CN110382743A - High-purity electrolytic copper - Google Patents
High-purity electrolytic copper Download PDFInfo
- Publication number
- CN110382743A CN110382743A CN201880015294.1A CN201880015294A CN110382743A CN 110382743 A CN110382743 A CN 110382743A CN 201880015294 A CN201880015294 A CN 201880015294A CN 110382743 A CN110382743 A CN 110382743A
- Authority
- CN
- China
- Prior art keywords
- electro
- deposition
- copper
- purity
- crystal
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention provides a kind of high-purity electrolytic copper, wherein, the purity of Cu in addition to gas componant O, F, S, C, Cl is 99.9999 mass % or more, and the content of S is 0.1 mass ppm or less, on the section of through-thickness by electron backscatter diffraction carried out crystal orientation measurement as a result, the area ratio of the crystal of the planar orientation with ± 10 ° of (101) less than 40%.
Description
Technical field
A kind of purity the present invention relates to Cu in addition to gas componant (O, F, S, C, Cl) is 99.9999 mass % or more
And by electrorefining electro-deposition in the high-purity electrolytic copper on the surface of cathode plate.
Patent application 2017-109244 of the application based on June 1st, 2017 in Japanese publication, on June 2nd, 2017
Japanese publication patent application 2017-110418 and on May 21st, 2018 Japanese publication patent application 2018-
No. 097318 and patent application 2018-097319 CLAIM OF PRIORITY, and its content is applied at this.
Background technique
The purity of Cu in addition to gas componant (O, F, S, C, Cl etc.) is the high-purity copper example of 99.9999 mass % or more
Such as it is used for sputtering target, bonding line, voice-frequency cable, accelerator purposes.
As the method for obtaining this high-purity copper, following electrolytic refining process is widely used: in the electrolysis with copper ion
The cathode for impregnating the anode plate being for example made of the copper sheet of 99.99 mass % of purity or so in liquid and being for example made of stainless steel plate
Plate, and be powered to these, make the copper electro-deposition of high-purity on the surface of cathode plate from there through cell reaction.Moreover,
By removing electro-deposition in the copper on the surface of cathode plate, cathode copper more higher than anode plate purity is obtained.
For example, disclosing in patent document 1, there are as below methods: will carry out electrorefining in copper sulfate solution and obtain
Copper further in aqueous solution of nitric acid with 100A/m2Current density below is electrolysed again, thus obtains high-purity electricity
Solve copper.
Also, disclose in patent document 2 it is a kind of define as impurity and comprising non-metallic inclusion partial size
And the high-purity copper of population.
Here, in above-mentioned electrolytic refining process, in order to control electro-deposition in the form of the copper on cathode plate, usually carry out by
The additive (such as animal glue) of cell reaction is inhibited to be added to the processing in electrolyte.However, above-mentioned animal glue contain sulphur at
Point, therefore the tendency that the sulfur content with the copper as obtained from electro-deposition rises.
Therefore, following content is disclosed in patent document 3: being contained to reduce the sulphur of the copper as obtained from electro-deposition
Amount, as additive, uses polyethylene glycol (PEG) or polyvinyl alcohol (PVA).
If its is not sufficiently effective or excessive for the additive of these control cell reactions, on surface of the electro-deposition in cathode plate
The surface of copper generate concave-convex, or to generate the electro-deposition such as dendrite abnormal.Electrolyte is caused to be trapped in the unusual part, it can not
The purity of cathode copper is sufficiently improved, therefore the control of additive is very important.
Patent document 1: Japanese Patent Publication 08-000990 bulletin (A)
Patent document 2: Japanese Unexamined Patent Publication 2005-307343 bulletin (A)
Patent document 3: No. 4620185 bulletins (A) of Japanese Patent No.
When having used previous additive, cell reaction in extra-inhibitory cathode plate, therefore there is electro-deposition stress
The tendency got higher.Warpage is generated in the copper on surface due to the electro-deposition stress in electro-deposition in cathode plate and is taken off in electrolysis
It falls, can not steadily manufacture cathode copper sometimes.Also, even if not fallen off in electrolysis in the case where obtained cathode copper, if
It removes and places from cathode plate, then generate warpage because of electro-deposition stress (residual stress) remained in cathode copper, exist
It is difficult to the problem of carrying out processing thereafter.
Summary of the invention
The invention is to complete in view of the foregoing, and the Cu's that its purpose is to provide a kind of in addition to gas componant is pure
Degree is 99.9999 mass % or more, and the content of S is 0.1 mass ppm hereinafter, being answered by electro-deposition when reducing electro-deposition
Power and can steadily be manufactured, and even if from cathode plate remove after warpage generation be inhibited and treatability
Excellent high-purity electrolytic copper.
In order to solve the above problems, high-purity electrolytic copper of the invention is characterized in that, except gas componant (O, F, S, C,
Cl the purity of the Cu other than) is 99.9999 mass % or more, and the content of S is 0.1 mass ppm hereinafter, in through-thickness
On section by electron backscatter diffraction carried out crystal orientation measurement as a result, the crystal of the planar orientation with ± 10 ° of (101)
The area ratio less than 40%.
In the high-purity electrolytic copper of the structure, in the section of through-thickness (that is, section of the direction of growth along electro-deposition
Face) on, the area ratio of the crystal with (101) ± 10 ° planar orientation is suppressed to less than 40%, therefore can by cell reaction
Inhibit the crystal growth with the planar orientation of ± 10 ° of (101) be it is larger, electro-deposition stress when electro-deposition reduces.Also, pass through
The orientation of crystal becomes at random, to disperse to strain.It is obtained the generation of warpage after being removed as a result, even if from cathode plate
Inhibit, and treatability is excellent.
Also, the purity of the Cu in addition to gas componant (O, F, S, C, Cl) is 99.9999 mass % or more, and S contains
Amount is 0.1 mass ppm hereinafter, can be consequently used for requiring the various uses of high-purity.
Here, in high-purity electrolytic copper of the invention, by electron backscattered preferably on the section of through-thickness
It is that diffraction has carried out crystal orientation measurement as a result, the area ratio of the crystal of the planar orientation with ± 10 ° of (111) is less than 15%.
