CN1234914C - Nano twin crystal copper material with ultrahigh strength and superhigh conductivity as well as preparation method - Google Patents
Nano twin crystal copper material with ultrahigh strength and superhigh conductivity as well as preparation method Download PDFInfo
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Abstract
The present invention relates to a nanocrystal metal material, particularly to a nano twin crystal copper material with ultrahigh strength and ultrahigh conductivity and a preparation method. An electrodeposit technique is used to prepare polycrystal Cu materials with high purity; the microstructure of the polycrystal Cu materials comprises crystal grains of 300 to 1000 submicrons, which approximately have equal axes. High-density twin crystal layer structures in different directions exist in the crystal grains, and twin crystal layers in the same direction are parallel to each other. The thickness of the twin crystal layers is from a plurality of NM to 100 NM, and the length is from 100 to 500 NM. Compared with the prior art, the present invention has favorable properties. When the material is stretched at the room temperature, the yield strength can reach 900MPa, and the breaking strength can reach 1086MPa. The ultrahigh strength of the material is greatly better than that of copper materials prepared from the same chemical ingredients with other various methods. Meanwhile, the tests of low-temperature resistance show that the material has favorable conductivity which approach to that of the ordinary coarse crystal copper materials, and the electric resistivity at the room temperature is from 1.75-0.02*10<-8> omega. M to 1.75 + 0.02*10<-8>omega. M, which is equal to 96% LACS.
Description
Technical field
The present invention relates to the nanocrystal metallic substance, specifically a kind of superstrength, ultra-high conductivity nano twin crystal copper product and preparation method.
Background technology
Copper and alloy thereof are human the application the earliest and the widest a kind of non-ferrous metal.China uses one of copper alloy country the earliest, and the abundant Zhou Shidai before more than 3700 years just brings into use bronze to make bronze object and weapon, and up to now, copper and alloy thereof are still most widely used metallic substance.The principal feature of copper and alloy thereof is a conduction, thermal conductivity is good, and at atmosphere, erosion resistance is good in seawater and the many media, and good plasticity and wear resistance arranged, being applicable to the various products that various plastic workings and castmethod are produced, is electric power, the electrician, the thermal technology, chemical industry, instrument, the indispensable metallic substance of industrial sectors such as shipbuilding and machinofacture.
For fine copper, though it has extraordinary conductivity, its intensity is very low.Therefore,, often need to take some particular processing methods to improve the intensity of material,, add the alloying element method, cold process etc. as the crystal grain thinning method in order to improve the mechanical property of copper product.No matter be which kind of enhancement method, when improving copper product intensity, all can lose its conductivity, for example, generally, can in copper, add in the industrial production the less alloying element of some harm (as Al, Fe, Ni, Sn, Cd, Zn, Ag, Sb etc.) to improve its intensity and hardness.But the adding of these alloying elements tends to make the electroconductibility of copper to descend significantly; In addition, small amount of Fe and Ni are influential to the magnetic of Cu, and be unfavorable to making compass and aeronautical instrument; Cd, Zn, Sn, Pb etc. are volatile in the high temperature high vacuum, are restricted when making the electron tube part.
In current modern science field, mechanical means, instrument apparatus and instrument device are all developing to high-speed, high-level efficiency, highly sensitive, less energy-consumption, microminiaturized direction, thereby are all copper product have been proposed higher composite request from precision, reliability or high combination property aspect.For example, the computer industry that is developing rapidly, in auto industry field, cableless communication industry (as the plug-in connector of Cell phone and Anode of lithium cell etc.), press (as manufacturing of multilayer printed circuit board and high-density printed circuit board etc.) or the like the high-tech product, demand to the novel high-performance copper product is also more and more higher, therefore how to solve to keep its this problem of excellent conductivity more and more challenging when increasing substantially copper product intensity again.
Nano crystal material is meant by superfine crystal grain to be formed, the single-phase or multiphase solid material of the class of characteristic dimension size in 1～100 nanometer range.Because its superfine little crystal grain and a large amount of interphase densities reach and are in crystal boundary and intragranular defective atom in a large number, nano material shows on physical and chemical performance and the huge difference of common micron order polycrystalline material, has peculiar mechanics, electricity, magnetics, optics, the performance of all many-sides such as calorifics and chemistry.
