CN100449038C - Process for preparing invor alloy foil - Google Patents
Process for preparing invor alloy foil Download PDFInfo
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- CN100449038C CN100449038C CNB2005101278087A CN200510127808A CN100449038C CN 100449038 C CN100449038 C CN 100449038C CN B2005101278087 A CNB2005101278087 A CN B2005101278087A CN 200510127808 A CN200510127808 A CN 200510127808A CN 100449038 C CN100449038 C CN 100449038C
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Abstract
The present invention belongs to the field of a precise alloy, and relates to a method for preparing invar alloy foil. The invar alloy of the present invention is a Fe-Ni alloy of which the nickel content is 35 to 37%(wt%). The method for preparing the invar alloy foil has the steps that an electrodeposition method is used, and electrolytic solution is sulfate system with low concentration of metal salt; meantime, a buffering agent, a complexing agent, a brightening agent and an adjuvant are added into the electrolytic solution, and 304 stainless steel and an I r oxide coating titanium plate are respectively used as cathode and anode materials; the electrodeposition has the technological parameters that the temperature is under 50 to 70DEG. C, the pH is 3.0 to 4.5, the current density is 1.0 to 10.0 A/dm<2>, the space between the cathode and the anode is 10 to 30mm, and the time for electrodeposition is 5 to 50 min. The cathode and the anode are arranged into the electrolytic solution, and then direct current is powered on to the electrolytic solution; the invar alloy is deposited on the cathode, and then a cathode plate is taken out for rinsing cleanly; after drying, the Fe-Ni alloy layer formed on the surface of the cathode plate is peeled down, and then the invar alloy foil is prepared.
Description
Technical field
The invention belongs to the Precise Alloy field, that is field of functional materials, relate to the preparation method of invor alloy foil.
Background technology
Invar alloy is an iron-nickel alloy, and wherein nickel content is 35～37% (wt%), because its magnetic property is good, snappiness is good, and dense structure, has been widely used in the components and parts in precision instrumentation, opticinstrument and the electronics.
The preparation method of Invar alloy is existing multiple, as cold plastic deformation, spatter film forming, melting and casting, the super quench of two rollers etc.Yet compare with above-mentioned technology of preparing, electrodip process has the following advantages: deposition layer has unique high-density and low hole; The chemical ingredients of easily coming control material on the technology by conditions such as change parameter, bath compositions; A large amount of easily preparation thin-film materials have higher productivity and excellent economy; The required equipment investment is relatively low.Therefore electrodip process is the most promising a kind of method of preparation Invar alloy thin-film material.
In the prior art, (" sufacing " 2000 the 25th interim " the thermal expansion research of electronickelling and iron nickel alloy film " Liu Xiaowei) and (Michel L, Trudean.Nanocrystalline Fe and Fe-RichedFe-Ni Through Electrodeposition.Nanostructured Materials, 1999,12:55～60) method that electrodip process prepares Invar alloy is all disclosed in the document, the part but aforesaid method still has some deficits, need further perfect, be that concentration of metal ions is bigger than normal, production cost is higher, electrolyte property is stable inadequately, and oxidation-resistance is lower, deposition layer hardness height, poor toughness.
Summary of the invention
The object of the present invention is to provide that a kind of electrolyte property is good, workable, production cost is relatively low, and the deposition layer surface-brightening is smooth, tension stress is little and the manufacture method of the invor alloy foil of good toughness,
Invar alloy of the present invention, promptly nickel content is the Fe-Ni alloy of 35～37% (wt%).
The preparation method of invor alloy foil of the present invention adopts electrodip process, and electrolytic solution has added buffer reagent, complexing agent, brightening agent and auxiliary simultaneously, and used 304 stainless steels, I for the sulfate system of low metal salt concentrations
rThe oxide coating titanium plate is respectively as negative electrode and anode material;
The concrete component of electrolytic solution is: NiSO
46H
2O 45～50g/L, FeSO
47H
2O 32～36g/L, NaCl 20～30g/L, buffer reagent 20～50g/L, complexing agent 20～50g/L, brightening agent 2～6g/L, auxiliary 0.1～1.2g/L; , addition of C eCl
37H
2O 0.1～1.0g/L;
Wherein buffer reagent be in boric acid, acetic acid, sodium-acetate, sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, the oxalic acid any or any two more than.
Complexing agent be in the Citrate trianion series any.
Brightening agent be in asccharin, thiocarbamide, butynediol or the propiolic alcohol any or any two more than.
Auxiliary be in benzene sulfinic acid sodium salt, sodium lauryl sulphate, the succsinic acid any or any two more than.
Electrodip process prepares the technological process of Invar alloy, be with 304 stainless steel plates after the oil removing as negative electrode, I
rThe oxide coating titanium plate is made anode.Electrolytic solution is put into electrolyzer, anode and cathode is placed electrolytic solution, keep certain distance each other, and pass to the direct current of certain hour, Invar alloy is deposited on the negative electrode, take out negative plate then and rinse well, drying is that micron-sized bright Fe-Ni alloy layer strips down with the thickness that its surface forms, and the alloy material of this film like is invor alloy foil.
The processing parameter of galvanic deposit is:
50～70 ℃ of temperature
pH 3.0～4.5
Current density 1.0～5.0A/dm
2.
Cathode and anode spacing 10～30mm
Electrodeposition time 5～50min
Electrolytic solution of the present invention adopts the sulfate system of low metal salt concentrations, is for stablizing the stress of electrolytic solution and minimizing Alloy Foil, improve the toughness and the surface quality of paper tinsel, having adopted a small amount of additive, and the cathode and anode material is adjusted; Brightening agent can reduce deposition layer fragility in the electrolytic solution, helps the raising of low current density district deposition layer light.Auxiliary and brightening agent not only can obtain the settled layer that planarization is good, internal stress is controlled simultaneously, and also have crystal grain thinning, dense structure, the effect of settled layer light.Addition of C eCl
3It mainly act as stablizes Fe in the electrolytic solution
2+Content improves the performance of electrolytic solution.
The above-mentioned relatively sulfate system of electrolytic solution adopts higher pH value, has reduced cathode hydrogen evolution, has reduced the crisp brittleness and the hole of settled layer.
Adopt 304 stainless steel plates as cathode base, the Fe-Ni alloy layer can easily be peeled off, and stainless steel plate also can use for a long time.This is because 304 stainless steel surface have formed one deck and had the oxide surface film of the densification of amorphous structure, with settled layer very big crystalline phase difference is arranged, thus " not bonding " characteristic of the alloy electrodeposition layer that forms.
Anode uses I
rThe oxide coating titanium plate is also referred to as the dimensional stability anode.In the electrolytic solution of sulfate system, it is the self stability height not only, and the life-span is long, helps controlling the yin, yang pole distance, and has the very high oxygen electro catalytic activity of analysing, and removes the gas that produces when electroplating easily, thereby reduces voltage, improves the quality of settled layer.
In the iron-nickel alloy deposition layer, need strict control Fe
3+Generate, because Fe
3+Easily formation oxyhydroxide colloid is mixed in the settled layer, thereby influences snappiness, the ductility of settled layer.In electrolytic solution, add a small amount of rare earth cerium chloride used as stabilizers, can obviously suppress Fe
2+Oxidation, electrolytic solution stability is greatly improved, increase the effect of cathodic polarization simultaneously in addition, cathode efficiency is reached more than 90%, the dispersive ability of electrolytic solution and the apparent mass of settled layer also all are improved and improve.
Based on abovementioned technology, the Alloy Foil flat appearance light that the inventive method is prepared, dense structure, snappiness is good; In the prepared Alloy Foil, nickel content is 35～37% (wt%), reaches the requirement of Invar alloy composition; The Alloy Foil thickness requirement is even, can reach 15～30 μ m.It can be applicable to the components and parts in precision instrumentation, opticinstrument and the electronics.
The invor alloy foil flat appearance light that the present invention is prepared, dense structure, snappiness is good; Iron nickel content reaches the requirement of Invar alloy composition; Alloy Foil thickness is even, can reach 15～30 μ m; The magnetic property excellence, can reach following index: saturation induction density reaches 1.5T, and coercive force is 0.35Oe, and maximum permeability reaches 5.5 * 10
4, it can be applicable to the components and parts in precision instrumentation, opticinstrument and the electronics.
Compared with prior art, the present invention has following advantage:
(1) adopt 304 stainless steel plates as cathode base, the surface has formed one deck and has had the oxide surface film of the densification of amorphous structure, with settled layer very big crystalline phase difference is arranged, thereby " not bonding " characteristic Fe-Ni alloy layer of the alloy electrodeposition layer that forms can be peeled off easily.
(2) anode uses I
rThe oxide coating titanium plate has the very high oxygen electro catalytic activity of analysing, and removes the gas that produces when electroplating easily, thereby reduces voltage, improves the quality of settled layer.
(3) electrolytic solution adopts the sulfate system of low metal salt concentrations, and adds a small amount of additive, can reduce deposition layer fragility, helps improving the light of low current density district deposition layer.But also but crystal grain thinning improves the density of tissue and reduces porosity.
(4) required equipment is simple, and higher productivity is arranged, so investment is little, production cost is low.
Embodiment
Embodiment
Adopt 3 batches of invor alloy foils of method for electrodeposition preparation of the present invention.The concrete chemical ingredients of 3 batches of Invar alloy is as shown in table 1.
Electrolytic solution has added buffer reagent, complexing agent, brightening agent, auxiliary rare earth cerium chloride simultaneously for the sulfate system of low metal salt concentrations, and the chemical ingredients of 3 batches of electrolytic solution is as shown in table 2.
Use 304 stainless steels, I
rThe oxide coating titanium plate is respectively as negative electrode and anode material.Anode and cathode is placed electrolytic solution, separated by a distance, and pass to the direct current of certain hour, Invar alloy is deposited on the negative electrode, the processing parameter of 3 batches of Invar alloy galvanic deposit is listed in the table 3, take out negative plate after the galvanic deposit and rinse well, drying strips down the Fe-Ni alloy layer that its surface forms, and promptly becomes invor alloy foil.Subsequently the thickness and the performance of 3 batches of invor alloy foils are tested, test result is listed in the table 4.
The chemical ingredients (wt%) of table 1 embodiment Invar alloy
The component (g/L) of table 2 embodiment electrolytic aqueous solution
The processing parameter of table 3 embodiment galvanic deposit
The thickness and the performance of table 4 embodiment invor alloy foil
Claims (5)
1. the preparation method of an invor alloy foil, adopt electrodip process, electrolytic solution is sulfate system, is anode and cathode with the metal, and places electrolytic solution, pass to the direct current of certain hour, Invar alloy is deposited on the negative electrode, takes out negative plate then and rinse well, drying strips down the Fe-Ni alloy layer that its surface forms, promptly become invor alloy foil, it is characterized in that:
1. adopt the electrolytic solution of the sulfate system of low metal salt concentrations, the concrete component of electrolytic solution is: NiSO
46H
2O 45～50g/L, FeSO
47H
2O 32～36g/L, NaCl 20～30g/L, buffer reagent 20～50g/L, complexing agent 20～50g/L, brightening agent 2～6g/L, auxiliary 0.1～1.2g/L, addition of C eCl
37H
2O 0.1～1.0g/L;
2. cathode base uses 304 stainless steels, and anode adopts Ir oxide coating titanium plate;
3. the processing parameter of galvanic deposit is:
50～70 ℃ of temperature
pH 3.0～4.5
Current density 1.0～5.0A/dm
2
Cathode and anode spacing 10～30mm
Electrodeposition time 5～50min.
2. the preparation method of invor alloy foil according to claim 1, it is characterized in that buffer reagent be in boron vinegar, acetic acid, sodium-acetate, sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, the oxalic acid any or any two more than.
3. the preparation method of invor alloy foil according to claim 1, it is characterized in that complexing agent be in the Citrate trianion series any.
4. the preparation method of invor alloy foil according to claim 1, it is characterized in that brightening agent be in asccharin, thiocarbamide, butynediol or the propiolic alcohol any or any two more than.
5. the preparation method of invor alloy foil according to claim 1, it is characterized in that auxiliary be in benzene sulfinic acid sodium salt, sodium lauryl sulphate, the succsinic acid any or any two more than.
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| CNB2005101278087A CN100449038C (en) | 2005-12-06 | 2005-12-06 | Process for preparing invor alloy foil |
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| CNB2005101278087A CN100449038C (en) | 2005-12-06 | 2005-12-06 | Process for preparing invor alloy foil |
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| CN100449038C true CN100449038C (en) | 2009-01-07 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775629A (en) * | 2010-03-11 | 2010-07-14 | 乔瀚文 | Electroplating solution for producing magnetically soft iron-nickel-molybdenum alloy foils |
| CN103243356A (en) * | 2012-10-11 | 2013-08-14 | 湖南理工学院 | Preparation method of iron-nickel-cobalt-molybdenum alloy foil by electrodeposition |
| CN104775077B (en) * | 2015-03-23 | 2016-08-24 | 河北钢铁股份有限公司 | Ultra-fine Grained invar alloy strip and preparation method thereof |
| CN107849681A (en) | 2015-07-17 | 2018-03-27 | 凸版印刷株式会社 | The manufacture method of metal mask base material, metal mask and metal mask |
| KR102509663B1 (en) | 2015-07-17 | 2023-03-14 | 도판 인사츠 가부시키가이샤 | Method for producing base for metal masks, method for producing metal mask for vapor deposition, base for metal masks, and metal mask for vapor deposition |
| JP6805830B2 (en) * | 2015-07-17 | 2020-12-23 | 凸版印刷株式会社 | Metal mask base material for vapor deposition, metal mask for vapor deposition, metal mask base material for vapor deposition, and metal mask for vapor deposition |
| CN108166024A (en) * | 2017-12-28 | 2018-06-15 | 安徽迈德福新材料有限责任公司 | The technique that a kind of electrodeposition process prepares iron-nickel alloy foil |
| CN108468072B (en) * | 2018-03-13 | 2020-05-05 | 阿德文泰克全球有限公司 | Iron-nickel alloy shadow mask and preparation method thereof |
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