CN105803501A - Preparation method for high-density twin crystal metal material - Google Patents
Preparation method for high-density twin crystal metal material Download PDFInfo
- Publication number
- CN105803501A CN105803501A CN201610144142.4A CN201610144142A CN105803501A CN 105803501 A CN105803501 A CN 105803501A CN 201610144142 A CN201610144142 A CN 201610144142A CN 105803501 A CN105803501 A CN 105803501A
- Authority
- CN
- China
- Prior art keywords
- preparation
- metal material
- high density
- density twin
- metal
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
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
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides a preparation method for a high-density twin crystal metal material. The preparation method comprises the following steps that S1, metal sheets with the good electrical conductivity are selected, after degreasing, rust removing and polishing treatment, a plurality of parallel grooves are ground in the surface of each metal sheet through abrasive paper, a flat protrusion strip is arranged between any two grooves, and the grooves and the protrusion strips are periodically arranged at intervals; and S2, a direct current electrolytic deposition method is used, high-purity water or a metal salt solution is selected as an electrolytic solution, the metal sheets ground in the step S1 are adopted as a cathode and an anode, and electrolytic deposition is conducted to obtain the high-density twin crystal metal material. The preparation method provided by the invention is simple in process and low in cost, and the uniformly distributed high-density twin crystal metal material with the growing crystal boundary interval being 2-5 nm can be obtained.
Description
Technical field
The present invention relates to the preparation method of a kind of high density twin metal material.
Background technology
Crystal boundary, lower state coherent grain boundary, is a kind of special microstructural defects.Twin boundary in nano material
The performances such as its optics, electronics, machinery there is important impact.Such as, the twin boundary in nano twin crystal metal
Efficiently hinder dislocation motion, thus improve the intensity of crystal, ductility and electric conductivity.Experiment (Science,
2009,323,607) and theoretical (nature, 2010,464,877) all confirm the intensity of nano twin crystal along with
The minimizing of crystal boundary spacing and increased.The most how to obtain twin boundaries spacing little and be evenly distributed highly dense
Degree nano twin crystal material, has important application prospect.
At present, the method preparing nano twin crystal mainly includes two aspects: be on the one hand top-to-bottom method, example
Such as plastic deformation method, local pressure deformation (Nat.Commun.2015,6,7648), wherein plastic deformation
Method, the twin metal material obtained by high pressure torsion deformation, twin density is relatively low and distribution at random can not
Control；On the other hand be bottom-to-top method, electro-deposition, magnetron sputtering (Appl.Phys.Lett., 2006,88,
173116), wherein electro-deposition includes DC electrodeposition and pulse current deposition (Chinese patent
CN102321896A), by regulation electric current density (referring to document: Acta Metallurgica Sinica, 2013,49,635),
The temperature (referring to document: Acta Metallurgica Sinica, 2012,48,1342) of electrolyte and impulse wave sedimentation rate
(Science, 2009,323,607) obtains nano twin crystal copper nanocrystallite, but the most disclosed document
And patent, in the nano twin crystal material obtained, most twin boundaries density is low and crystal boundary distribution is random, it is thus achieved that
Density nano metal twin material that is high and that be evenly distributed is the most difficult.Therefore, a kind of high density twin is found
The preparation method of metal material, is the direction the most primarily studied, this area.
Summary of the invention
It is smaller than 10nm and the more uniform twin of crystal boundary distribution owing to there is presently no acquisition twin boundaries
Metal material, therefore, based on technical problem present in prior art, the present invention proposes one and can prepare
The method of high density nano twin crystal metal material, i.e. polish specific sheet metal surface texture, by fine setting
The distribution of sheet metal sheet resistance obtains periodic current distribution, thus it is little and be evenly distributed to obtain crystal boundary spacing
High density twin metal material.
The invention provides the preparation method of a kind of high density twin metal material, comprise the steps,
S1: choose the sheet metal with excellent conductive performance, after oil removing, rust cleaning, polishing, use sand paper
Polish some grooves being parallel to each other on described sheet metal surface, be smooth between groove described in any two
Raised line, described groove and described raised line are period distances arrangement；
S2: use DC electrodeposition method, electrolyte selects high purity water or metal salt solution, negative electrode and sun
The sheet metal in S1 after polishing is all selected in pole, carries out electro-deposition, obtains high density twin metal material.