On engineering is used, for strengthening material, often adopt the crystal grain thinning method, to be a kind of crystal boundary that utilizes a large amount of existence improve the intensity of material in restriction or anchoring dislocation motion for this, can be by famous Hall-Petch relation (σ=σ
0+ kd
-1/2) describe.Yet this strengthening effect is not unrestricted monotonically increasing along with the minimizing of grain-size, and after grain-size reduces to a certain degree, especially reaches nanometer scale, this strengthening effect will not exist.In fact, experimental observation and computer simulation work all shows, when the grain refining of material when nanometer scale or crystal grain have enough little size, strengthening effect weakens or disappears, and softening effect can occur then.This is actual to be owing to when grain-size is enough little, promptly near the equilibrium distance between dot matrix meta mistake, that is to say that crystal grain inside only can hold a small amount of (even not having) dislocation.At this time the ability of crystal boundary motion can increase substantially (rotate as crystal boundary, slide etc.), and the crystal boundary athletic meeting reduces the intensity that causes material.Therefore, for nano material, must limit obstruction dislocation motion and crystal boundary motion simultaneously in order further to improve intensity.
Adopting solution strengthening is the motion that hinders the dot matrix dislocation effectively with interpolation second enhancement method mutually equally, thereby material is strengthened.And adopt cold process (or plastic deformation method) to strengthen also is the further motion that hinders dislocation by a large amount of dislocations that produce in the deformation process.Therefore, all enhancement methods all are based on the motion that a large amount of defectives of introducing (as crystal boundary, dislocation, point defect and second phase or the like) hinder dislocation.These defectives have also increased the dispersion effect to electronics when hindering dislocation motion, therefore also just caused the conductivity of material to descend.
For example, common coarse crystal fine copper tensile yield strength (σ at room temperature
y) only be 0.035GPa, this is than low about two orders of magnitude of theoretical prediction value, and unit elongation is about 60%.The intensity of cold work (cold rolling attitude) back Cu material increases σ
yBe about 250GPa.The yield strength of nanometer copper product has increased significantly than coarse crystal copper, people (document 1:Sanders, P.G., Eastman, J.A.﹠amp such as U.S. scientist J.R.Weertman; Weertman, J.R., Elastic and tensile behaviorof nanocrystalline copper and palladium, Acta Mater.45,4019-4025 (1997)) grain-size of utilizing the inert-gas condensation method to prepare is about the nanometer crystal copper material of 30nm, when room temperature tensile, its yield strength can reach 365MPa.(document 2:Suryanarayana such as professor R.Suryanarayana, R.et al., Mechanical properties of nanocrystalline copperproduced by solution-phase synthesis, J.Mater.Res.11,439-448 (1996)) utilizes the copper nanoparticle of Prepared by Ball Milling, after again this copper nanoparticle purification coldmoulding being gone out, obtain the yield strength that grain-size is about the nanometer copper of 26nm and be about 400MPa, the unit elongation of these two kinds of samples is all very little by about 1～2%.Domestic Lu Lei, people such as Lu Ke (number of patent application: 01114026.7) utilize the electrolytic deposition technology to prepare the block nanometer copper product of grain-size equally for 30nm, show that it is 119MPa that this deposition attitude nanometer copper sample has its room temperature yield strength of low angle boundary (this is different with traditional big angle crystal boundary that nano material had), unit elongation is 30%.If it is this deposition attitude nanocrystal copper sample is at room temperature rolling, the average grain size of its sample is constant, but crystal grain and intergranule misorientation increase, and dislocation desity increases in the sample, this yield strength with rolling attitude nanometer crystal copper material of same chip size diverse microcosmic structure increases substantially, can reach 425MPa, but extensibility decline only is 1.4%.People such as J.R.Weertman (document 3:Legros, M., Elliott, B.R., Rittner, M.N., Weertman, J.R.﹠amp; Hemker, K.J., Microsample tensiletesting of nanocrystalline metals, Philos.Mag.A.80,1017-1026 (2000)) utilize miniature nanocrystalline copper sample (＜1mm〉obtained yield strength when stretching up to 535MPa.Utilize making Nano surface to prepare nanometer copper sample (document 4:Y.M.Wang, D.Pan, K.Lu, K.J.Hemker and E.Ma., Microsample tensile testing of nanocrystalline Cu, ScriptaMater., 48,1581-1586 (2003)), (thickness of sample is about 11～14 μ m to tiny sampler, gauge length is long to be 1.7mm, and the gauge length cross section is 0.5 * 0.015mm