In this case, on the section of through-thickness (that is, along section of the direction of growth of electro-deposition), have
(111) the area ratio of the crystal of ± 10 ° of planar orientation is suppressed to less than 15%, therefore may also suppress and have by cell reaction
(111) crystal growth of ± 10 ° of planar orientation is larger, and electro-deposition stress when electro-deposition reduces.Also, pass through taking for crystal
Tropism further becomes at random, to disperse to strain.Pressed down the generation of warpage after being removed as a result, even if from cathode plate
System, and treatability is excellent.
Also, in high-purity electrolytic copper of the invention, in the section of through-thickness (that is, along the growth side of electro-deposition
To section) on, the aspect ratio b/a preferably indicated with the long axis a of crystal grain and the short axle b orthogonal with long axis a is less than 0.33
The area ratio of crystal grain is less than 40%.
In this case, aspect ratio b/a is suppressed to lower less than the area ratio of 0.33 crystal grain, therefore can discharge product
The strain in crystal grain is stored, is inhibited the generation of warpage after being removed even if from cathode plate, and treatability is excellent.
In addition, in high-purity electrolytic copper of the invention, Cu's preferably in addition to gas componant (O, F, S, C, Cl) is pure
Degree is 99.99999 mass % or more, and the content of S is 0.02 mass ppm or less.
In this case, the purity of the Cu in addition to gas componant (O, F, S, C, Cl) is 99.99999 mass % or more,
And the content of S is 0.02 mass ppm hereinafter, in turn, additionally it is possible to suitable for requiring the purposes of the copper of higher purity.
In accordance with the invention it is possible to provide a kind of following high-purity electrolytic copper: the purity of the Cu in addition to gas componant is
99.9999 mass % or more, and the content of S is 0.1 mass ppm hereinafter, by reducing electro-deposition stress energy when electro-deposition
It is enough steadily to be manufactured, and be inhibited after being removed even if from cathode plate the generation of warpage and treatability is excellent.
Detailed description of the invention
Figure 1A is the outline figure of the high-purity electrolytic copper in embodiments of the present invention, is its main view.
Figure 1B is the outline figure of the high-purity electrolytic copper in embodiments of the present invention, is its A-A cross-sectional view.
Specific embodiment
Hereinafter, being illustrated to high-purity electrolytic copper involved in one embodiment of the present invention.
As illustrated in figures 1A and ib, the high-purity electrolytic copper 10 of present embodiment passes through yin of electro-deposition when electrorefining
It is obtained on the surface of pole plate 1, in the state of being removed from cathode plate 1 plate-like (as high-purity electrolytic copper plate).Also,
On cathode plate 1 in electrorefining, in order to prevent electro-deposition in the cathode copper on two faces of cathode plate 1 it is mutual contact simultaneously
The cathode copper of desired size is obtained, is configured with the glue that electro-deposition prevents in the peripheral portion in addition to the top of cathode plate 1
Band etc..In addition, in the present embodiment, the thickness t of high-purity electrolytic copper 10 is in the range of 1mm≤t≤100mm.Also, it is high
The wide W of the plate of the purity cathode copper 10 and long L of plate is respectively in the range of 0.05m≤W≤5m, in the range of 0.05m≤L≤5m.
The composition of the high-purity electrolytic copper 10 of present embodiment is the Cu in addition to O, F, S, C, Cl as gas componant
Purity be 99.9999 mass % (6N) or more, and the content of S be 0.1 mass ppm or less.In addition, except as gas componant
O, the purity of the Cu other than F, S, C, Cl is preferably 99.99999 mass % (7N) or more.Except as O, F of gas componant, S, C,
The upper limit value of the purity of Cu other than Cl is simultaneously not particularly limited, but preferably 99.999999 mass % (8N) are below.Also, S
Content be preferably 0.02 mass ppm or less.The lower limit value of the content of S is simultaneously not particularly limited, but preferably 0.001 mass
Ppm or more.
In addition, the analysis of impurity element is able to use glow discharge mass spectrometry analytical equipment (GD-MS) Lai Jinhang.
Moreover, in the high-purity electrolytic copper 10 of present embodiment, by electron backscatter diffraction to through-thickness
It is that section (in Figure 1B be Section A-A) has carried out crystal orientation measurement as a result, the crystal of the planar orientation with ± 10 ° of (101)
The area ratio is less than 40%.
Also, in the high-purity electrolytic copper of present embodiment 10, by electron backscatter diffraction to through-thickness
Section (in Figure 1B be Section A-A) carried out crystal orientation measurement as a result, it is preferred that the crystalline substance of the planar orientation with ± 10 ° of (111)
The area ratio of body is less than 15%.
Here, in the present embodiment, it, will be adjacent in the crystal orientation analysis carried out by electron backscatter diffraction method
Pixel between misorientation be that 5 ° or more of boundary is considered as crystal boundary and measures the crystal of the planar orientation with ± 10 ° of (101)
The area ratio of the crystal of the area ratio and the planar orientation with ± 10 ° of (111).
In addition, (being in fig. ib A-A in the section of through-thickness in the high-purity electrolytic copper 10 of present embodiment
Section) on, the aspect ratio b/a preferably indicated with the long axis a of crystal grain diameter and the short axle b orthogonal with long axis a is less than 0.33
The area ratio of crystal grain is less than 40%.
Here, in the present embodiment, it, will be adjacent in the crystal orientation analysis carried out by electron backscatter diffraction method
Pixel between misorientation to be that crystal grain that 5 ° or more of boundary is considered as crystal boundary, and will identify that carries out oval approximate, calculating should
The ratio between elliptical major diameter a and minor axis b are aspect ratio b/a, and measure the area ratio of crystal grain of the aspect ratio b/a less than 0.33.
It (is in fig. ib A-A in the section of through-thickness also, in the high-purity electrolytic copper of present embodiment 10
Section) on, preferably average crystal grain diameter is in 15 μm or more and 35 μm or less of range.