Preferably, in S1, selected sheet metal is silver strip or copper sheet.
It is highly preferred that described metal length of a film 2cm～4cm, wide 1cm～2cm, thick 0.5cm～0.6cm.
It is highly preferred that the distance of described negative electrode and described anode is 1cm～5cm, voltage 10V～30V, electricity
Solve liquid temp 5 °～30 °, sedimentation time 10min～30min.
Preferably, in S1, the particle diameter of described sand paper is 0.5mm～8mm.
It is highly preferred that the particle diameter of described sand paper is 1mm～2mm.
It is highly preferred that in S1, when using sand papering, the length along sheet metal is polished in the same direction.
Preferably, in S2, the concentration of described metal salt solution is 0.001mol/L～0.05mol/L.
It is highly preferred that the concentration of described metal salt solution is 0.005mol/L～0.01mol/L
It is highly preferred that described slaine is silver nitrate or copper sulfate.
The preparation method of the high density twin metal material that the present invention provides, preparation technology is simple, low cost,
Taken advantage of a situation in the same direction by the sheet metal sand for surface paper crossed in based process and to polish some being parallel to each other
Groove, uses the sand paper parallel long axis direction polishing metal electrode of different size, can obtain different electrode rule
Lattice.Using this sheet metal as electrode, utilize electro-deposition method, the polishing vestige formed due to sheet metal surface
Increase surface area, decrease resistance so that electrode surface resistance mechanical periodicity, cause further electrode
Current cycle changes, and forms periodic current distribution on sheet metal surface, and coherence twin boundaries can reduce interface
Can, therefore create substantial amounts of twin, thus obtaining growth crystal boundary spacing is 2-5nm, and be evenly distributed
High density twin metal material.
Accompanying drawing explanation
The electrode schematic top plan view that Fig. 1 provides for the embodiment of the present invention 1；
The electrode schematic side view that Fig. 2 provides for the embodiment of the present invention 1；
The TEM of the high density nano twin crystal silver structure that Fig. 3 is prepared for the electrode that the embodiment of the present invention 1 provides
Figure；
The SAED figure of the high density twin silver structure that Fig. 4 is prepared for the electrode that the embodiment of the present invention 1 provides.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that technical scheme and can be practiced,
Below in conjunction with specific embodiment, the invention will be further described, but illustrated embodiment is not as to the present invention's
Limit.
Embodiment 1
The preparation method of a kind of high density twin ag material, comprises the steps,
Choose the silver strip 1 of long 2cm wide 1cm thickness 0.5cm, concrete as it is shown in figure 1, with clear water and go
Dirty powder removes surface grease and dust etc., then removes oxide on surface with dilute hydrochloric acid, after polishing, then uses particle diameter
Sand paper for 1mm is polished twice by same direction along the length of silver strip at a side surface, polish respectively
Some grooves being parallel to each other are smooth raised line, described groove and described raised line between any two groove in
Period distances arranges；The vertical view of this silver strip and schematic side view, the most as shown in Figure 1-2, once after polishing
Spacing G1 between each groove is 1mm, after secondary polishing, at the arbitrary neighborhood two formed of once polishing
New groove is defined again between individual groove.In Fig. 1,102 is the groove formed during polishing for the first time, 101
The groove formed during for second time polishing.
Using two electrode DC electro-deposition methods, negative electrode and anode all select the silver strip after above-mentioned steps process,
Electrolyte selects high purity water, and the spacing of negative electrode and anode is 2cm, voltage 30V, electrolyte temperature 25 °,
Sedimentation time 30min, it is thus achieved that high density twin ag material, during it will be clear that use, two electricity
The reeded one side of polishing of pole is oppositely arranged.
The high density twin ag material prepared is as shown in Figure 3 and Figure 4；Fig. 3 is high density twin ag material
Transmission electron microscope photo, this sample is formed by the 2-5nm that is parallel to each other is nanocrystalline, nanocrystalline
Border be twin boundaries, crystal boundary parallel and distribution the most uniform.The SEAD pattern of grain boundaries is such as
Shown in Fig. 4, comprise two set speckles, be the obvious characteristic of twin.