2) the room temperature tensile result show that its yield strength can reach 760MPa, but almost do not have unit elongation.As seen from the above analysis, no matter be to adopt work hardening method or crystal grain thinning method (nano material) at present, resulting pure Cu YIELD STRENGTH all is limited.The copper product room temperature compression experiment that the grain-size of utilizing the severe plastic deformation method to prepare simultaneously is about 109nm shows that its yield strength is about 400MPa, and its room temperature (293K) resistivity is up to 2.46 * 10
-8Ω m (only being 68%IACS) .[document 5:R.K.Islamgaliev, K.Pekala, M.Pekala and R.Z.Valiev., Phys.Stat.Sol., (a) .559-566,162 (1997) .]
Summary of the invention
The purpose of this invention is to provide a kind of nano twin crystal copper product and preparation method with superstrength ultra-high conductivity.
To achieve these goals, technical scheme of the present invention is as follows:
Superstrength ultra-high conductivity nano twin crystal copper product, its microtexture is formed by being bordering on equiaxial sub-micron grain, having mean thickness in crystal grain inside is the twin lamellae structure of the different orientation of 43～15nm, be orientated between the identical twin lamellae and be parallel to each other, the thickness of twin lamellae does not wait from several nanometers to 100nm, and its length is 100～500nm;
In addition, have following character: density is 8.93 ± 0.03g/cm
3, purity is 99.997 ± 0.02at%, rate of extension is 6 * 10 at ambient temperature
-3s
-1, its yield strength can reach 900 ± 10MPa, and unit elongation is 13.5 ± 0.5%; Described submicron grain size is 300-1000nm; Resistivity when room temperature (293K) is 1.75 ± 0.02 * 10
-8Ω m (be equivalent to specific conductivity g=96%IACS wherein IACS be International annealed copper standard abbreviation).Temperature coefficient of resistance is 6.78 * 10
-11K
-1
The preparation method of superstrength ultra-high conductivity nano twin crystal copper product:
Utilize the electrolytic deposition technology of preparing, electrolytic solution is selected the pure level of electronics high purity copper CuSO for use
4Solution adds and joins high-purity ion exchanged water or high-purity-grade distilled water, and pH value is 0.5～1.5, and anode is selected 99.99% fine copper plate for use, and negative electrode is coated with the iron plate or the mild steel plate of Ni-P amorphous layer for the surface;
Electrolytic process parameter: pulse current density is 40～100A/cm
2, adopt pulse mode to electroplate; ON time (t
On) be 0.01～0.05s, turn-off time (t
Off) be 1～3s, the negative electrode anode pole distance is 50～150mm, and anode cathode area ratio is 30～50: 1, and electrolyte temperature is 15～30 ℃; Electrolytic solution adopts the induction stirring mode; The high-purity N aCl aqueous solution of the aqueous gelatin solution of additive: 0.02～0.2ml/15～25% concentration and 0.2～1.0ml/15～25% concentration.
The present invention has following advantage:
1. has good character.The present invention utilizes in the electrolytic deposition technology reasonably technological process and processing parameter under the effect of pulsed current, prepare copper product with nano level twin lamellae structure, the thickness of this twin lamellae does not wait from several nanometers to 100nm, its length is approximately 100～500nm, has unique microtexture;
Material of the present invention has very high room temperature yield strength, can reach 900MPa, and this intensity is far above the yield strength with the nanometer copper sample of the suitable grain-size of other traditional method preparation.And this sample has extraordinary electroconductibility, and (293K) electric conductivity can reach 96%ICAS under the room temperature.
