CN115341248A - Nano twin crystal copper material with (110) orientation and preparation method thereof - Google Patents

Nano twin crystal copper material with (110) orientation and preparation method thereof Download PDF

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CN115341248A
CN115341248A CN202210888293.6A CN202210888293A CN115341248A CN 115341248 A CN115341248 A CN 115341248A CN 202210888293 A CN202210888293 A CN 202210888293A CN 115341248 A CN115341248 A CN 115341248A
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copper material
twin crystal
orientation
copper
nano
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韦小丁
张鹏
马瑜薇
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Peking University
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    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a nanometer twin crystal copper material with (110) orientation and a preparation method thereof, wherein the nanometer twin crystal copper material comprises an isometric crystal tissue and a strip tissue, the isometric crystal tissue is arranged at the bottom of the nanometer twin crystal copper material, and the average grain size of the nanometer twin crystal copper material is between 300 and 900 nm; with the increase of the thickness of the nanometer twin crystal copper material, the strip-shaped tissue appears; the length-width ratio of the monomer in the strip-shaped structure is more than 1: 100, the strip-shaped structure contains a twin crystal lamella, a twin crystal plane of the twin crystal lamella is perpendicular to a growth plane, the twin crystal lamella has (110) orientation, and the average thickness of the twin crystal lamella is less than 150 nm. The invention adopts the direct current electrolytic deposition technology to prepare the nanometer twin crystal copper material with high-density twin crystal and the twin crystal plane vertical to the growth plane, the nanometer twin crystal copper material has (110) orientation, and can obtain larger strength and toughness while having high thermal stability and conductivity of the twin crystal boundary.

Description

Nano twin crystal copper material with (110) orientation and preparation method thereof
Technical Field
The invention relates to the technical field of electrolytic copper material preparation, in particular to a nano twin crystal copper material with (110) orientation and a preparation method thereof.
Background
The electrolytic copper material is an indispensable material in the fields of electronic circuits, lithium ion batteries and the like. In the field of electronic circuits, electrical interconnects are an important component of very large scale integrated circuits and nano-electromechanical devices, which require highly conductive, strong and stable wires. Emerging three-dimensional integrated circuit technologies also require signal transmission, power supply, and heat dissipation between vertically stacked integrated circuit chips through-silicon via wiring systems, which must be deposited with high aspect ratios through dielectric-encased structures. In a lithium ion battery, copper foil is widely used as a current collector of an anode of the lithium ion battery, and graphite expands by about 13% when used as an anode and silicon may significantly increase in volume to 300% when used as an anode during charge and discharge, which may cause a conventional electrolytic copper foil to fail. Therefore, in order to solve the above problems, it is necessary to improve the mechanical properties of copper foil while obtaining high thermal and electrical conductivity of copper.
Generally, copper foil can be strengthened by solution/precipitation hardening, strain hardening, and grain refinement. However, these strengthening methods inevitably reduce the conductivity due to distorted crystal lattice and grain boundary-induced electron scattering. The nano sintered copper foil can improve the mechanical strength of the material and keep the good ductility and conductivity of the material, but is not satisfactory in the aspects of ultimate tensile strength and thermal stability. Nano twin strengthening is widely recognized as a fifth strengthening mechanism of metals. Researches show that the compact nano-scale sigma 3 coherent twin crystal boundary in the nano-twin crystal copper foil can improve the thermal stability, electromigration resistance, corrosion resistance/oxidation resistance and the like of copper metal. In addition, the nano twinned copper can maintain excellent electrical conductivity of copper while improving strength/toughness. The outstanding performance of the nanometer twin crystal copper enables the nanometer twin crystal copper to have wide application prospects in the fields of advanced electronic industry, new energy, 5G telecommunication equipment, flexible wearable equipment and the like.
Considering the convenience and low cost of large-scale preparation, the existing nano twin crystal copper material is mainly prepared by an electroplating method, and the prepared copper material has a nano twin crystal tissue with columnar crystal and strong (111) texture, and the twin crystal plane is parallel to the deposition surface. Patent CN 113621998A, a nano-twin copper foil and a preparation method thereof, CN 110724981A, a preparation method of a copper film material with a full nano-twin tissue structure, CN 109136987A, a gradient nano-twin copper block material and a temperature control preparation method thereof, and CN 112941586A nano-twin copper components all adopt a direct current electroplating mode to obtain columnar crystals and (111) texture copper foils, and comprehensively utilize the high toughness, high heat conductivity and electric conductivity of the nano-twin copper material for application and development.