Embodiment 2
The preparation method of a kind of high density twin copper product, comprises the steps,
Choose the copper sheet of long 4cm width 2cm thickness 0.6cm, with clear water and abstergent remove surface grease and
Dust etc., then remove oxide on surface with dilute hydrochloric acid, after polishing, then with the sand paper that particle diameter is 1mm on surface
Length along copper sheet is polished twice by same direction, polish some grooves being parallel to each other, and any two
Being smooth raised line between individual groove, described groove and raised line are period distances arrangement；
Using two electrode DC electro-deposition methods, electrolyte selects molar concentration to be that 0.005mol/L copper sulfate is molten
The distance that liquid, negative electrode and anode all select above-mentioned steps to have reeded copper sheet, negative electrode and anode after processing is
4cm, voltage 20V, electrolyte temperature 20 °, sedimentation time 20min, high density twin copper material can be obtained
Material.
Embodiment 3
The preparation method of a kind of high density twin ag material, comprises the steps,
Choose the silver strip of long 2cm width 1cm thickness 0.5cm, with clear water and abstergent remove surface grease and
Dust etc., then remove oxide on surface with dilute hydrochloric acid, after polishing, then with the sand paper that particle diameter is 2mm on surface
Length along silver strip is polished three times by same direction, polish some grooves being parallel to each other respectively, appoints
Anticipating between two grooves is smooth raised line, and described groove and described raised line are period distances arrangement；This silver strip
Overlook and schematic side view, the most as shown in Figure 1-2.
Using two electrode DC electro-deposition methods, negative electrode and anode all select the silver strip after above-mentioned steps process,
The distance that electrolyte selects higher molar concentration to be 0.01mol/L silver nitrate solution, negative electrode and anode is 5cm,
Voltage 10V, electrolyte temperature 30 °, sedimentation time 30min, obtain high density twin ag material.
To the high density twin copper product obtained by embodiment 2 and embodiment 3 and high density twin ag material sample
Product are tested, and the transmission electron microscope photo obtained is similar to embodiment 1, are also to be put down by crystal boundary
The more uniform nanocrystalline composition of 2-5nm of row and distribution.
The preparation method of high density twin copper product and high density twin ag material is only done by above-described embodiment
Example, but it is not limited to both materials, as long as the sheet metal with excellent conductive performance can pass through
Said method obtains high density twin structure.
Concrete, after the sheet metal of excellent conductive performance is polished particular groove, as electrode, by
Arranging by groove and smooth two parts unit period distances in sheet metal surface, groove part is relative to evener
Point adding surface area, its resistance reduces relatively, compares flat portion, increases electric current density, groove and
The current cycle distribution of flat portion, coherence twin boundaries can reduce interface energy, therefore create substantial amounts of
Twin boundary, can be obtained by electro-deposition method.
Embodiment described above is only the preferred embodiment lifted by absolutely proving the present invention, and it protects model
Enclose and be not limited to this.The equivalent that those skilled in the art are made on the basis of the present invention substitutes or conversion,
All within protection scope of the present invention, protection scope of the present invention is as the criterion with claims.
Claims (10)
1. the preparation method of a high density twin metal material, it is characterised in that comprise the steps,
S1: choose the sheet metal with excellent conductive performance, after oil removing, rust cleaning, polishing, use sand paper
Polish some grooves being parallel to each other on described sheet metal surface, be smooth between groove described in any two
Raised line, described groove and described raised line are period distances arrangement；
S2: use DC electrodeposition method, electrolyte selects high purity water or metal salt solution, negative electrode and sun
The sheet metal in S1 after polishing is all selected in pole, carries out electro-deposition, obtains high density twin metal material.
The preparation method of high density twin metal material the most according to claim 1, it is characterised in that
In S1, selected sheet metal is silver strip or copper sheet.
The preparation method of high density twin metal material the most according to claim 2, it is characterised in that
Described metal length of a film 2cm～4cm, wide 1cm～2cm, thick 0.5cm～0.6cm.
The preparation method of high density twin metal material the most according to claim 2, it is characterised in that
The distance of described negative electrode and described anode is 2cm～5cm, voltage 10V～30V, electrolyte temperature 5 °～
30 °, sedimentation time 10min～30min.
The preparation method of high density twin metal material the most according to claim 1, it is characterised in that
In S1, the particle diameter of described sand paper is 0.5mm～8mm.
The preparation method of high density twin metal material the most according to claim 5, it is characterised in that
The particle diameter of described sand paper is 1mm～2mm.
The preparation method of high density twin metal material the most according to claim 1, it is characterised in that
In S1, when using sand papering, the length along described sheet metal is polished in the same direction.
The preparation method of high density twin metal material the most according to claim 1, it is characterised in that
In S2, the concentration of described metal salt solution is 0.001mol/L～0.05mol/L.
The preparation method of high density twin metal material the most according to claim 8, it is characterised in that
The concentration of described metal salt solution is 0.005mol/L～0.01mol/L.
The preparation method of high density twin metal material the most according to claim 8 or claim 9, its feature
Being, described slaine is silver nitrate or copper sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610144142.4A CN105803501B (en) | 2016-03-08 | 2016-03-08 | A kind of preparation method of high density twin metal material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610144142.4A CN105803501B (en) | 2016-03-08 | 2016-03-08 | A kind of preparation method of high density twin metal material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105803501A true CN105803501A (en) | 2016-07-27 |
| CN105803501B CN105803501B (en) | 2018-08-14 |
Family
ID=56468370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610144142.4A Expired - Fee Related CN105803501B (en) | 2016-03-08 | 2016-03-08 | A kind of preparation method of high density twin metal material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105803501B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108754605A (en) * | 2018-06-22 | 2018-11-06 | 东北大学 | The device and method of electro-deposition oriented growth metal single crystal in aqueous electrolyte |
| CN112941586A (en) * | 2019-11-23 | 2021-06-11 | 苹果公司 | Nano twin crystal copper component |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498987A (en) * | 2002-11-01 | 2004-05-26 | 中国科学院金属研究所 | Nano twin crystal copper material with ultrahigh strength and superhigh conductivity as well as preparation method |
| CN101144172A (en) * | 2007-07-20 | 2008-03-19 | 哈尔滨工程大学 | High corrosion resistance nano twin crystal nickel coating and preparation method thereof |
| CN101403096A (en) * | 2008-11-06 | 2009-04-08 | 哈尔滨工程大学 | Nano-twin crystal aluminum surface film material with high corrosion resistance and method of producing the same |
| CN102400188A (en) * | 2010-09-10 | 2012-04-04 | 中国科学院金属研究所 | (111) texture nano-grade twin crystal Cu block material and preparation method thereof |
| US20120135260A1 (en) * | 2010-11-05 | 2012-05-31 | The California Institute Of Technology | Fabrication of nano-twinned nanopillars |
| US20130122326A1 (en) * | 2011-11-16 | 2013-05-16 | National Chiao Tung University | Electrodeposited Nano-Twins Copper Layer and Method of Fabricating the Same |
| US20130270121A1 (en) * | 2012-04-12 | 2013-10-17 | National Tsing Hua University | Method for fabricating copper nanowire with high density twins |
| TW201542888A (en) * | 2014-05-02 | 2015-11-16 | Univ Nat Chiao Tung | Nano-twinned Ni layer, method for manufacturing the same, and electrical connecting structure, substrate and package structure containing the same |
-
2016
- 2016-03-08 CN CN201610144142.4A patent/CN105803501B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498987A (en) * | 2002-11-01 | 2004-05-26 | 中国科学院金属研究所 | Nano twin crystal copper material with ultrahigh strength and superhigh conductivity as well as preparation method |
| CN101144172A (en) * | 2007-07-20 | 2008-03-19 | 哈尔滨工程大学 | High corrosion resistance nano twin crystal nickel coating and preparation method thereof |
| CN101403096A (en) * | 2008-11-06 | 2009-04-08 | 哈尔滨工程大学 | Nano-twin crystal aluminum surface film material with high corrosion resistance and method of producing the same |
| CN102400188A (en) * | 2010-09-10 | 2012-04-04 | 中国科学院金属研究所 | (111) texture nano-grade twin crystal Cu block material and preparation method thereof |
| US20120135260A1 (en) * | 2010-11-05 | 2012-05-31 | The California Institute Of Technology | Fabrication of nano-twinned nanopillars |
| US20130122326A1 (en) * | 2011-11-16 | 2013-05-16 | National Chiao Tung University | Electrodeposited Nano-Twins Copper Layer and Method of Fabricating the Same |
| US20130270121A1 (en) * | 2012-04-12 | 2013-10-17 | National Tsing Hua University | Method for fabricating copper nanowire with high density twins |