2. applicability is extremely strong.Because this copper product has special nanometer scale twin lamellae structure among the present invention, makes material have very high intensity, also have very high conductivity (because twin boundary is a kind of highly stable interface structure) and thermostability simultaneously.Therefore, the nano twin crystal copper product of this superstrength ultra-high conductivity has important value to the development of the computer industry that develops rapidly and cableless communication industry and press.
3. the preparation method is simple.The present invention utilizes traditional electrolytic deposition technology, only needs to improve processing condition, controls suitable deposition parameter and can obtain this nano twin crystal copper product with superstrength ultra-high conductivity of nano twin crystal tissue.
Description of drawings
Fig. 1-1 observes picture for the TEM photo light field of electrolytic deposition nano twin crystal copper product twin of the present invention.
Fig. 1-2 is the statistical Butut of the grain-size of the TEM photo of electrolytic deposition nano twin crystal copper product twin of the present invention.
Fig. 1-3 is the statistical Butut of the twin lamellae thickness of the TEM photo of electrolytic deposition nano twin crystal copper product twin of the present invention.
Fig. 2-1 is the HRTEM photo of electrolytic deposition nanometer crystal copper material twin of the present invention
Fig. 2-2 is the electron diffraction pattern of the HRTEM photo of electrolytic deposition nanometer crystal copper material twin of the present invention, and wherein T is a twin, and A is a matrix, and A and T be twin each other.
Fig. 3 is under the room temperature condition, the stress strain curve of nano twin crystal copper product of the present invention and coarse-grain copper product.
Fig. 4 is the low-temperature resistance (4K～296K) compare of nano twin crystal copper product of the present invention and common coarse-grain copper product.
Embodiment
Following structure drawings and Examples describe the present invention in detail.
1. utilize the electrolytic deposition technology to prepare flake nano twin crystal Cu material
Electrolytic deposition equipment: monopulse electrolytic deposition equipment
The used electrolytic solution of electrolytic deposition requires: the pure level of electronics CuSO
4Solution, beavy metal impurity content in the strict control electrolytic solution, electrolyte institute water should be high-purity deionized water, and electrolyte acidity is: PH=1.
The moon, anode requires: anode is that purity is higher than 99.99% fine copper plate, negative electrode is coated with the iron plate of Ni-P amorphous layer for the surface.
2. electrolytic process parameter: pulse current density is 50A/cm
2, pulse mode is electroplated; ON time (t
On) be 0.02s, turn-off time (t
Off) be 2s, the negative electrode anode pole distance is 100mm, anode, cathode area ratio are 50: 1; Electrolysis temperature is 20 ℃, and electrolytic solution adopts the induction stirring mode.
Additive: gelatin: 0.1ml/l (aqueous gelatin solution of 15% concentration);
High-purity N aCl:0.6ml/l (the NaCl aqueous solution of 15% concentration).
Prepare ultra-high purity, high-compactness, have the laminar Cu material of nanometer scale twin crystal (1nm=10
-9M), this nano twin crystal Cu material (only is 0.22T in room temperature
m, T
mMelting temperature for material) yield strength is 900 ± 10MPa, and resistivity is 1.75 ± 0.02 * 10
-8Ω m (being equivalent to 96%IACS).
Chemical analysis results shows that the purity of deposition attitude nanometer Cu sample is 99.998at%.The trace impurity chemical composition content is as shown in the table:
| Element | Micro content (%) | Element | Micro content (%) |
| Bi Sb As Pb Fe | ＜0.00003 0.00005 0.0001 0.00005 0.001 | Sn Ag Co Zn Ni | ＜0.0001 0.0002 0.00003 0.00005 0.00005 |
With Archimedes principle measure sample density is 8.93 ± 0.03g/cm
3, be equivalent to the pure Cu theoretical density of polycrystal (8.96g/cm
3) 99.7%.High-resolution electron microscope is observed nanocrystal Cu material, and (300～1000nm) crystal grain are formed by being bordering on equiaxial submicron, the twin lamellae structure that has highdensity different orientation in crystal grain inside, (shown in Fig. 1-1,1-2, the 1-3) is parallel to each other between the twin lamellae of same orientation.The thickness of twin lamellae does not wait from several nanometers to 100nm, and average twin lamellae thickness is about 15nm, and its length is approximately 100～500nm.Dislocation desity in the sample is very little.Most of twin-plane boundaries belong to complete interface, and also there be (Fig. 1-1,1-2,1-3 are shown in Fig. 2-1, the 2-2) in some partial dislocation.