The excellent performance of the nano twin crystal copper material mainly comes from a nano sigma 3 coherent twin crystal boundary. For example, high toughness properties are achieved through complex interactions of dislocations in the crystal with twin boundaries. While dislocation slip is affected by the orientation of the nano twins and a significant dependence of material strength on the nano twins orientation and loading direction was experimentally observed [ d.c Jang, x.y.li, h.j.gao, j.r.greenr.nature Nanotechnology,2012; z.you, x.li, l.gui, q.lu, t.zhu, h.gao, l.lu.acta Materialia,2013]. When the angle (theta) between the stress direction and the twin crystal plane is 90 degrees, the nanometer twin crystal in the copper material can exert the maximum strengthening effect; when theta is 0 degree, the strengthening effect is inferior; when θ is 45 degrees, the strengthening effect is the worst. The strengthening effect of the nano twin crystal copper material which is widely prepared at present and has a twin crystal plane parallel to a deposition plane and a (111) texture in the length direction (theta is 0 ℃) is not optimal.
Disclosure of Invention
In view of the above, the present invention aims to provide a nano twin crystal copper material with (110) orientation and a preparation method thereof, so as to prepare a nano twin crystal copper material with a high density twin crystal and a twin crystal plane perpendicular to a growth plane, so that the nano twin crystal copper material has both high thermal stability and electrical conductivity of twin crystal boundaries and greater strength and toughness.
According to one aspect of the invention, a nano twinned copper material with (110) orientation is provided, which comprises an equiaxed crystal structure and a strip structure, wherein:
the bottom of the nanometer twin crystal copper material is the equiaxial crystal structure, and the average grain size is between 300 and 900 nm;
with the increase of the thickness of the nanometer twin crystal copper material, the strip-shaped tissue appears;
the aspect ratio of the monomer in the strip-shaped structure is more than 1: 100, the strip-shaped structure contains twin crystal lamella, the twin crystal plane of the twin crystal lamella is perpendicular to the growth plane, the twin crystal lamella has (110) orientation, and the average thickness of the twin crystal lamella is less than 150 nm.
In the scheme, the volume ratio of the equiaxed crystal tissue and the strip-shaped tissue in the nano twin crystal copper material is adjustable, wherein the volume ratio of the strip-shaped tissue is 10-90%.
In the scheme, the average grain size of the isometric crystal structure is 400-700nm, the aspect ratio of the monomer in the strip-shaped structure is 1: 150-1: 200, and the average thickness of the twin crystal lamella is 50-100nm.
In the scheme, the orientation of the nano twin crystal copper material is changed from random orientation to strong (110) texture from bottom to top, namely (110) orientation.
In the scheme, the thickness of the nanometer twin crystal copper material is 50-350 μm. Optionally, the thickness of the nanometer twin crystal copper material is 150-300 μm.
According to another aspect of the invention, a method for preparing nano twin crystal copper material with (110) orientation is also provided, the method adopts direct current electrolytic deposition technology, a copper plate is used as anode material, a Ti plate is used as cathode, and the area ratio of the anode to the cathode is more than 10:1, the distance between the anode and the cathode is 10-20cm;
in the direct-current electrolytic deposition technology, the adopted electrolyte comprises the following components in percentage by weight: divalent copper ion Cu 2+ 20-100g/L; hydrogen ion H + 0.07-2mol/L; chloride ion Cl - 40-80mg/L; additive, 5-20mg/L; the balance of deionized water;
in the direct-current electrolytic deposition technology, a constant current mode is adopted, and the current density is 20-80mA/cm 2 The temperature of the electrolyte is 5-30 ℃, and the deposition time is 30 min-16 h.
In the scheme, the copper plate is a high-purity copper plate with the copper content of more than 99.99%, the Ti plate is a pure Ti plate, the area ratio of the anode to the cathode is 12: 1-20: 1, and the distance between the anode and the cathode is 12-15cm.
In the above aspect, in the electrolyte, divalent copper ions (Cu) 2+ ) The content of (A) is 40-80g/L; hydrogen ion (H) + ) The content of (A) is 1-1.5mol/L; chloride ion (Cl) - ) The content of (A) is 50-60mg/L; the content of the additive is 6-12mg/L.
In the above aspect, in the electrolyte, cu 2+ From copper sulfate, copper sulfate hydrate, or a mixture of copper sulfate and copper chloride; h + Derived from hydrochloric acid or sulfuric acid; cl - Derived from hydrochloric acid or sodium chloride.
In the scheme, in the electrolyte, the additive comprises gelatin and sodium polydithio-dipropyl sulfonate (SPS), and the weight ratio of the gelatin to the sodium polydithio-dipropyl sulfonate (SPS) is 2: 1 to 1: 3. Optionally, the weight ratio of the gelatin to the sodium polydithio-dipropyl sulfonate SPS is from 1: 1 to 1: 2.