In the present embodiment, in the crystal orientation analysis carried out by electron backscatter diffraction method, by adjacent picture
The boundary that misorientation between element is 5 ° or more is considered as crystal boundary, and obtained crystal grain is round with round progress of the same area
The circular diameter is considered as crystal grain diameter and calculates each crystal grain diameter by approximation.At this point, a part for crystal grain is measuring
Crystal grain outside the visual field, other than measure object.Also, average crystal grain diameter is calculated according to following formula.
[mathematical expression 1]
rave: average crystal grain diameter
S: particle area
R: particle diameter
N: population
In addition, preferably the glossiness on surface is 2 or more in the high-purity electrolytic copper 10 of present embodiment.
In the present embodiment, according to JIS Z 8741:1997 (correspond to ISO 2813:1994 and ISO 7668:
1986), using vancometer with the central portion on 60 ° of the incidence angle surfaces to high-purity electrolytic copper 10 (in figure 1A for point P) into
Row measurement.
Hereinafter, section (the edge of the through-thickness to the high-purity electrolytic copper 10 of regulation present embodiment as described above
Electro-deposition is in the section of the direction of growth of the copper on the surface of cathode plate 1) on the planar orientation with ± 10 ° of (101) crystal
The area ratio, planar orientation with ± 10 ° of (111) crystal the area ratio, with the long axis a of crystal grain diameter and with long axis a just
The area ratio of crystal grain of the aspect ratio b/a less than 0.33 that the short axle b of friendship is indicated, average crystal grain diameter, high-purity electrolytic copper table
The reason of glossiness in face, is illustrated.
(the area ratio: less than 40% of the crystal with (101) ± 10 ° planar orientation)
In copper electro-deposition in the surface of cathode plate 1 and when crystal growth, if the crystal of the planar orientation with ± 10 ° of (101)
It is grown to larger, is then difficult to discharge generated strain when copper electro-deposition, electro-deposition stress is got higher.Therefore, in the copper of electro-deposition
In be easy to produce warpage.
Therefore, in the present embodiment, by the crystalline substance of the planar orientation on the section of through-thickness with (101) ± 10 °
The area ratio of body is set as less than 40%, and ratio occupied by the crystal grown along a direction is set as lower.
The face with ± 10 ° of (101) in addition, in order to further suppress electro-deposition stress, on the section of through-thickness
The area ratio of the crystal of orientation is preferably 30% or less.The planar orientation with ± 10 ° of (101) on the section of through-thickness
The lower limit value of the area ratio of crystal is simultaneously not particularly limited, but is preferably set to 5% or more.
(the area ratio: less than 15% of the crystal with (111) ± 10 ° planar orientation)
In copper electro-deposition in the surface of cathode plate 1 and when crystal growth, if the crystal of the planar orientation with ± 10 ° of (111)
It is grown to larger, is then difficult to discharge generated strain when copper electro-deposition, electro-deposition stress is got higher.Therefore, in the copper of electro-deposition
In be easy to produce warpage.Here, by the way that the area ratio of the crystal of the planar orientation with ± 10 ° of (111) is set as holding less than 15%
It easily discharges generated strain, electro-deposition stress when copper electro-deposition to be lower, the warpage of the copper of electro-deposition can be further suppressed.
Therefore, in the present embodiment, by the crystalline substance of the planar orientation on the section of through-thickness with (111) ± 10 °
The area ratio of body is set as less than 15%, and ratio occupied by the crystal grown along a direction is set as lower.
The face with ± 10 ° of (111) in addition, in order to further suppress electro-deposition stress, on the section of through-thickness
The area ratio of the crystal of orientation is preferably 10% or less.The planar orientation with ± 10 ° of (111) on the section of through-thickness
The lower limit value of the area ratio of crystal is simultaneously not particularly limited, but is preferably set to 2% or more.
(the area ratio of crystal grain of the aspect ratio b/a less than 0.33: 40% or less)
When electro-deposition in the aspect ratio of the crystal grain of the copper on the surface of cathode plate 1 less than 0.33 when, crystal grain becomes elongated, meeting
The a large amount of strains of savings.Therefore, there is the stress remained in high-purity electrolytic copper 10 to become relatively high tendency.Here, passing through
The area ratio of crystal grain of the aspect ratio b/a less than 0.33 is set as 40% hereinafter, can will remain in high-purity electrolytic copper 10
Stress is suppressed to substantially low.
Therefore, in the present embodiment, by the face of crystal grain of the aspect ratio b/a less than 0.33 on the section of through-thickness
Product rate is defined as 40% or less.
In addition, in order to further suppress the stress remained in high-purity electrolytic copper 10, crystalline substance of the aspect ratio b/a less than 0.33
The area ratio of grain is preferably 20% or less.The lower limit value of the area ratio of crystal grain of the aspect ratio b/a less than 0.33 is not limited especially
It is fixed, but it is preferably set to 5% or more.
(average crystal grain diameter: 15 μm or more and 35 μm or less)
If crystal grain diameter is fine, position that the crystal of electro-deposition is fused to each other becomes more, and when fusion, generated strain was accumulated
It stores, the tendency got higher on the whole with electro-deposition stress.On the other hand, if crystal grain diameter is coarse, cathode copper surface therewith
Become coarse, therefore has and be easy to be involved in electrolyte and the tendency of the purity of cathode copper reduction when electro-deposition.
Therefore, in the present embodiment, average crystal grain diameter is set in 15 μm or more and 35 μm or less of range.It is flat
Equal crystal grain diameter is more preferably located in 15 μm or more and 30 μm or less of range.
(the glossiness on surface: 2 or more)
If generating bumps in the surface of the copper on the surface of cathode plate 1 in electro-deposition, electrolyte is trapped in concave-convex
Part, the tendency that the purity with cathode copper reduces.
Therefore, in the high-purity electrolytic copper of present embodiment 10, the glossiness on surface is set as 2 or more.
In addition, the glossiness on the surface of high-purity electrolytic copper 10 is preferably 3 or more.The upper limit value of the glossiness on surface is not
It is particularly limited, but is preferably set to 4.5 or less.
Here, when making copper, smoothly electro-deposition is answered when improving glossiness on the surface of cathode plate 1 with electro-deposition
The tendency that power is got higher, therefore more preferably the degree of orientation of regulation crystal reduces the stress remained in cathode copper as described above
(residual stress), to inhibit the generation of warpage.