The room temperature tensile of electrolytic deposition nano twin crystal crystal copper: Figure 3 shows that the true stress-strain curve under the electrolytic deposition nanocrystal Cu sample room temperature,, provided the stress strain curve of coarse-grain copper product among the figure simultaneously for relatively.As can be seen from the figure, when rate of extension be 6 * 10
-3s
-1The time, the yield strength σ of electrolytic deposition twin nanocrystal Cu
y=900 ± 10Mpa, unit elongation are 13.5%.Fig. 4 is the low-temperature resistance (4K～296K) compare of nano twin crystal copper product of the present invention and common coarse-grain copper product.The room temperature resistivity that has the Cu material of nano twin crystal structure as can be seen only is 1.75 ± 0.02 * 10
-8Ω m is suitable with the room temperature resistivity of common coarse crystal Cu material.
Difference from Example 1 is:
1) utilize the electrolytic deposition technology to prepare flake nano crystal Cu material: the pure grade high-purity copper sulfate of used for electrolyte electronics CuSO
4Solution adds and joins the high purity aquae destillata, and acidity is PH=0.5; Cathode and anode: anode is that purity is higher than 99.99% fine copper plate, and negative electrode is coated with the iron plate of Ni-P amorphous layer for the surface, and anode cathode area ratio is 30: 1.
2) additive: the aqueous gelatin solution 0.02ml/l of 5% concentration, the high-purity N aCl aqueous solution 0.2ml/l of 5% concentration; Electrolytic process parameter: pulse current density is 80A/cm
2, ON time (t
On) be 0.05s, turn-off time (t
Off) be 3s; The cathode and anode pole span is 50mm, and electrolyte temperature is 15 ℃;
Can prepare high purity, high-compactness, laminar twin nanocrystal Cu material under these processing condition equally, this nanocrystal of transmission electron microscope observation Cu material is also formed by being bordering on equiaxial sub-micron grain, the twin lamellae structure that has highdensity different orientation in crystal grain inside, the mean thickness of twin lamellae is about 30nm, and the dislocation desity in the sample is also very little.This nanocrystal Cu material is 810MPa in the yield strength of room temperature, and room temperature resistivity is 1.927 ± 0.02 * 10
-8Ω m.
Embodiment 3
Difference from Example 1 is:
1) utilize the electrolytic deposition technology to prepare flake nano crystal Cu material: the pure grade bluestone CuSO of used for electrolyte electronics
4Solution adds and joins high purity distilled water, and acidity is PH=1.5; Cathode and anode: anode is that purity is higher than 99.99% fine copper plate, and negative electrode is the surperficial mild steel plate that is coated with the Ni-P amorphous layer, and anode cathode area ratio is 40: 1.
2) additive: the aqueous gelatin solution 0.15ml/l of 25% concentration, the high-purity N aCl aqueous solution 1.0ml/l of 25% concentration; Electrolytic process parameter: pulse current density is 40A/cm
2, ON time (t
On) be 0.01s, turn-off time (t
Off) be 1s; The cathode and anode pole span is 150mm, and electrolysis temperature is 25 ℃;
Also can prepare high purity, high-compactness, laminar twin nanocrystal Cu material under these processing condition.This nanocrystal of transmission electron microscope observation Cu material is also formed by being bordering on equiaxial sub-micron grain, has the twin lamellae structure of highdensity different orientation in crystal grain inside, and the mean thickness of twin lamellae is about 43nm.Dislocation desity in the sample is also very little.This nanocrystal Cu material is 650MPa in the yield strength of room temperature, and room temperature resistivity is 2.151 ± 0.2 * 10
-8Ω m.
Comparative example 1
Common annealing attitude coarse crystal fine copper (grain-size is about 100 μ m) at room temperature stretches, its fracture limit strength σ
Uts≤ 200MPa, yield strength σ
y≤ 35MPa, unit elongation δ≤60%.The breaking tenacity and the yield strength of the common coarse crystal fine copper after cold rolling can be brought up to 290MPa and 250MPa respectively, and its unit elongation is about 8%.Therefore, for its limit yield strength of common coarse crystal fine copper (no matter being annealed state or cold rolling attitude) often less than 250MPa.
Comparative example 2
People such as U.S. scientist R.Suryanarayana utilize the nanocrystal Cu powder of mechanical alloying technology preparation, and extrusion forming after purifying is prepared into the nanocrystal Cu sample (grain-size is 26nm) of block.The yield strength of this sample can reach 400MPa under the stretched state.
Comparative example 3
People such as U.S. scientist J.Weertman utilize inert-gas condensation method and high vacuum (10
-5～10
-6Pa) (pressure is generally 1～5GPa) to original position pressurization technology, prepares the solid nano crystal copper product of average grain size at 22～110nm, and the density of sample is about 96% of theoretical density, and microstrain is bigger in the sample.The static stretching experiment result of room temperature shows that the more common coarse crystal copper product of the intensity of this nanometer crystal copper material has raising by a relatively large margin, and its breaking tenacity can be up to 415Mpa～480MPa, and yield strength can reach 300Mpa～360MPa.The intensity of sample and the preparation technology of sample and average grain size have relation, and be tiny more as grain-size, and its intensity is high more, and grain-size is thick more, and its intensity is lower, and plasticity reducing and reduce with grain-size.When grain-size was reduced to 22nm, yield strength reached maximum (360MPa), and grain-size continues to reduce, and yield strength has also reduced.But utilize its resistivity of sample of this method preparation can increase substantially poor electric conductivity.
Comparative example 4
People such as U.S. scientist J.Weertman utilize the inert-gas condensation legal system to be equipped with nanometer powder, with this powder in 150 ℃ of extrusion formings (pressure is generally 1.4GPa), prepare the solid nano crystal copper product of average grain size at 26nm, the density of sample is 99% of theoretical density.The tensile property result shows that this sample has higher yield strength, can reach 535MPa in very little sample (the whole length of sample is about 3mm, and the cross-sectional area of stretch section is 200 * 200 μ m).But this mechanical property result who obtains in small sample is difficult to the mechanical property result of the macroscopical sample of representative.
Comparative example 5
Domestic Lu Lei, people such as Lu Ke utilize the electrolytic deposition technology to prepare the block nanometer copper product of grain-size for 30nm, show that it is 119MPa that this deposition attitude nanometer copper sample has its room temperature yield strength of low angle boundary (this is different with traditional big angle crystal boundary that nano material had), unit elongation is 30%.If it is this deposition attitude nanocrystal copper sample is at room temperature rolling, the average grain size of its sample is constant, but crystal grain and intergranule misorientation increase, and dislocation desity increases in the sample, this yield strength with rolling attitude nanometer crystal copper material of same chip size diverse microcosmic structure increases substantially, can reach 425MPa, but extensibility decline only is 1.4%.
Comparative example 6
Russian scientist R.Z.Valiev (R.K.Islamgaliev, P.Pekala, M.Pekala and R.E.Valiev, Plys.Stat.Sol. (a) 162,559 (1997)) utilize the severe plastic deformation method to obtain the pure copper material of submicron order, its average grain size is 210nm, and sample compactness is better, but remnants are very big.At room temperature stretch, its ultimate breaking strength can reach 500MPa, and unit elongation is about 5%, and the resistance under this material room temperature is bigger, and resistivity is ρ=2.24 * 10
-8Ω m (being equivalent to specific conductivity g=70%IACS).
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| CN118835284A (en) * | 2024-06-21 | 2024-10-25 | 中国科学院深圳先进技术研究院 | Plating solution additive, preparation method thereof, nano twin crystal copper electroplating solution and application |
| CN120060939B (en) * | 2025-01-26 | 2025-12-02 | 大连理工大学 | A nano-twinned copper electroplating additive and electroplating solution |
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2003
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