In the scheme, in the direct-current electrolytic deposition technology, the current density is matched with the weight ratio of gelatin to sodium polydithio-dipropyl sulfonate (SPS) in the additive, the gelatin/SPS is increased, the current density is reduced, and the relationship between the gelatin/SPS and the current density meets 1: 30-1: 100. Optionally, the relationship between the gelatin/SPS and the current density satisfies 1: 50 to 1: 90.
In the scheme, the current density is 30-55mA/cm 2 The temperature of the electrolyte is 15-25 ℃, and the deposition time is 4-16 h.
In the scheme, in the direct-current electrolytic deposition technology, the components in the electrolyte are kept uniform all the time by using magnetic stirring.
According to the technical scheme, the invention has the following beneficial effects:
1. the nanometer twin crystal copper material with (110) orientation and the preparation method thereof provided by the invention have the advantages that the nanometer twin crystal copper material with high-density twin crystal and the twin crystal plane vertical to the growth plane is prepared by adopting the direct current electrolytic deposition technology, the nanometer twin crystal copper material has (110) orientation, and the nanometer twin crystal copper material has high thermal stability and electrical conductivity of a twin crystal boundary and simultaneously obtains higher strength and toughness.
2. According to the nanometer twin crystal copper material with the (110) orientation and the preparation method thereof, the twin crystal plane in the nanometer twin crystal copper material is vertical to the growth plane, so that the nanometer twin crystal copper material can obtain higher strength and plasticity by utilizing a strengthening mechanism that the twin crystal and the stress direction form an angle of 90 degrees, and the application range of the nanometer twin crystal copper material is further expanded.
3. According to the nano twin crystal copper material with (110) orientation and the preparation method thereof, the nano twin crystal copper material with different microstructures can be obtained by adjusting the components of the electrolyte and the parameters of the electrodeposition process, the controllable adjustment of the material performance is realized, and the application scene of the material is enlarged.
4. The nanometer twin crystal copper material with (110) orientation and the preparation method thereof provided by the invention can control the reduction speed of copper ions at the cathode by adjusting the current density and the electrolyte temperature, and can regulate and control the thickness of the nanometer twin crystal copper material and the size of equiaxial crystals and twin crystals.
5. According to the nanometer twin crystal copper material with (110) orientation and the preparation method thereof provided by the invention, the nanometer twin crystal copper material with (110) orientation, which contains different strip tissues and isometric crystal proportions, can be prepared by regulating the weight proportion of gelatin and sodium polydithio-dipropyl sulfonate (SPS), and the twin crystal plane contained in the nanometer twin crystal copper material is vertical to the growth plane.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1a is a back-scattered electron mode (BSE) picture of a cross section of a nano twin copper material having a (110) orientation provided by the present invention, white arrows indicate a growth direction of the copper material during an electroplating process;
FIG. 1b is a magnified back-scattered electron mode (BSE) image of the tissue strip of FIG. 1 a;
fig. 1c is an X-ray diffraction pattern of a nano twin crystal copper material with (110) orientation provided by the present invention, which shows that the out-of-plane texture is (110), i.e. has (110) orientation;
FIG. 1d shows the appearance of the growth surface of the electroplated copper material under a light mirror.
Fig. 2 is a back scattered electron mode (BSE) picture of a cross section of a nano twinned copper material with (110) orientation according to example 1 of the present invention, and white arrows indicate the growth direction of the copper material during electroplating.
Fig. 3 is a back scattered electron mode (BSE) picture of a cross section of a nano twinned copper material having a (110) orientation according to example 2 of the present invention, and white arrows indicate a growth direction of the copper material during an electroplating process.
Fig. 4 is a back scattered electron mode (BSE) picture of a cross section of a nano twinned copper material with (110) orientation according to example 3 of the present invention, and white arrows indicate the growth direction of the copper material during electroplating.
Figure 5 is an engineering stress strain curve of nano twinned copper material with (110) orientation according to examples 1-3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments and the accompanying drawings.
Aiming at the defect that the strengthening effect obtained in the length direction (theta is 0 degree) of the currently widely prepared nanometer twin crystal copper material with a (111) texture, which is parallel to a deposition plane, does not reach the best, the invention provides a nanometer twin crystal copper material with (110) orientation and a preparation method thereof, wherein the nanometer twin crystal copper material with high-density twin crystal and a twin crystal plane vertical to a growth plane is prepared by adopting a direct-current electrolytic deposition technology, has (110) orientation, and can obtain higher strength and toughness while having high thermal stability and conductivity of a twin crystal boundary.