Then, the manufacturing method of the high-purity electrolytic copper of present embodiment 10 is illustrated.
In the manufacturing method of the high-purity electrolytic copper 10 of present embodiment, use copper sulfate solution as electrolyte,
The sulfuric acid concentration of electrolyte is located in the range of 10g/L or more and 300g/L or less, by copper concentration be located at 5g/L or more and
In the range of 90g/L or less, chloride ion concentration is located in the range of 5mg/L or more and 150mg/L or less.
Moreover, in the manufacturing method of the high-purity electrolytic copper 10 of present embodiment, the additive that is added in electrolyte
With feature.In the present embodiment, as be described hereinafter, using additive A class (silver-colored depressant), (the electro-deposition form control of additive B class
Preparation), addition of C class (stress relaxation agent) this 3 kinds of additives.
(additive A class: silver-colored depressant)
Additive A class (silver-colored depressant) is made of tetrazolium or derivatives thereof (hereinafter referred to as four azoles).It is derivative as tetrazolium
Object, such as it is able to use 5- amino -1H-TETRAZOLE, 5- methyl-1 H- tetrazolium, 5- phenyl -1H-TETRAZOLE, 1- methyl -5- ethyl -1H-
Tetrazolium etc..
By the way that above-mentioned four azole to be added in electrolyte, the silver ion complexation in electrolyte is hindered to be precipitated, it can
Reduce the content of the Ag as impurity.In addition, the content of the Ag in the high-purity electrolytic copper of present embodiment preferably 0.1 mass
Ppm is hereinafter, more preferable 0.001 mass ppm or more and 0.09 mass ppm or less.
Here, can sufficiently inhibit the eutectoid of silver by the way that the additive amount of four azoles is set as 0.1mg/L or more.Another party
Face can inhibit the production of large dendritic crystal by the way that the additive amount of four azoles is set as 20mg/L hereinafter, electro-deposition state becomes stable
Raw, purity is sufficiently improved.
According to the above, in the present embodiment, the additive amount of four azoles is set in 0.1mg/L or more and 20mg/L or less
In the range of.In addition, the upper limit of the additive amount of four azoles is preferably set to 10mg/L or less.
(additive B class: electro-deposition form controlling agent)
Additive B class (electro-deposition form controlling agent) by polyoxyethylene list phenyl ether or polyoxyethylene naphthyl ether (hereinafter referred to as
For polyoxyethylene list phenyl ethers) composition.
By the way that polyoxyethylene list phenyl ethers to be added in electrolyte, the surface of cathode copper is smoothened, and can also
The generation of the precipitations such as dendrite inhibition exception.Thereby, it is possible to reduce being involved in for electrolyte to be further reduced the amount of the impurity such as sulphur.
Here, when the additive amount of polyoxyethylene list phenyl ethers is 10mg/L or more or when 500mg/L or less, Neng Gouchong
Divide and reduces impurity level.
According to the above, in the present embodiment, the additive amount of polyoxyethylene list phenyl ethers is set in 10mg/L or more
And in the range of 500mg/L or less.The additive amount of polyoxyethylene list phenyl ethers is more preferably set as 50mg/L or more and 300mg/L
Below.
(addition of C class: stress relaxation agent)
Addition of C class (stress relaxation agent) is by polyvinyl alcohol or modified polyvinylalcohol (hereinafter referred to as polyvinyl alcohol) group
At.As modified polyvinylalcohol, such as it is able to use polyoxyethylene-modified polyvinyl alcohol, ethylene modified polyvinyl alcohol, carboxyl and changes
Property polyvinyl alcohol etc..
By the way that polyvinyl alcohol to be added in electrolyte, it is able to suppress crystal and is grown in a direction, pass through taking for crystal
Tropism becomes at random, to disperse to strain.By the way that further polyvinyl alcohol is added in electrolyte, can suitably mitigate
The electro-deposition inhibitory effect of additive, therefore can be by the size coarsening of crystal grain.Thereby, it is possible to reduce electro-deposition stress, example
Electro-deposition stress when such as can be by with 20~100 μm of electro-deposition of film thickness is reduced to 50MPa or less.In addition, the copper film of electro-deposition
Thickness it is thicker, the tendency become much larger in the inside of copper film with electro-deposition stress is more put aside in strain.
Here, can sufficiently reduce electro-deposition stress by the way that the additive amount of polyvinyl alcohol is set as 1mg/L or more.Separately
On the one hand, by the way that the additive amount of polyvinyl alcohol is set as 100mg/L hereinafter, the effect for reducing electro-deposition stress can be given full play to
Fruit can be reliably suppressed the generation of large dendritic crystal.
According to the above, in the present embodiment, the additive amount of polyvinyl alcohol is set in 1mg/L or more and 100mg/L
In following range.In addition, the upper limit of the additive amount of polyvinyl alcohol is preferably set to 50mg/L or less.
Also, by the way that the saponification rate in polyvinyl alcohol is set as 70mol% or more, it can sufficiently reduce electro-deposition and answer
Power.On the other hand, by the way that saponification rate is set as 99mol% or less, it can be ensured that dissolubility can reliably dissolve in electrolyte.
According to the above, in the present embodiment, by the saponification rate in polyvinyl alcohol be located at 70mol% or more and
In the range of 99mol% or less.Saponification rate in polyvinyl alcohol is more preferably set as 75mol% or more and 95mol% or less.
In addition, partly-hydrolysed type structure of the basic structure of polyvinyl alcohol by the fully saponified type of hydroxyl and with acetate
At the degree of polymerization of polyvinyl alcohol is the sum of the rwo, and average degree of polymerization is the average value of the degree of polymerization.In addition, average polymerization
Degree can be measured according to the polyvinyl alcohol test method of defined in JIS K 6726:1994.
Here, can sufficiently reduce electro-deposition stress by the way that the average degree of polymerization of polyvinyl alcohol is set as 200 or more.
On the other hand, by the way that the average degree of polymerization of polyvinyl alcohol is set as 2500 hereinafter, electro-deposition stress can be reduced sufficiently, and
The yield for being able to suppress cathode copper due to electro-deposition inhibitory effect reduces.
According to the above, in the present embodiment, the average degree of polymerization of polyvinyl alcohol is located at 200 or more and 2500 or less
In the range of.
The copper (4NCu) by 99.99 mass % of purity or more is impregnated in the electrolyte for being added to additive as described above
The copper sheet of composition impregnates stainless steel plate and leads to as cathode plate 1, and between the anode plate and cathode plate 1 as anode plate
Thus electricity makes copper electro-deposition on the surface of cathode plate 1.
Moreover, being electrolysed by removing electro-deposition in the copper on the surface of cathode plate 1 to manufacture the high-purity of present embodiment
Copper 10.
Here, current density when by by electro-deposition is set as 150A/m2More than, it is able to suppress partial size coarsening.Also,
The eutectoid quantitative change that Ag is able to suppress relative to Cu is more, so as to inhibit the amount of the Ag in cathode copper to increase.On the other hand, pass through
Current density when by electro-deposition is set as 190A/m2Below, it can be ensured that partial size is able to suppress electro-deposition stress and gets higher.Also, example
Such as in copper sulfate electrolyte, it is able to suppress compared with anodic solution speed, the copper sulphate generated from anodic solution is dissolved in
Slowing in electrolyte, and be able to suppress the crystal covering anode surface of copper sulphate and hinder to be powered so as to cause interpolar electricity
The increase of pressure.
According to the above, in the present embodiment, preferably by electro-deposition when current density be located at 150A/m2Above and
190A/m2In following range.Current density when electro-deposition is more preferably located at 155A/m2Above and 185A/m2Range below
It is interior.
Also, electrolyte temperature when by by electro-deposition is set as 30 DEG C or more, it can be ensured that partial size is able to suppress electro-deposition
Stress is got higher.In addition, the crystal of copper sulphate is difficult to be formed on anode surface for example in copper sulfate solution, it is logical to be able to suppress obstruction
Increase that is electric and leading to voltage across poles.Electrolyte temperature when on the other hand, by by electro-deposition is set as 35 DEG C hereinafter, can press down
Granulation diameter coarsening.Further, it is possible to which the saturation solubility of the Ag ion in electrolyte is inhibited to get higher, and inhibit the Ag in electrolyte
The rising of ion concentration, so that the amount of the Ag in cathode copper be inhibited to increase.
According to the above, in the present embodiment, preferably by electro-deposition when electrolyte temperature be located at 30 DEG C or more and 35 DEG C
In following range.
According to the high-purity electrolytic copper 10 of present embodiment as constructed as above, in the section of through-thickness (along electro-deposition
The direction of growth section) on, less than 40%, therefore the area ratio of the crystal of planar orientation with ± 10 ° of (101) is suppressed to
It is larger, electro-deposition stress when electro-deposition by the crystal growth that cell reaction can inhibit the planar orientation with ± 10 ° of (101)
It is suppressed to lower.Also, become at random, to be easy release strain by the orientation of crystal.It is can inhibit as a result, from cathode plate 1
The generation of the warpage of the high-purity electrolytic copper 10 of the plate of upper removing, and treatability is excellent.
Also, the purity of the Cu in addition to gas componant (O, F, S, C, Cl) is 99.9999 mass % or more, and S contains
Amount be 0.1 mass ppm hereinafter, it is preferred that the purity of the Cu in addition to gas componant (O, F, S, C, Cl) be 99.99999 mass % with
On, and the content of S is 0.02 mass ppm hereinafter, can be consequently used for requiring the various uses of high-purity copper.
Also, in the present embodiment, on the section of through-thickness (along the section of the direction of growth of electro-deposition), tool
There is the area ratio of the crystal of the planar orientation of ± 10 ° of (111) to be suppressed to less than 15%, therefore tool may also suppress by cell reaction
The crystal growth for having the planar orientation of ± 10 ° of (111) be it is larger, electro-deposition stress when electro-deposition is suppressed to lower.Also, it is logical
The orientation for crossing crystal further becomes at random, to be easy release strain.It can inhibit the plate removed from cathode plate 1 as a result,
The generation of the warpage of high-purity electrolytic copper 10, and treatability is excellent.
In addition, in the present embodiment, on the section (along the section of the direction of growth of electro-deposition) of through-thickness, with
The aspect ratio b/a that the long axis a of the crystal grain diameter and short axle b orthogonal with long axis a is indicated is small less than the area ratio of 0.33 crystal grain
In 40%, therefore when can inhibit electro-deposition, crystal is grown to larger in a direction, and electro-deposition stress when electro-deposition reduces.By
This, is inhibited the generation of warpage after removing even if from cathode plate 1, and treatability is excellent.
Also, in the high-purity electrolytic copper of present embodiment 10, average crystal grain diameter is set as 15 μm or more, therefore
The position that crystal grain is fused to each other tails off, and stress when electro-deposition reduces.On the other hand, by average crystal grain diameter be set as 35 μm with
Under, therefore cathode copper surface is also smooth, the purity of cathode copper is also able to maintain 99.9999 mass % or more.Remain on height as a result,
Stress in purity cathode copper 10 tails off, and is able to suppress the generation of warpage, and can obtain the copper of high-purity.
In addition, in the high-purity electrolytic copper 10 of present embodiment, the glossiness on the surface of high-purity electrolytic copper 10 be 2 with
On, therefore be able to suppress impurity and be sucked into, it can be realized high purity as described above.Also, working as makes copper smoothly electro-deposition
When on the surface of cathode plate 1, with the tendency that electro-deposition stress is got higher, but pass through the orientation of regulation crystal as described above
Electro-deposition stress, can be suppressed to lower by degree.
Also, in the present embodiment, 3 kinds of additives are added in electrolyte as described above, therefore can be obtained
The high-purity electrolytic copper 10 of purity is high and smooth surface.Further, it is possible to which electro-deposition stress when by electro-deposition is suppressed to lower, energy
The high-purity electrolytic copper 10 that enough steadily manufacture residual stress are few and the generation of warpage is inhibited.
