
CN110331316B (zh) 一种高强耐热石墨烯铝复合导体材料及制备方法
Wang et al. Preparation of electro-reduced graphene oxide/copper composite foils with simultaneously enhanced thermal and mechanical properties by DC electro-deposition method
Duan et al. Effect of current density on the microstructure and magnetic properties of electrodeposited Co2FeSn Heusler alloy
US20220042195A1 (en) Method for preparing copper-based graphene/aluminum composite wire with high electrical conductivity
WO2020229881A1 (en) A method for the manufacture of graphene oxide from expanded kish graphite
Muxi et al. Research progress on preparation technology of graphene-reinforced aluminum matrix composites
CN1181224C (zh) 一种高强度高导电性纳米晶体铜材料的制备方法
Cong et al. Effect of La2O3 addition on copper matrix composites reinforced with Al2O3 ceramic particles
CN102031490B (zh) 一种高强度高导电性纳米晶体铜材料及制备方法
WO2004094699A1 (en) Nano invar alloys and a process of producing the same
Zhang et al. Introduction of nanotwins into nanoprecipitations strengthened CoCrNiMo0. 2 alloy to achieve strength and ductility trade-off: A comparative research
Tao et al. Effect of high contents of nickel and silicon on the microstructure and properties of Cu–Ni–Si alloys
Zheng et al. Mechanical properties and electrical conductivity of nano-La2O3 reinforced copper matrix composites fabricated by spark plasma sintering
CN101220425A (zh) 一种高强度钠米级晶体镍材料及其制备方法
Xu et al. GO/MgO/Mg interface mediated strengthening and electromagnetic interference shielding in AZ31 composite
CN110408976B (zh) 一种具有组织可控的石墨烯/纳米孪晶复合材料及其制备方法
Ding et al. Microstructure evolution and aging hardening in a Cu-25Ni-25Mn alloy
US20200269314A1 (en) Boron-nitride nanoplatelet(s)/metal nanocomposite powder and preparing method thereof
Chaudhari et al. Structure and properties of dual oxide particles doped Ni-Fe/In2O3-WO3 functional nanocomposite coatings
CN107460378B (zh) 一种Al-Si-Fe-Mg-Cu合金导体材料及其制备方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2006021878

Country of ref document: US

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 10532674

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2004547350

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2003757640

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2003757640

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 10532674

Country of ref document: US