The technical principle adopted by the invention is as follows: sodium polydithio-dipropyl sulfonate (SPS) accelerates the nucleation of grains to refine the grains by depolarization effect during the electrolytic deposition process, which is contrary to the effect of gelatin. Copper is generally deposited by two-dimensional nucleation in the presence of a single additive gelatin and eventually forms a columnar grain microstructure (FT-type, (111) texture). When SPS is added, the two additives in the electrolyte adsorb competitively and then form constantly changing local deposition conditions on the surface, and when SPS replaces the pre-adsorbed gelatin on the deposition surface, new particles nucleate on top of the existing particles. This dynamic situation can lead to the formation of equiaxed crystals (UD type), in which the deposited material grows by three-dimensional nucleation. According to the Winand diagram, the FT type (111) texture nanometer twin crystal structure is formed after the UD type isometric crystal is formed. From an energy perspective, however, (111) texture occurs because it has the lowest surface energy, while (110) texture minimizes the strain energy accumulated in the material, and twin boundaries occur as a result of the coordinated lattice distortion that reduces the strain energy. In addition, the exchange current density of the copper (110) plane during electrodeposition is five times that of the (111) plane, which promotes rapid growth of the (110) structure, resulting in high aspect ratio structures. Therefore, as the thickness of the deposited copper increases, the strain energy becomes larger, promoting vertical twinning with high aspect ratio, (110) texture.
In view of the above mechanism, the present invention designs and prepares a nanometer twin crystal copper material with (110) texture by adjusting the ratio of SPS and gelatin, as shown in fig. 1a to 1d, fig. 1a is a back scattered electron mode (BSE) picture of the cross section of the nanometer twin crystal copper material with (110) orientation provided by the present invention, white arrows indicate the growth direction of the copper material during electroplating, fig. 1b is an enlarged back scattered electron mode (BSE) picture of the strip-shaped structure in fig. 1a, fig. 1c is an X-ray diffraction pattern of the nanometer twin crystal copper material with (110) orientation provided by the present invention, indicating that the out-of-plane texture is (110), i.e. has (110) orientation, and fig. 1d is the appearance of the growth surface of the electroplated copper material provided by the present invention under a light mirror.
The preparation process of the nano twin crystal copper material with (110) texture shown in fig. 1a to 1d is as follows: continuously changing the weight ratio of gelatin and SPS in the electrolyte, and adjusting SPS and gelatin to a critical state, wherein the critical state is marked by coexistence of a smooth area and a rough area visible to naked eyes on the surface of electrodeposited copper, at the moment, a partial area at the edge part of the copper represents an area where isometric crystal copper is located, and a rough area in the middle of the copper is a vertical twin crystal area converted from isometric crystal, which is specifically shown in figure 1 d. Then, the weight ratio of SPS to gelatin and the matched current density are finely adjusted, and the nano twin crystal copper material containing different strip tissues and isometric crystal ratios can be prepared. Furthermore, the reduction speed of copper ions at the cathode is controlled by adjusting the current density and the temperature of the electrolyte, so that the thickness of the nano twin crystal copper material and the sizes of equiaxial crystals and twin crystals can be regulated and controlled.
According to the embodiment of the invention, a nanometer twin crystal copper material with (110) orientation is provided, which comprises an isometric crystal tissue and a strip tissue, wherein the isometric crystal tissue is arranged at the bottom of the nanometer twin crystal copper material, and the average grain size of the nanometer twin crystal copper material is 300-900 nm; with the increase of the thickness of the nanometer twin crystal copper material, the strip-shaped tissue appears; the aspect ratio of the monomer in the strip-shaped structure is more than 1: 100, the strip-shaped structure contains twin crystal lamella, the twin crystal plane of the twin crystal lamella is perpendicular to the growth plane, the twin crystal lamella has (110) orientation, and the average thickness of the twin crystal lamella is less than 150 nm.
In an embodiment of the present invention, a volume ratio of the equiaxial crystal tissue and the strip-shaped tissue in the nano twinned copper material is adjustable, wherein the volume ratio of the strip-shaped tissue is between 10% and 90%, and optionally, the volume ratio of the strip-shaped tissue is 10%, 20%, 23.6%, 30%, 40%, 50%, 56.1%, 60%, 70%, 80%, 81.3%, or 90%.
In the embodiment of the present invention, the average grain size of the equiaxed crystal structure is between 400nm and 700nm, and optionally, the average grain size of the equiaxed crystal structure may be 400nm, 500nm, 600nm or 700nm.
In the embodiment of the present invention, the aspect ratio of the monomers in the bar-shaped tissue is 1: 150 to 1: 200, and optionally, the aspect ratio of the monomers in the bar-shaped tissue may be 1: 150, 1: 160, 1: 170, 1: 180, 1: 190, or 1: 200.
In the embodiment of the invention, the average thickness of the twin crystal lamella is 50-100nm, and optionally, the average thickness of the twin crystal lamella can be 50nm, 60nm, 70nm, 80nm, 90nm or 100nm.
In the embodiment of the invention, the orientation of the nanometer twin crystal copper material is changed from random orientation to strong (110) texture, namely (110) orientation from bottom to top.
In the embodiment of the present invention, the thickness of the nano twinned crystal copper material is 50-350 μm, alternatively, the thickness of the nano twinned crystal copper material may be 150-300 μm, for example, the thickness of the nano twinned crystal copper material is 145 μm, 150 μm, 187 μm, 200 μm, 250 μm or 300 μm.
In the embodiment of the invention, the prepared nano twin crystal copper material with (110) orientation has the following properties: the purity is more than 99.99 percent, the tensile strength and the uniform elongation rate under the room temperature condition can be regulated and controlled by utilizing the proportion of the strip-shaped tissues, the achievable tensile strength is 300-500MPa, and the uniform elongation rate is 7-30 percent.
According to the embodiment of the invention, the method for preparing the nano twin crystal copper material with the (110) orientation is also provided, the method adopts a direct current electrolytic deposition technology, utilizes a copper plate as an anode material and a Ti plate as a cathode, the area ratio of the anode to the cathode is more than 10:1, and the distance between the anode and the cathode is 10-20cm; in the direct-current electrolytic deposition technology, the adopted electrolyte comprises the following components in percentage by weight: divalent copper ion Cu 2+ 20-100g/L; hydrogen ion H + 0.07-2mol/L; chloride ion Cl - 40-80mg/L; additive, 5-20mg/L; the balance of deionized water; in the direct-current electrolytic deposition technology, a constant current mode is adopted, and the current density is 20-80mA/cm 2 The temperature of the electrolyte is 5-30 ℃, and the deposition time is 30 min-16 h.
In the embodiment of the invention, the copper plate is a high-purity copper plate with copper content more than 99.99%, the Ti plate is a pure Ti plate, the area ratio of the anode and the cathode is 12: 1-20: 1, and optionally the area ratio of the anode and the cathode can be 12: 1, 13: 1, 14: 1, 15: 1, 16: 1, 17: 1, 18: 1, 19: 1 or 20: 1; the distance between the anode and the cathode is 12-15cm, alternatively the distance between the anode and the cathode may be 12cm, 13cm, 14cm or 15cm.
In the electrolyte of the embodiment of the present invention, divalent copper ions (Cu) 2+ ) In an amount of 40-80g/L, optionally, divalent copper ions (Cu) 2+ ) The content of (b) may be 40g/L, 50g/L, 60g/L, 70g/Lg/L or 80g/L.
In the electrolyte of the embodiment of the invention, hydrogen ions (H) + ) In an amount of 1 to 1.5mol/L, optionally, hydrogen ion (H) + ) The content of (b) may be 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L or 1.5mol/L.
In the electrolytic solution of the embodiment of the invention, chloride ions (Cl) - ) In an amount of 50-60mg/L, optionally, chloride ion (Cl) - ) The content of (b) may be 50mg/L, 52mg/L, 54mg/L, 56mg/L, 58mg/L or 60mg/L.
In the electrolyte of the embodiment of the invention, the content of the additive is 6-12mg/L, and optionally, the content of the additive can be 6mg/L, 8mg/L, 10mg/L or 12mg/L.
In the electrolyte of the embodiment of the invention, cu 2+ From copper sulfate, copper sulfate hydrate, or a mixture of copper sulfate and copper chloride; h + Derived from hydrochloric acid or sulfuric acid; cl - Derived from hydrochloric acid or sodium chloride.
In the electrolyte of the embodiment of the invention, the additive comprises gelatin and sodium polydithio-dipropyl sulfonate SPS, and the weight ratio of the gelatin to the sodium polydithio-dipropyl sulfonate SPS (namely gelatin/SPS) is 2: 1 to 1: 3. Alternatively, the gelatin/SPS is from 1: 1 to 1: 2, for example the gelatin/SPS may be 1: 1, 1: 1.2, 1: 1.4, 1: 1.6, 1: 1.7 or 1: 2.
In the direct-current electrolytic deposition technology of the embodiment of the invention, the current density is matched with the weight ratio of gelatin to sodium polydithiodipropionate SPS in the additive, the gelatin/SPS is increased, the current density is reduced, and the relationship between the gelatin/SPS and the current density meets 1: 30-1: 100. Optionally, the relationship between the gelatin/SPS and the current density satisfies 1: 50 to 1: 90, such as 1: 50, 1: 60, 1: 70, 1: 80 or 1: 90.
In the embodiment of the invention, the current density is 30-55mA/cm 2 Alternatively, the current density may be 30mA/cm 2 、35mA/cm 2 、40mA/cm 2 、45mA/cm 2 、50mA/cm 2 、55mA/cm 2 。
In the embodiment of the present invention, the temperature of the electrolyte is 15 to 25 ℃, and optionally, the temperature of the electrolyte may be 15 ℃,20 ℃ or 25 ℃.
In the embodiment of the present invention, the deposition time is 4h to 16h, and optionally, the deposition time may be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, or 16h.
In the direct-current electrolytic deposition technology of the embodiment of the invention, the components in the electrolyte are always kept uniform by magnetic stirring, and the rotating speed of the magnetic stirring is as follows: 300-1000r/min, and optionally, the rotation speed of the magnetic stirring can be 350r/min, 500r/min or 800r/min.
According to the nano twin crystal copper material with the (110) orientation and the preparation method thereof provided by the embodiment of the invention, the nano twin crystal copper material with high-density twin crystals and the twin crystal plane vertical to the growth plane is prepared by adopting a direct-current electrolytic deposition technology, has the (110) orientation, and can obtain higher strength and toughness while having high thermal stability and conductivity of a twin crystal boundary. Because the twin crystal plane in the nanometer twin crystal copper material is vertical to the growth plane, the nanometer twin crystal copper material can obtain higher strength and plasticity by utilizing the strengthening mechanism that the twin crystal and the stress direction form 90 degrees, and the application range of the nanometer twin crystal copper material is further expanded. By adjusting the components of the electrolyte and the parameters of the electrodeposition process, the nano twin crystal copper material with different microstructures can be obtained, the controllable adjustment of the material performance is realized, and the application scene of the material is enlarged. The reduction speed of copper ions at the cathode is controlled by adjusting the current density and the temperature of the electrolyte, and the thickness of the nano twin crystal copper material and the sizes of equiaxial crystals and twin crystals can be regulated and controlled. By regulating the weight ratio of gelatin to Sodium Polydithiodipropyl Sulfonate (SPS), a nano twin crystal copper material containing different strip tissues and isometric crystal ratios and having (110) orientation can be prepared, and a twin crystal plane contained in the nano twin crystal copper material is vertical to a growth plane.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1: preparation and tensile testing of nano twin crystal copper material with (110) orientation
The embodiment utilizes the constant current mode of the electrochemical workstation to provide stable current with the current density of 30mA/cm 2 . The area of the anode plate is 150cm 2 Cathode Ti plate area of 12cm 2 The distance between the two opposite surfaces is 10cm. The electrolyte comprises the following components: 60g/L of Cu 2+ 0.1mol/L of H + 60mg/L of Cl - (ii) a 10mg/L of additive, wherein the weight ratio of the gelatin to the SPS is 1: 3. During the electroplating process, the components in the electrolyte are kept uniform all the time by using magnetic stirring (500 r/min), and the temperature of the electrolyte is 15 ℃. The DC electrodeposition time is 8h.
The prepared nano twin crystal copper material has the area of 12cm 2 The average thickness was 187. Mu.m as measured by a micrometer screw. Specifically, as shown in fig. 2, fig. 2 is a back scattered electron mode (BSE) picture of a cross section of a nano-twin copper material with a (110) orientation according to example 1 of the present invention, and white arrows indicate a growth direction of the copper material during electroplating. The side of the lower part of the nanometer twin crystal copper material close to the titanium substrate is an isometric crystal structure, and the grain size is smaller; as the thickness increases, streaky tissue appears, at a rate of approximately 23.6%. The twin thickness in the strip structure is below 100nm. The copper material has good toughness, can be directly taken down from the titanium plate substrate, and has no defects of pinholes, pockmarks and the like.
In the examples, the room temperature stretching results of the nano twinned copper material are shown in figure 5, example curve 1. The test conditions were: the tensile test sample is formed by cutting and shearing by using a wire, the length, the width and the thickness of a tensile section are respectively 10mm multiplied by 3mm multiplied by 0.181mm, the tensile performance is tested by adopting a SEMTester100-MTI tensile tester, and the tensile speed is 3mm/min. The mechanical property of the nanometer twin crystal copper material is as follows: the tensile strength is 340MPa, and the uniform elongation is 25.8%.
Example 2: preparation and tensile testing of nano twin crystal copper material with (110) orientation
The embodiment utilizes the constant current mode of the electrochemical workstation to provide stable current with the current density of 40mA/cm 2 . The area of the anode plate is 150cm 2 Cathode Ti plate area 12cm 2 The distance between the two opposite sides is 12cm. The electrolyte comprises the following components: 70g/L of Cu 2+ 0.08mol/L of H + 50mg/L of Cl - (ii) a 12mg/L of additive, wherein the weight ratio of gelatin and SPS is 1: 2. During the electroplating process, the components in the electrolyte are kept uniform all the time by using magnetic stirring (500 r/min), and the temperature of the electrolyte is 15 ℃. The DC electrodeposition time is 8h.
The prepared nano twin crystal copper material has the area of 12cm 2 The average thickness was determined by a micrometer screw to be 145 μm. Specifically, as shown in fig. 3, fig. 3 is a back scattered electron mode (BSE) picture of a cross section of a nano-twin copper material with a (110) orientation according to example 2 of the present invention, and white arrows indicate the growth direction of the copper material during electroplating. The side of the lower part of the nanometer twin crystal copper material close to the titanium substrate is an isometric crystal structure, and the grain size is smaller; as the thickness increases, streaky tissue occurs at a rate of approximately 56.1%. The twin thickness in the strip-shaped structure is below 100nm. The copper material has good toughness, can be directly taken down from the titanium plate substrate, and has no defects of pinholes, pockmarks and the like.
In the examples, the room temperature tensile results of the nano twinned copper material are shown in the example 2 curve in fig. 5. The test conditions were: the tensile test sample is formed by cutting with a wire, the length, width and thickness of the tensile section are respectively 10mm multiplied by 3mm multiplied by 0.140mm, the tensile property is tested by adopting a SEMTester100-MTI tensile tester, and the tensile rate is 3mm/min. The mechanical property of the nanometer twin crystal copper material is as follows: the tensile strength was 402MPa, and the uniform elongation was 11.8%.
Example 3: preparation and tensile testing of nano twinned copper material with (110) orientation
The embodiment utilizes the constant current mode of the electrochemical workstation to provide stable current with the current density of 50mA/cm 2 . The area of the anode plate is 150cm 2 Cathode Ti plate area of 12cm 2 The distance between the two opposite surfaces is 15cm. The electrolyte comprises the following components: 80g/L of Cu 2+ 0.07mol/L of H + 45mg/L of Cl - (ii) a 15mg/L of additive, wherein the weight ratio of gelatin and SPS is 1: 1. During the electroplating process, the components in the electrolyte are kept uniform all the time by using magnetic stirring (500 r/min), and the temperature of the electrolyte is 15 ℃. The DC electrodeposition time is 8h.
The prepared nano twin crystal copper material has the area of 12cm 2 Spiral testThe average thickness was measured by a micrometer to be 150. Mu.m. Specifically, as shown in fig. 4, fig. 4 is a back scattered electron mode (BSE) picture of a cross section of a nano twin crystal copper material with (110) orientation according to example 3 of the present invention, and white arrows indicate a growth direction of the copper material during an electroplating process. The side of the lower part of the nanometer twin crystal copper material close to the titanium plate substrate is an isometric crystal structure, and the crystal grain size is smaller; as the thickness increased, streaky tissue appeared at a rate of approximately 81.3%. The twin thickness in the strip structure is below 100nm. The copper material has good toughness, can be directly taken down from the titanium plate substrate, and has no defects of pinholes, pockmarks and the like.
In the examples, the room temperature stretching results of the nano twinned copper material are shown in the example 3 curve of fig. 5. The test conditions were: the tensile test sample is formed by cutting with a wire, the length, width and thickness of the tensile section are respectively 10mm multiplied by 3mm multiplied by 0.145mm, the tensile property is tested by adopting a SEMTester100-MTI tensile tester, and the tensile rate is 3mm/min. The mechanical property of the nanometer twin crystal copper material is as follows: the tensile strength is 465MPa, and the uniform elongation is 8.1 percent.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (16)

1. A nanometer twin crystal copper material with (110) orientation comprises an isometric crystal tissue and a strip-shaped tissue, and is characterized in that:
the bottom of the nanometer twin crystal copper material is the equiaxial crystal structure, and the average grain size is between 300 and 900 nm;
with the increase of the thickness of the nanometer twin crystal copper material, the strip-shaped tissue appears;
the length-width ratio of the monomer in the strip-shaped structure is more than 1: 100, the strip-shaped structure contains a twin crystal lamella, a twin crystal plane of the twin crystal lamella is perpendicular to a growth plane, the twin crystal lamella has (110) orientation, and the average thickness of the twin crystal lamella is less than 150 nm.
2. The nano twin copper material with (110) orientation as claimed in claim 1, wherein the volume ratio of the equiaxial crystal tissue and the strip-shaped tissue in the nano twin copper material is adjustable, wherein the volume ratio of the strip-shaped tissue is between 10% and 90%.
3. The nano twin crystal copper material with (110) orientation as claimed in claim 1, wherein the average grain size of the equiaxed crystal structure is between 400-700nm, the aspect ratio of the monomer in the strip-shaped structure is 1: 150 to 1: 200, and the average thickness of the twin crystal sheet layer is 50-100nm.
4. The nano twin crystal copper material with (110) orientation as claimed in claim 1, characterized in that the orientation of the nano twin crystal copper material is changed from random orientation to strong (110) texture, i.e. (110) orientation, from bottom to top.
5. The nano twin copper material with (110) orientation as claimed in claim 1, characterized in that the thickness of the nano twin copper material is 50-350 μm.
6. The nano twin copper material with (110) orientation as claimed in claim 5, wherein the thickness of the nano twin copper material is 150-300 μm.
7. A method for preparing nanometer twin crystal copper material as defined in any one of claims 1 to 6, characterized in that the method adopts direct current electrolytic deposition technique, uses copper plate as anode material, uses Ti plate as cathode, the area ratio of anode and cathode is more than 10:1, the distance between anode and cathode is 10-20cm;
in the direct-current electrolytic deposition technology, the adopted electrolyte comprises the following components in percentage by weight: divalent copper ion Cu 2+ 20-100g/L; hydrogen ion H + 0.07-2mol/L; chloride ion Cl - 40-80mg/L; additive for foodAdding 5-20mg/L of additive; the balance of deionized water;
in the direct-current electrolytic deposition technology, a constant current mode is adopted, and the current density is 20-80mA/cm 2 The temperature of the electrolyte is 5-30 ℃, and the deposition time is 30 min-16 h.
8. The method for preparing nanometer twin crystal copper material as claimed in claim 7, characterized in that the copper plate is high purity copper plate with copper content more than 99.99%, the Ti plate is pure Ti plate, the area ratio of anode and cathode is 12: 1-20: 1, the distance between anode and cathode is 12-15cm.
9. The method for preparing nano twinned copper material as claimed in claim 7, characterized in that in said electrolyte, divalent copper ions (Cu) 2+ ) The content of (A) is 40-80g/L; hydrogen ion (H) + ) The content of (A) is 1-1.5mol/L; chloride ion (Cl) - ) The content of (A) is 50-60mg/L; the content of the additive is 6-12mg/L.
10. The method for preparing nano twinned copper material as claimed in claim 9, characterized in that in said electrolyte, cu is present 2+ From copper sulfate, copper sulfate hydrate, or a mixture of copper sulfate and copper chloride; h + Derived from hydrochloric acid or sulfuric acid; cl - Derived from hydrochloric acid or sodium chloride.
11. The method for preparing nano twin crystal copper material as claimed in claim 7, wherein in the electrolyte, the additive comprises gelatin and sodium polydithiodipropanesulfonate SPS, and the weight ratio of the gelatin to the sodium polydithiodipropanesulfonate SPS is 2: 1 to 1: 3.
12. The method for preparing nano twinned copper material as claimed in claim 11, characterized in that the weight ratio of said gelatin to sodium polydithiodipropanesulfonate SPS is 1: 1 to 1: 2.
13. The method for preparing nano twin crystal copper material as recited in claim 11, characterized in that in the direct current electrolytic deposition technique, the current density matches the weight ratio of gelatin to sodium polydithiodipropanesulfonate SPS in the additive, gelatin/SPS rises, current density falls, and the relationship between gelatin/SPS and the current density satisfies 1: 30-1: 100.
14. The method for preparing nano twinned copper material as claimed in claim 13, characterized in that the relationship between said gelatin/SPS and said current density satisfies 1: 50-1: 90.
15. The method for preparing nano twin crystal copper material as claimed in claim 13, wherein the current density is 30-55mA/cm 2 The temperature of the electrolyte is 15-25 ℃, and the deposition time is 4-16 h.
16. The method for preparing nano twin crystal copper material as recited in claim 7, characterized in that in the direct current electrolytic deposition technique, the components in the electrolyte are kept uniform all the time by using magnetic stirring.
CN202210888293.6A 2022-07-26 2022-07-26 Nano twin crystal copper material with (110) orientation and preparation method thereof Pending CN115341248A (en)

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