More than, embodiments of the present invention are illustrated, but the present invention is not limited to this, is not departing from the invention
The range of technical idea can suitably change.
For example, in the present embodiment, using copper sulfate solution as electrolyte to be illustrated, but do not limit
In this, copper nitrate aqueous solution also can be used.
Embodiment
Hereinafter, being illustrated to the result of the evaluation test for the high-purity electrolytic copper for having rated aforementioned present embodiment.
As electrolyte, the sulfuric acid comprising sulfuric acid 50g/L, copper sulfate pentahydrate 197g/L, hydrochloric acid 50mg/L is prepared
Copper liquor and comprising nitric acid 5g/L, cupric nitrate trihydrate 190g/L, hydrochloric acid 50mg/L copper nitrate aqueous solution both.It will
Used electrolyte is shown in table 2.
Moreover, additive A class, additive B class shown in table 1, addition of C class are added to like that as shown in table 2 respectively
In above-mentioned electrolyte.
As anode plate, use that sulphur concentration is 5 mass ppm or less and silver concentration is 8 mass ppm or less, purity is
The cathode copper (4NCu) of 99.99 mass % or more.In addition, having used anode (anode bag), generated to avoid from anode plate
Mud (ス ラ イ system) be drawn into cathode copper.
As cathode plate, the stainless steel plate being made of SUS316 has been used.
In current density 150A/m2, implement electrolysis under conditions of 30 DEG C of bath temperature.In addition, for additive A class, addition
Agent B class, addition of C class have fed the amount of reduction gradually to maintain the concentration at initial stage.
With condition as above, make copper electro-deposition in having obtained example of the present invention and comparative example on the stainless steel plate as cathode plate
Cathode copper.
In addition, about the cathode copper that progress glossiness, composition analysis, section structure are observed, by implementing 7 with above-mentioned condition
Its electro-deposition and manufactured.
Also, about the cathode copper of evaluation amount of warpage, by implementing 24 hours electro-deposition and systems with above-mentioned condition
It makes.
(composition analysis)
Measurement sample is acquired from the central part of obtained cathode copper, is filled using GD-MS (glow discharge mass spectrometry analysis)
Set the VG-9000 of manufacture (VG MICROTRACE company) determine Ag, Al, As, Au, B, Ba, Be, Bi, C, Ca, Cd, Cl, Co,
Cr、F、Fe、Ga、Ge、Hg、In、K、Li、Mg、Mn、Mo、Na、Nb、Ni、O、P、Pb、Pd、Pt、S、Sb、Se、Si、Sn、Te、Th、
The content of Ti, U, V, W, Zn, Zr.Wherein, add up to all the components in addition to gas componant (O, F, S, C, Cl), as miscellaneous
The total amount of matter.Measurement result is shown in table 3.
(section structure observation)
Measurement sample is acquired from the central part of obtained cathode copper, by ion milling method to the growth along electro-deposition
The section in direction (thickness direction of cathode copper) is processed, and using with the EBSD device (OIM of EDAX/TSL company manufacture
Data Collection) the FE-SEM JSM-7001FA of manufacture (JEOL, Ltd.) with 1000 μm of 3500 μ m of measurement range,
3 μm of step-length of measurement is measured, and uses its data and analysis software (the OIM Data Analysis of EDAX/TSL company manufacture
Ver.5.2 it) is analyzed.
Moreover, there is the crystal of the planar orientation of ± 10 ° of (101) with condition evaluating documented in above embodiment
The area ratio, planar orientation with ± 10 ° of (111) crystal the area ratio, with the long axis a of crystal grain diameter and orthogonal with long axis a
Short axle b indicate crystal grain of the aspect ratio b/a less than 0.33 the area ratio, average crystal grain diameter.Show the results of the evaluation table 3.
(glossiness)
The glossiness on the surface of cathode copper uses vancometer (NIPPON DENSHOKU INDUSTRIES Co., LTD.
The HANDY GLOSSMETER PG-1M of manufacture is simultaneously surveyed according to JIS Z 8741:1997 with 60 ° of incidence angle of condition
It is fixed.In addition, measurement site is set as the electro-deposition surface side central part of cathode copper.Show the results of the evaluation table 3.
(amount of warpage)
As described above, by electro-deposition in 24 hours obtain on one side for 10cm square plate shape cathode copper, by it
It is removed from cathode plate, electro-deposition surface side placed 24 hours upward and on plate.Moreover, assay plate and cathode copper
The distance of 4 jiaos of short transverse is evaluated 4 points of the average value as amount of warpage.Show the results of the evaluation table 3.
(electro-deposition stress)
With condition identical with table 1 and table 2, strain gage type precision stress gauge (YAMAMOTO-MS Co., Ltd. system is used
Make) determine electro-deposition stress.The value of electro-deposition stress has used the value after electro-deposition 2 hours.Cathode plate has used heavy in electricity
The back side in product face is pasted with the incidental dedicated copper cathode sheets of above-mentioned strain gage type precision stress gauge of deformeter.By measurement result
It is shown in table 3.
[table 1]
[table 2]
[table 3]
In comparative example 1-3,6, the area ratio of the crystal with (101) ± 10 ° planar orientation is more than 40%, cathode copper
Warpage becomes larger.Also, electro-deposition stress when confirming electro-deposition under the same conditions is got higher.
In comparative example 4,5,6, the content of S is more, and the total amount of impurity also becomes relatively high.Also, glossiness reduces, thus it is speculated that
Generation is concave-convex when electro-deposition and electrolyte is captured, therefore purity reduces.
In contrast, the area ratio of the crystal with (101) ± 10 ° planar orientation is less than in example 1-7 of the present invention
40%, the warpage of cathode copper is not observed.Also, it confirms electro-deposition stress when carrying out electro-deposition with the same terms to be lower.
In addition, the content of S is few, the total amount of impurity is also suppressed to lower, can obtain the cathode copper of high-purity.
It is arrived according to identified above, in accordance with the invention it is possible to which the purity for providing a kind of Cu in addition to gas componant is
99.9999 mass % or more, and the content of S is 0.1 mass ppm hereinafter, by reducing electro-deposition stress energy when electro-deposition
It is enough steadily to be manufactured, and be inhibited after being removed even if from cathode plate the generation of warpage and treatability is excellent
High-purity electrolytic copper.
Industrial availability
In accordance with the invention it is possible to the purity for providing a kind of Cu in addition to gas componant is 99.9999 mass % or more, and
And the content of S is 0.1 mass ppm hereinafter, can steadily be manufactured by electro-deposition stress when reducing electro-deposition, and
Being inhibited generation for warpage after being removed even if from cathode plate and the excellent high-purity electrolytic copper of treatability.
Symbol description
1- cathode plate, 10- high-purity electrolytic copper.
Claims (4)
1. a kind of high-purity electrolytic copper, which is characterized in that
The purity of Cu in addition to gas componant O, F, S, C, Cl is 99.9999 mass % or more, and the content of S is 0.1 mass
Ppm hereinafter,
Carry out that crystal orientation measures by electron backscatter diffraction on the section of through-thickness as a result, having (101)
The area ratio of the crystal of ± 10 ° of planar orientation is less than 40%.
2. high-purity electrolytic copper according to claim 1, which is characterized in that
Carry out that crystal orientation measures by electron backscatter diffraction on the section of through-thickness as a result, having (111)
The area ratio of the crystal of ± 10 ° of planar orientation is less than 15%.
3. high-purity electrolytic copper according to claim 1 or 2, which is characterized in that
It is small with the aspect ratio b/a that the long axis a of crystal grain and the short axle b orthogonal with long axis a are indicated on the section of through-thickness
In 0.33 crystal grain the area ratio less than 40%.
4. high-purity electrolytic copper according to any one of claim 1 to 3, which is characterized in that
The purity of Cu in addition to gas componant O, F, S, C, Cl is 99.99999 mass % or more, and the content of S is 0.02 matter
Measure ppm or less.
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017109244 | 2017-06-01 | ||
JP2017-109244 | 2017-06-01 | ||
JP2017110418 | 2017-06-02 | ||
JP2017-110418 | 2017-06-02 | ||
JP2018-097319 | 2018-05-21 | ||
JP2018097319A JP7454329B2 (en) | 2017-06-01 | 2018-05-21 | High purity electrical copper plate |
JP2018097318A JP7172131B2 (en) | 2017-06-02 | 2018-05-21 | Manufacturing method of high-purity electrolytic copper |
JP2018-097318 | 2018-05-21 | ||
PCT/JP2018/021178 WO2018221724A1 (en) | 2017-06-01 | 2018-06-01 | High-purity electrolytic copper |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110382743A true CN110382743A (en) | 2019-10-25 |
CN110382743B CN110382743B (en) | 2022-04-08 |
Family
ID=64454826
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201880015294.1A Active CN110382743B (en) | 2017-06-01 | 2018-06-01 | High purity electrolytic copper |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN110382743B (en) |
WO (2) | WO2018221734A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111057981A (en) * | 2019-12-16 | 2020-04-24 | 上海浦帮机电制造有限公司 | Low-purity copper rod purification method |
CN114293227A (en) * | 2021-12-16 | 2022-04-08 | 虹华科技股份有限公司 | Processing technology of high-purity copper product for aerospace |
TWI838979B (en) | 2021-11-29 | 2024-04-11 | 日商Jx金屬股份有限公司 | Brittle Electrodeposited Copper |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20220025486A1 (en) * | 2018-12-13 | 2022-01-27 | Mitsubishi Materials Corporation | Pure copper plate |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63203784A (en) * | 1987-02-19 | 1988-08-23 | Nippon Mining Co Ltd | Production of high purity electrolytic copper |
JPH02294495A (en) * | 1989-05-09 | 1990-12-05 | Dowa Mining Co Ltd | Purified solution for obtaining ultrahigh purity copper and electrolyzing method |
JPH03140489A (en) * | 1989-10-27 | 1991-06-14 | Furukawa Electric Co Ltd:The | Production of high-purity copper |
JPH04365889A (en) * | 1991-06-11 | 1992-12-17 | Hitachi Cable Ltd | Electrolytic refining method for copper |
JPH06173063A (en) * | 1992-12-01 | 1994-06-21 | Mitsubishi Materials Corp | Production of high purity copper |
JP2004315849A (en) * | 2003-04-11 | 2004-11-11 | Mitsubishi Materials Corp | Method for manufacturing high-purity electrolytic copper |
CN1681960A (en) * | 2002-07-16 | 2005-10-12 | 霍尼韦尔国际公司 | Copper sputtering targets and methods of forming copper sputtering targets |
US20080223728A1 (en) * | 2004-01-29 | 2008-09-18 | Nippon Mining & Metals Co., Ltd. | Ultrahigh-Purity Copper and Process for Producing the Same |
CN101985700A (en) * | 2010-11-19 | 2011-03-16 | 金川集团有限公司 | Method for preparing ultrapure copper ingot |
CN105814233A (en) * | 2013-12-13 | 2016-07-27 | 普莱克斯 S.T.技术有限公司 | Diffusion bonded copper sputtering target assembly |
WO2017033694A1 (en) * | 2015-08-24 | 2017-03-02 | 三菱マテリアル株式会社 | High purity copper sputtering target material |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08990B2 (en) | 1989-01-11 | 1996-01-10 | 同和鉱業株式会社 | Ultra high purity copper manufacturing method |
JP4419161B2 (en) | 1999-10-27 | 2010-02-24 | Dowaホールディングス株式会社 | Method for producing electrolytic copper foil |
JP4518262B2 (en) | 2004-03-23 | 2010-08-04 | 三菱マテリアル株式会社 | High purity electrolytic copper and its manufacturing method |
WO2010038641A1 (en) | 2008-09-30 | 2010-04-08 | 日鉱金属株式会社 | High-purity copper and process for electrolytically producing high-purity copper |
JP6183592B2 (en) * | 2012-06-14 | 2017-08-23 | 三菱マテリアル株式会社 | Method for electrolytic refining of high purity electrolytic copper |
JP6733313B2 (en) | 2015-08-29 | 2020-07-29 | 三菱マテリアル株式会社 | High-purity copper electrolytic refining additive and high-purity copper manufacturing method |
JP6733314B2 (en) | 2015-09-29 | 2020-07-29 | 三菱マテリアル株式会社 | High-purity copper electrolytic refining additive and high-purity copper manufacturing method |
TWI705159B (en) * | 2015-09-30 | 2020-09-21 | 日商三菱綜合材料股份有限公司 | Additive for high-purity copper electrolytic refining, method of producing high-purity copper, and high-purity electrolytic copper |
US10150158B2 (en) | 2015-12-17 | 2018-12-11 | General Electric Company | Method and assembly for forming components having internal passages using a jacketed core |
JP2017110418A (en) | 2015-12-17 | 2017-06-22 | 大成建設株式会社 | Building structure |
JP2018097319A (en) | 2016-12-16 | 2018-06-21 | 株式会社沖データ | Developing unit and image forming apparatus |
JP6822117B2 (en) | 2016-12-16 | 2021-01-27 | 株式会社リコー | Fixing device and image forming device |
-
2018
- 2018-06-01 WO PCT/JP2018/021228 patent/WO2018221734A1/en active Application Filing
- 2018-06-01 WO PCT/JP2018/021178 patent/WO2018221724A1/en active Application Filing
- 2018-06-01 CN CN201880015294.1A patent/CN110382743B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63203784A (en) * | 1987-02-19 | 1988-08-23 | Nippon Mining Co Ltd | Production of high purity electrolytic copper |
JPH02294495A (en) * | 1989-05-09 | 1990-12-05 | Dowa Mining Co Ltd | Purified solution for obtaining ultrahigh purity copper and electrolyzing method |
JPH03140489A (en) * | 1989-10-27 | 1991-06-14 | Furukawa Electric Co Ltd:The | Production of high-purity copper |
JPH04365889A (en) * | 1991-06-11 | 1992-12-17 | Hitachi Cable Ltd | Electrolytic refining method for copper |
JPH06173063A (en) * | 1992-12-01 | 1994-06-21 | Mitsubishi Materials Corp | Production of high purity copper |
CN1681960A (en) * | 2002-07-16 | 2005-10-12 | 霍尼韦尔国际公司 | Copper sputtering targets and methods of forming copper sputtering targets |
JP2004315849A (en) * | 2003-04-11 | 2004-11-11 | Mitsubishi Materials Corp | Method for manufacturing high-purity electrolytic copper |
US20080223728A1 (en) * | 2004-01-29 | 2008-09-18 | Nippon Mining & Metals Co., Ltd. | Ultrahigh-Purity Copper and Process for Producing the Same |
CN101985700A (en) * | 2010-11-19 | 2011-03-16 | 金川集团有限公司 | Method for preparing ultrapure copper ingot |
CN105814233A (en) * | 2013-12-13 | 2016-07-27 | 普莱克斯 S.T.技术有限公司 | Diffusion bonded copper sputtering target assembly |
WO2017033694A1 (en) * | 2015-08-24 | 2017-03-02 | 三菱マテリアル株式会社 | High purity copper sputtering target material |
Non-Patent Citations (1)
Title |
---|
易光斌: "电解铜箔组织性能及其翘曲产生机理研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111057981A (en) * | 2019-12-16 | 2020-04-24 | 上海浦帮机电制造有限公司 | Low-purity copper rod purification method |
TWI838979B (en) | 2021-11-29 | 2024-04-11 | 日商Jx金屬股份有限公司 | Brittle Electrodeposited Copper |
CN114293227A (en) * | 2021-12-16 | 2022-04-08 | 虹华科技股份有限公司 | Processing technology of high-purity copper product for aerospace |
Also Published As
Publication number | Publication date |
---|---|
WO2018221734A1 (en) | 2018-12-06 |
WO2018221724A1 (en) | 2018-12-06 |
CN110382743B (en) | 2022-04-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110382743A (en) | High-purity electrolytic copper | |
CN102245788A (en) | Aluminum alloy foil for current collector and method for producing the same | |
US10396363B2 (en) | Copper foil, negative electrode current collector and negative electrode material for non-aqueous secondary battery | |
CN106480475B (en) | Additive for electrolytic refining of high-purity copper and method for producing high-purity copper | |
JP7454329B2 (en) | High purity electrical copper plate | |
JP6773935B2 (en) | Zinc foil, negative electrode active material material for primary batteries using this, and manufacturing method of zinc foil | |
TWI788361B (en) | High-purity electrolytic copper | |
KR20210028682A (en) | High-strength and corrosion-resistant magnesium alloy material and its manufacturing method | |
JP6740801B2 (en) | High-purity copper electrolytic refining additive and high-purity copper manufacturing method | |
US10407785B2 (en) | Additive for high-purity copper electrolytic refining and method of producing high-purity copper | |
JP4874039B2 (en) | Aluminum alloy foil for electrolytic capacitor cathode and alloy foil used therefor | |
TWI810414B (en) | Corrosion Resistant CuZn Alloy | |
US20220074024A1 (en) | Metal structures | |
JP7172131B2 (en) | Manufacturing method of high-purity electrolytic copper | |
JP2023029573A (en) | High-purity electrolytic copper | |
TWI838979B (en) | Brittle Electrodeposited Copper | |
JP5626582B2 (en) | Phosphorus copper anode for electrolytic copper plating and electrolytic copper plating method using the same | |
JP2024002369A (en) | NEGATIVE ELECTRODE MATERIAL AND CURRENT COLLECTOR MATERIAL FOR Mg SECONDARY BATTERY, AND Mg SECONDARY BATTERY USING THE SAME | |
US10793956B2 (en) | Additive for high-purity copper electrolytic refining and method of producing high-purity copper | |
Medhat et al. | The Effect of Environmental Parameters on the Corrosion Behavior of Simple Shear Extruded AZ91 Magnesium Alloys | |
CN113056569A (en) | Copper electrode material | |
KR20200128097A (en) | Electro-Co plating method using Co anode and Co anode | |
Zhang et al. | Microstructures of RE 0. 5 Sr 0. 5 CoO 3-delta/YSZ Thin Films |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |