KR20160077463A - Fe-Ni ALLOY ELECTROLYTES AND METHOD FOR MANUFACTURING Fe-Ni ALLOY USING THE SAME - Google Patents
Fe-Ni ALLOY ELECTROLYTES AND METHOD FOR MANUFACTURING Fe-Ni ALLOY USING THE SAME Download PDFInfo
- Publication number
- KR20160077463A KR20160077463A KR1020140187078A KR20140187078A KR20160077463A KR 20160077463 A KR20160077463 A KR 20160077463A KR 1020140187078 A KR1020140187078 A KR 1020140187078A KR 20140187078 A KR20140187078 A KR 20140187078A KR 20160077463 A KR20160077463 A KR 20160077463A
- Authority
- KR
- South Korea
- Prior art keywords
- alloy
- electrolytic solution
- electrolyte
- iron
- nickel
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/12—Electroforming by electrophoresis
- C25D1/14—Electroforming by electrophoresis of inorganic material
- C25D1/16—Metals
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention relates to the production of iron-nickel (Fe-Ni) alloys and, more particularly, to an electrolyte used for producing Fe-Ni alloys by electroforming and a method for producing Fe- .
Description
The present invention relates to the production of iron-nickel (Fe-Ni) alloys and, more particularly, to an electrolyte used for producing Fe-Ni alloys by electroforming and a method for producing Fe- .
The Fe-Ni alloy has a low coefficient of thermal expansion (CTE) and is used as an encapsulating material for an organic light-emitting diode and a fine metal mask (FMM), and is attracting attention as a collector of a secondary battery or a substrate of an electronic device It is a situation.
Meanwhile, as a method for producing the Fe-Ni alloy, there is a method of casting iron and nickel into ingot, and rolling and annealing repeatedly to form a thin film. However, such an ingot casting method requires complicated processes such as melting, forging, hot rolling, heat treatment, cold rolling, and heat treatment of an alloy, and the rolling process requires a large scale facility and is a process with great energy consumption. Further, in the case of manufacturing a thin film material, since rolling and heat treatment are repeated, not only the process becomes complicated but also a lot of shape defects such as crowns are generated and the yield rate is lowered.
Recently, Fe-Ni alloy thin films should be economically provided to meet the trend of thinning of displays and electronic devices. Therefore, EF (Electro-Forming) is a manufacturing method of Fe-Ni alloy which can relatively easily adjust the thickness with low manufacturing cost.
The electrophotographic method is generally carried out by providing a drum or a belt-shaped negative electrode in an electrolytic bath containing an electrolytic solution, and a pair of arc-shaped positive electrodes opposing the negative electrode, supplying the electrolytic solution continuously through the supply nozzle, And the Fe-Ni alloy is electrodeposited on the surface of the negative electrode drum.
The electrolytic solution is required for the electrolytic solution, and the electrolytic solution basically contains an iron compound supplying iron ions and a nickel compound supplying nickel ions, and usually, iron ion is added to the nickel plating solution. Since the concentration of iron and nickel in the electrolytic solution is different from that of iron and nickel when precipitated, metal ions of the electrolytic solution and various additives are important for obtaining a useful Fe-Ni alloy (Patent Documents 1 to 3).
An aspect of the present invention is to provide an iron-nickel alloy electrolyte capable of continuously producing an excellent Fe-Ni alloy and improving the longevity of the electrolyte in the production of an Fe-Ni alloy using the electroplating method and a method of manufacturing an iron- .
One aspect of the present invention provides an electrolytic solution containing an iron compound and a nickel compound for producing an Fe-Ni alloy by electroplating, wherein the electrolytic solution contains an iron-nickel alloy electrolyte containing carbonate in a range of 10 to 100 g / L .
Another aspect of the present invention is a method for producing an Fe-Ni alloy by electrolytic solution using an electrolytic solution containing an iron compound and a nickel compound,
And supplying a carbonate to the electrolyte solution so that the carbonate concentration is 10 to 100 g / L.
The present invention relates to a process for preparing a Fe-Ni alloy by using a electrolytic process, in which a carbonate such as CaCO 3 or BaCO 3 is added to an electrolyte to remove SO 4 2 - Thereby improving the longevity of the electrolytic solution and enabling the continuous production of a Fe-Ni alloy of excellent quality.
FIG. 1 is a schematic view showing the use of CaSO 4 as an electrolyte in the present invention.
When the Fe-Ni alloy is manufactured using the electroplating method, the characteristics of the Fe-Ni alloy vary depending on the high internal stresses of the iron and nickel contained in the electrolyte and the particle size structure upon precipitation. The additives and concentrations are important.
It is also important to control the deviation of the electrolyte during production to obtain a homogeneous Fe-Ni alloy. In particular, the concentration of Fe, Ni ions and various ions in the electrolytic solution must be maintained for a long time without any variation. As the Fe-Ni alloy is manufactured using the electroplating method, Fe and Ni ions present in the electrolyte are precipitated and released. In order to maintain the Fe and Ni ions, FeSO 4 , NiSO 4 , . However, when iron sulfate (FeSO 4 ) and nickel sulfate (NiSO 4 ) are added, the SO 4 anion (SO 4 2 - ) separated from the metal is continuously concentrated in the electrolyte, Problems arise. Accordingly, the inventors of the present invention have recognized such a problem and devised a method for solving the problem, thereby leading to the present invention.
Hereinafter, the present invention will be described in detail. First, an electrolytic solution used in the production of an Fe-Ni alloy using the electrolytic process in the present invention will be described in detail. The electrolytic solution of the present invention contains an iron compound and a nickel compound, and the carbonate is preferably contained at a concentration of 10 to 100 g / L.
(FeSO 4 ) and nickel sulfate (NiSO 4 ) are consumed in order to precipitate Fe and Ni ions of the electrolytic solution and thereby to supplement Fe and Ni when the Fe-Ni alloy is continuously produced by using the electrolyte solution . In this process, SO 4 2- ions in the electrolyte decrease the pH of the electrolytic solution, which is a factor that hinders the production of the Fe-Ni alloy. Normally, when the pH is lower than 1, Fe-Ni alloy can not be produced. Therefore, in order to remove such SO 4 2 - , the electrolytic solution of the present invention includes a carbonate. The carbonate may be CaCO 3 , BaCO 3, or the like.
The CaCO 3 contained in the electrolytic solution of the carbonate is reacted by the following reaction formula.
CaCO 3 + 2H + + SO 4 2 - ? CaSO 4 + H 2 O + CO 2
In other words, the increased SO 4 2 - in the electrolyte is precipitated with CaSO 4 , and the generated H + is removed by H 2 O, which can solve the problem of concentration of SO 4 2 - and decrease in pH during continuous production . BaCO 3 has the same function. If the concentration of carbonate in the electrolytic solution is less than 10 g / L, it is difficult to sufficiently remove SO 4 2 - which is elongated, and if it exceeds 100 g / L, the dissolution limit of the carbonate is exceeded.
On the other hand, the electrolytic solution has an iron concentration of 1 to 40 g / L, a nickel concentration of 5 to 80 g / L, a pH stabilizer of 5 to 40 g / L, a stress relieving agent of 1.0 to 20 g / To 3.5 g / L.
The iron concentration and the nickel concentration depend on the composition of the Fe-Ni alloy. When the iron concentration and the nickel concentration are lower than the above-mentioned range, the nickel content of the Fe-Ni alloy is lowered. If the iron concentration and the nickel concentration are higher than the above range, the metal ions are excessively increased in the electrolyte.
The pH stabilizer exhibits an effect of increasing the pH range at which the alloy is produced. When the pH is less than the above range, the pH buffer zone is reduced.
The stress relaxation agent has an effect of reducing the internal stress at the time of formation of the Fe-Ni alloy. When the content is less than the above range, the internal stress of the alloy becomes worse and the alloy is peeled off during production. It is hard to expect further effect.
The conductive auxiliary improves the flow of current in the electrolytic solution. If the content is lower than the above range, there is a problem that the voltage is increased.
The Fe reducing agent prevents the Fe 2 + from being oxidized to Fe 3 + inside the electrolyte. When the ratio of Fe 3+ increases, the internal stress of the alloy increases. In the case of severe reduction, the alloy is not formed. .
The remaining solvent of the electrolytic solution is preferably pure water, more preferably ultra pure water.
Hereinafter, the method for producing the Fe-Ni alloy of the present invention will be described in detail. The Fe-Ni alloy of the present invention is manufactured using the electroforming method. The electrolytic solution according to the present invention is produced by providing a cathode and an anode in an electrolytic bath containing the electrolytic solution of the present invention and applying an electric potential through a current device so that the Fe-Ni alloy is electrodeposited on the surface of the cathode.
The present invention includes a step of supplying carbonate to the electrolytic solution so as to have a concentration of 10 to 100 g / L in the process of preparing the Fe-Ni alloy using the electrolytic process. As mentioned above, CaCO 3 , BaCO 3 and the like can be used for the carbonate.
On the other hand, as the Fe-Ni alloy is produced, SO 4 precipitates such as CaSO 4 and BaSO 4 are formed in the electrolyte and are continuously concentrated. Accordingly, the invention is by using a pole method process for producing a Fe-Ni alloy is SO 4 formed in the electrolyte And removing the precipitate. The SO 4 The precipitate can be removed by precipitating an electrolyte to remove precipitates or by using a filter to remove CaSO 4 or BaSO 4. It is more effective to use the above-described precipitation method and a method using a filter together.
FIG. 1 is a schematic illustration of a step of removing CaSO 4 according to the present invention. As shown in FIG. 1, CaSO 4 formed in an electrolyte is precipitated and removed. After the CaSO 4 not precipitated is removed through a filter system, A circulating system for use in the production of Fe-Ni alloys may be used.
The electrolytic solution is supplied to the skimmer tank through the supply tank, and the spent electrolyte is overflowed into the reservoir as the alloy is produced in the tank. In the storage tank, the spent Fe and Ni ions are supplied, and the electrolyte from the storage tank is supplied to the SO 4 Precipitates are precipitated and removed, and if necessary, they are fed to the feed tank after passing through a filter system to be circulated for use in the production of Fe-Ni alloy.
It is preferable that the above-mentioned electric-field conditions have a pH of 1.0 to 5.0, a current density of 1 to 80 A / dm 2, an electrolyte temperature of 40 to 90 ° C, and a flow rate of 0.2 to 5 m / sec. Where the flow rate refers to the velocity of the electrolyte supplied to the barrel in the feed tank.
According to the present invention, even when the Fe-Ni alloy is continuously produced by the electrolytic plating method, the pH of the electrolytic solution is not lowered, and thus a Fe-Ni alloy of excellent quality can be continuously produced.
Hereinafter, embodiments of the present invention will be described in detail. The following examples are for the purpose of understanding the present invention and are not intended to limit the present invention.
(Example)
An electrolytic solution containing an Fe concentration of 17 g / L, an Ni concentration of 35 g / L, a stress relieving agent of 5 g / L as an additive, 20 g / L of a conductive auxiliary agent and 1.0 g / L of an antioxidant was prepared, A Fe-Ni alloy thin film was produced on a cylindrical negative electrode made of titanium under a condition of a temperature of 65 캜 and a flow rate of 1.0 m / s, and then peeling off the Fe-Ni alloy thin film. Thick Fe-42wt% Ni alloy thin film.
At this time, as shown in Table 1 below, CaCO 3 was added to the electrolytic solution, and the alloy thin film was continuously prepared for 48 hours, and then the state of the electrolytic solution and the state of the produced thin film were evaluated.
Evaluation of Fe-Ni alloy thin film (foil)
1) Foil formation: The film is formed without bursting (good), cracking, bursting or inability to form during foil formation (poor)
2) Foil curling: Foil length 50cm, Width 6cm, Both ends lift 2cm or less (Good), 2cm or more (Bad)
3) Surface appearance Stripe: White stripe on surface 5cm X 5cm or more in line within 1cm (bad), missing (good)
As shown in Table 1, it was confirmed that the Fe-Ni alloy exhibited good characteristics even after 48 hours of the inventive example of the present invention. Particularly when CaCO 3 was added in an amount of 10 g / L or more It was confirmed that the lowering width of the pH was alleviated and the curling of the foil was improved.
On the other hand, as a result of measuring the residual SO 4 2 - concentration in the electrolytic solution in Comparative Example 1 and Inventive Example 2, 133.5 g / L was measured in Comparative Example 1, and 100.75 g / L was measured in Inventive Example 2 there was. That is, in the invention example 2, at least about 30% SO 4 2 - and the reduction occurs, it could be confirmed that the use of an electrolyte solution for a long time.
Claims (9)
The carbonate is CaCO 3 BaCO 3, and at least one of the iron-nickel alloy electrolyte.
The electrolytic solution preferably has an iron concentration of 1 to 40 g / L, a nickel concentration of 5 to 80 g / L, a pH stabilizer of 5 to 40 g / L, a stress relaxation agent of 1.0 to 20 g / g / L. < / RTI >
And supplying a carbonate to the electrolyte so that the carbonate concentration is 10 to 100 g / L.
The carbonate is CaCO 3 And at least one of BaCO 3 iron-nickel alloy method.
The method of manufacturing an iron-nickel alloy according to claim 1, further comprising the step of removing SO 4 precipitates formed in the electrolyte solution.
Wherein the SO 4 precipitates are at least one of CaSO 4 and BaSO 4 .
Wherein the removal of the SO 4 precipitates is carried out using one or two of the following methods: precipitation and removal using a filter.
Further comprising the step of removing the SO 4 precipitate and then producing an Fe-Ni alloy by using an electrolyte solution from which SO 4 precipitates have been removed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140187078A KR20160077463A (en) | 2014-12-23 | 2014-12-23 | Fe-Ni ALLOY ELECTROLYTES AND METHOD FOR MANUFACTURING Fe-Ni ALLOY USING THE SAME |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140187078A KR20160077463A (en) | 2014-12-23 | 2014-12-23 | Fe-Ni ALLOY ELECTROLYTES AND METHOD FOR MANUFACTURING Fe-Ni ALLOY USING THE SAME |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20160077463A true KR20160077463A (en) | 2016-07-04 |
Family
ID=56500911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140187078A KR20160077463A (en) | 2014-12-23 | 2014-12-23 | Fe-Ni ALLOY ELECTROLYTES AND METHOD FOR MANUFACTURING Fe-Ni ALLOY USING THE SAME |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20160077463A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220009065A (en) | 2020-07-15 | 2022-01-24 | 현대제철 주식회사 | Steel sheet having high strength and high formability and method for manufacturing the same |
| KR20220041506A (en) | 2020-09-25 | 2022-04-01 | 현대제철 주식회사 | Steel sheet having high strength and high formability and method for manufacturing the same |
| KR20220064749A (en) | 2020-11-12 | 2022-05-19 | 현대제철 주식회사 | Steel sheet having high strength and high formability and method for manufacturing the same |
| KR20220081173A (en) | 2020-12-08 | 2022-06-15 | 현대제철 주식회사 | Steel sheet having high strength and high formability and method for manufacturing the same |
| DE112020004666T5 (en) | 2019-09-30 | 2022-06-23 | Hyundai Steel Company | STEEL SHEET WHICH HAS HIGH STRENGTH AND HIGH FORMABILITY AND METHOD OF MAKING THE SAME |
| DE112020005673T5 (en) | 2019-11-20 | 2022-09-01 | Hyundai Steel Company | Steel sheet with high strength and high formability and method for its production |
| KR20230077509A (en) | 2021-11-25 | 2023-06-01 | 현대제철 주식회사 | Ultra high strength galva-annealed steel sheet having excellent surface properties and method of manufacturing the same |
-
2014
- 2014-12-23 KR KR1020140187078A patent/KR20160077463A/en active Search and Examination
Non-Patent Citations (3)
| Title |
|---|
| 특허문헌 1: 미국 등록특허 US4,440,609 |
| 특허문헌 2: 미국 등록특허 US4,101,387 |
| 특허문헌 3: 미국 등록특허 US4,052,254 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112020004666T5 (en) | 2019-09-30 | 2022-06-23 | Hyundai Steel Company | STEEL SHEET WHICH HAS HIGH STRENGTH AND HIGH FORMABILITY AND METHOD OF MAKING THE SAME |
| DE112020005673T5 (en) | 2019-11-20 | 2022-09-01 | Hyundai Steel Company | Steel sheet with high strength and high formability and method for its production |
| KR20220009065A (en) | 2020-07-15 | 2022-01-24 | 현대제철 주식회사 | Steel sheet having high strength and high formability and method for manufacturing the same |
| KR20220041506A (en) | 2020-09-25 | 2022-04-01 | 현대제철 주식회사 | Steel sheet having high strength and high formability and method for manufacturing the same |
| KR20220064749A (en) | 2020-11-12 | 2022-05-19 | 현대제철 주식회사 | Steel sheet having high strength and high formability and method for manufacturing the same |
| KR20220081173A (en) | 2020-12-08 | 2022-06-15 | 현대제철 주식회사 | Steel sheet having high strength and high formability and method for manufacturing the same |
| KR20230077509A (en) | 2021-11-25 | 2023-06-01 | 현대제철 주식회사 | Ultra high strength galva-annealed steel sheet having excellent surface properties and method of manufacturing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20160077463A (en) | Fe-Ni ALLOY ELECTROLYTES AND METHOD FOR MANUFACTURING Fe-Ni ALLOY USING THE SAME | |
| EP3239363B1 (en) | Fe-ni alloy metal foil having excellent heat resilience and method for manufacturing same | |
| KR20170061717A (en) | High strength, high heat-resistance electrolytic copper foil, and manufacturing method for same | |
| JP5706045B2 (en) | Electrolytic copper foil and manufacturing method thereof | |
| TWI518210B (en) | Electrolytic copper foil and method for manufacturing the same and surface-treated copper foil using the electrolytic copper foil | |
| EP2535443A1 (en) | Metal electrowinning system, and electrowining method using the system | |
| CN106544703A (en) | Perforation Copper Foil foil machine and its production technology | |
| CN104357886A (en) | Method for chemically depositing diffused tin-zinc crystal nucleus on surface of high-purity aluminum foil for medium/high-voltage positive electrode | |
| CN103774193A (en) | Method for electrolytic-depositing dispersed zinc crystal nucleuses on surface of medium-high voltage electronic aluminum foil | |
| CN112176366B (en) | Electrolyte of high-ductility electrolytic copper foil and application | |
| CN103060842A (en) | Method for preparing electrodeposited cobalt under large flow | |
| CN111020643B (en) | Double-sided smooth copper foil and preparation method and device thereof | |
| EP3540832A1 (en) | Electrolytic copper foil for secondary battery and method for producing same | |
| CN110085429B (en) | Method for pulse deposition of nano tin dots on medium-high voltage anode aluminum foil for aluminum electrolytic capacitor | |
| CN103108995B (en) | Nickel pH adjustment method and equipment | |
| KR20160077466A (en) | Fe-Ni ALLOY ELECTROLYTES AND METHOD FOR MANUFACTURING Fe-Ni ALLOY USING THE SAME | |
| TW201529479A (en) | Process for producing indium hydroxide powder, and cathode | |
| KR100485808B1 (en) | electroplating bath for copper-nickel alloy and method for manufacturing thin film using said electroplating bath | |
| KR101778402B1 (en) | Fe-Ni ALLOY METAL FOIL HAVING EXCELLENT HEAT RESILIENCE AND METHOD FOR MANUFACTURING THE SAME | |
| JP2011006747A (en) | Aluminum foil for electrolytic capacitor | |
| JPS63307291A (en) | Manufacture of high-purity copper | |
| KR102280086B1 (en) | Trivalent chromium electroplating solution and electroplating method for using the same | |
| CN105586630A (en) | Method for improving quality of black film of copper and phosphorus anode in semiconductor packaging | |
| CN206783786U (en) | Electrolytic copper foil and electric assembly using same | |
| US20150053574A1 (en) | Metal electrowinning anode and electrowinning method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application | ||
| AMND | Amendment |