| TW201542888A (en) * | 2014-05-02 | 2015-11-16 | Univ Nat Chiao Tung | Nano-twinned Ni layer, method for manufacturing the same, and electrical connecting structure, substrate and package structure containing the same |
Non-Patent Citations (5)
| Title |
|---|
| JIXIANG FANG等: "Silver nanowires growth via branch fragmentation of electrochemically grown silver dendrites", 《CHEMCOMM》 * |
| T.KILNER等: "On the Formation of Growth Twins in Electrodeposited Silver", 《J.ELECTROCHEM.SOC.:ELECTROCHEMICAL SCIENCE》 * |
| U KLEMENT等: "Characterization of multiple twinned structural units in pulse-electrodeposited nickel", 《IOP CONF. SERIES: MATERIALS SCIENCE AND ENGINEERING》 * |
| 张允诚等: "《电镀手册》", 31 January 2007, 国防工业出版社 * |
| 成宇浩等: "温度对电沉积纳米孪晶Ni显微结构及纳米压痕力学性能的影响", 《金属学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108754605A (en) * | 2018-06-22 | 2018-11-06 | 东北大学 | The device and method of electro-deposition oriented growth metal single crystal in aqueous electrolyte |
| CN112941586A (en) * | 2019-11-23 | 2021-06-11 | 苹果公司 | Nano twin crystal copper component |
| US11901585B2 (en) | 2019-11-23 | 2024-02-13 | Apple Inc. | Nanotwin copper components |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105803501B (en) | 2018-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chettah et al. | Effect of the electrochemical technique on nanocrystalline ZnO electrodeposition, its structural, morphological and photoelectrochemical properties | |
| CN102770972A (en) | Photovoltaic cell, including a crystalline silicon oxide passivation thin film, and method for producing same | |
| US20150136212A1 (en) | Electrical contacts to nanostructured areas | |
| JP2015504599A (en) | Thermal expansion control type flexible metal substrate material having texture structure | |
| CN102856430A (en) | Preparation method for bismuth titanate nanowire solar cells | |
| JP2012064839A (en) | Crystal silicon based solar cell and method of manufacturing the same | |
| CN105803501A (en) | Preparation method for high-density twin crystal metal material | |
| CN103225104A (en) | Single crystal anatase titanium dioxide nano-tube array and preparation method thereof | |
| Drabczyk et al. | Influence of screen printing parameters on the front metallic electrodes geometry of solar cells | |
| CN102899683A (en) | Preparation method of Ti-based nano-CeO2/PbO2 modified electrode | |
| CN104528887A (en) | Preparation method of Ti/SnO2-Sb thin film electrode for sewage deep treatment | |
| CN103590087A (en) | TiO2 nanotube array film with periodically-changing inner aperture and adjustable period and preparation method thereof | |
| CN106119922B (en) | A kind of cuprous oxide is electrodeposited in composite material on TiOx nano chip arrays film and preparation method thereof | |
| CN108281550A (en) | Based on the titania-doped perovskite solar cell and preparation method thereof of magnesium | |
| CN104233433A (en) | Method for preparing cuprous oxide thin film | |
| Tsuchiya et al. | Metallurgical aspects on the formation of self-organized anodic oxide nanotube layers | |
| Wang et al. | Synthesis and characterization of TiO2 nanotube film on fluorine-doped tin oxide glass | |
| AL-Zahrani et al. | Effect of hydrothermal growth temperature and time on physical properties and photoanode performance of zno nanorods | |
| CN103147041B (en) | The preparation method of transparent conductive oxide film | |
| CN103882393B (en) | Transfer is inverted template and is prepared orderly germanium nanopoint battle array | |
| CN102864465A (en) | Preparation method of high-activity Ti/Pr2O3-PbO2 modified electrode | |
| Sasano et al. | Pulse electrodeposition of CuO thin films to improve crystallinity for the enhancement of photoelectrochemical response | |
| CN108977848A (en) | A kind of Cu2The preparation method of the Quito O layer photocathode thin-film material | |
| JP2007088434A (en) | Photovoltaic device | |
| JP2014512684A (en) | 2D crystalline coating based on the integration of ZnO on a conductive plastic substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| DD01 | Delivery of document by public notice |
Addressee: Patent of Shanxi Datong University The person in charge Document name: payment instructions |
|
| DD01 | Delivery of document by public notice | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180814 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |