JPH01104792A - Production of electrolytic fe-ni alloy foil - Google Patents
Production of electrolytic fe-ni alloy foilInfo
- Publication number
- JPH01104792A JPH01104792A JP26187687A JP26187687A JPH01104792A JP H01104792 A JPH01104792 A JP H01104792A JP 26187687 A JP26187687 A JP 26187687A JP 26187687 A JP26187687 A JP 26187687A JP H01104792 A JPH01104792 A JP H01104792A
- Authority
- JP
- Japan
- Prior art keywords
- foil
- alloy
- electrolytic
- ions
- cathode
- 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.)
- Pending
Links
- 239000011888 foil Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 229910000990 Ni alloy Inorganic materials 0.000 title description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 39
- 239000000956 alloy Substances 0.000 claims abstract description 39
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 33
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 230000003746 surface roughness Effects 0.000 claims abstract description 12
- 229910001257 Nb alloy Inorganic materials 0.000 claims abstract description 7
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims abstract description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 40
- 238000000034 method Methods 0.000 description 37
- -1 iron ions Chemical class 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- PWHVEHULNLETOV-UHFFFAOYSA-N Nic-1 Natural products C12OC2C2(O)CC=CC(=O)C2(C)C(CCC2=C3)C1C2=CC=C3C(C)C1OC(O)C2(C)OC2(C)C1 PWHVEHULNLETOV-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007519 figuring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000889 permalloy Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、高強度で靭性に優れており、高透磁率材料で
あるＮｉの含有率が２０〜５０％と高いＦｅ −Ｎｉ合
金箔を電解により連続的に製造する方法に関するもので
ある。Detailed Description of the Invention [Industrial Application Field] The present invention provides a Fe-Ni alloy foil that has high strength, excellent toughness, and has a high Ni content of 20 to 50%, which is a high magnetic permeability material. The present invention relates to a continuous production method using electrolysis.
近年、極薄鉄箔は感磁性やシールド性等に優れた特性を
有しているので紙やプラスチックとの複合材として例え
ば地図、ゲーム盤、フロッピーディスクケース、コンピ
ューターケース用シールド材等に利用されるようになっ
てきた。In recent years, ultra-thin iron foil has excellent properties such as magnetic sensitivity and shielding properties, so it has been used as a composite material with paper and plastic, for example, for maps, game boards, floppy disk cases, shielding materials for computer cases, etc. It's starting to happen.
従来、このような極薄鉄箔を製造する方法としては、圧
延法と電解法とがあった。Conventionally, methods for manufacturing such ultra-thin iron foil include a rolling method and an electrolytic method.
圧延法は、熱延コイルを冷間圧延で中間厚さに仕上げた
薄鉄板を出発素材として焼鈍と冷間圧麺とを繰り返して
所定の厚さにまで圧延する方法であリ、最近では５声程
度のものまで製造が可能となってきている。しかしなが
ら、この圧延法では箔厚用の圧延機で冷間圧延と焼鈍と
を何回も繰り返して行なわなければならないので、生産
性や歩留りが非常に悪く、生産コストが高いという問題
点があった。The rolling method is a method in which a hot-rolled coil is cold-rolled to an intermediate thickness and a thin iron plate is used as a starting material, and then annealing and cold rolling are repeated to roll it to a predetermined thickness. It has become possible to manufacture devices that are as loud as the voice. However, with this rolling method, cold rolling and annealing must be repeated many times in a rolling mill for foil thickness, resulting in very low productivity and yield, and high production costs. .
また電解法は、全屈製回転ドラムを陰極として鉄イオン
を含む電解液中で回転ドラム上に鉄を電着させつつ順次
これを剥離して鉄箔を連続的に製造する方法であり、厚
さの薄い純鉄の箔が一挙に得られる利点はあるが、この
電解法で得られる鉄箔は圧延法で得られる鉄箔に比べて
強度が低く、厚さが薄くなるほど金属製回転ドラムから
の剥離や巻き取りが困難となり、一応２０ｉＩｎ程度が
製造可能な極薄鉄箔の厚さの下限とされているが、それ
以上の厚さにおいても２０ｐに近づくほどトラブルが発
生しており、極薄鉄箔を安定して製造することが困難で
あるという問題点があった。In addition, the electrolytic method is a method in which iron is electrodeposited on a rotating drum in an electrolytic solution containing iron ions using a fully curved rotating drum as a cathode, and then peeled off sequentially to produce iron foil continuously. Although the advantage is that thin pure iron foil can be obtained all at once, the iron foil obtained by this electrolytic method has lower strength than the iron foil obtained by rolling method, and the thinner the thickness, the more This makes peeling and winding difficult, and the lower limit of the thickness of ultra-thin iron foil that can be manufactured is approximately 20iIn, but even with thicker thicknesses, problems occur as the thickness approaches 20p. There was a problem in that it was difficult to stably produce thin iron foil.
上述したように電解法によって純鉄から成る極薄鉄箔を
安定して製造することにおいて種々の問題点があったが
、この問題点の大きな原因は純鉄がその強度や靭性にお
いて劣っていることにあり、ＮｉとＦｅとの合金箔とす
れば強度や靭性が格段に優れたものとなると共にその高
い透磁率から上記用途に使用するのに非常に有効である
ことが考えられる。As mentioned above, there have been various problems in stably manufacturing ultra-thin iron foil made of pure iron using the electrolytic method, but the main reason for these problems is that pure iron is inferior in strength and toughness. In particular, an alloy foil of Ni and Fe would have significantly superior strength and toughness, and its high magnetic permeability would make it very effective for use in the above-mentioned applications.
しかしながら、純鉄から成る極薄鉄箔ではなく、鉄と他
の金属との合金から成る極薄箔を電解法により製造しよ
うとすると、鉄と他の金属とを所定の割合で陰極面に析
出させるのに鉄イオンと他の金属のイオンとをどのよう
な濃度にした電解液を使用するか、そしてその電解液の
温度やｐＨをどのような範囲にして電流密度をどのよう
な範囲として電解を実施するか、更に陰極ドラム表面の
陰極面に析出した合金電解箔をその陰極面からどのよう
な素材を使用すれば容易に剥離することができるかなど
種々の問題点があり、特に鉄と共に合金を構成する金属
がＮｉであって製造する合金電解箔のＮｉ含有率が２０
〜５０％と非常に高い場合には上記問題点は全く解決さ
れていないためにＦｅ−Ｎｉ合金がパーマロイと略称さ
れているように優れた透磁率を有していることが判って
いながらＦｅ −Ｎｉ合金電解箔が製造されていなかっ
たのである。However, when trying to produce ultra-thin foil made of an alloy of iron and other metals using the electrolytic method instead of ultra-thin iron foil made of pure iron, iron and other metals are deposited on the cathode surface in a predetermined ratio. What concentration of iron ions and other metal ions should be used in the electrolytic solution to achieve electrolysis, and what range of temperature and pH of the electrolyte should be used, and what range of current density should be used to achieve electrolysis? There are various problems, such as whether to carry out the process and what kind of material should be used to easily peel off the alloy electrolytic foil deposited on the cathode surface of the cathode drum surface. The metal constituting the alloy is Ni and the Ni content of the manufactured alloy electrolytic foil is 20
If it is very high, such as ~50%, the above problems have not been solved at all, and even though it is known that Fe-Ni alloy has excellent magnetic permeability, as shown in the abbreviation "permalloy", Fe - Ni alloy electrolytic foil had not yet been manufactured.
本発明者等は、上記従来技術の問題点を解決してＮｉ含
有率が２０〜５０％のＦｅ −Ｎｉ合金電解箔を製造す
べく鋭意研究の結果、使用する電解液としては８０〜１
５０ｇ／ｌのＦｅ＋＋イオンと２０〜１２０ ｇ ／
ＱのＮｉ＋＋イオンとを含有する水溶液から成る電解液
を使用し、種々の実験から電流密度と温度範囲とｐｌ（
どの最適範囲を究明すると共に、陰極ドラムと。ての材
質と表面粗度Ｒａとを成る特定のもとすれば陰極面に析
出せしめたＦｅ −Ｎｉ合金電解箔を良好に剥離させて
Ｆｅ −Ｎｉ合金電解箔を製造できることを究明して本
発明を完成したのである。The inventors of the present invention have conducted intensive research to solve the problems of the prior art described above and manufacture Fe-Ni alloy electrolytic foil with a Ni content of 20 to 50%.
50 g/l Fe++ ions and 20-120 g/l
Using an electrolyte consisting of an aqueous solution containing Ni++ ions of Q, various experiments revealed that the current density, temperature range, and pl(
Along with figuring out which optimal range, the cathode drum and. The present invention has been made based on the findings that Fe-Ni alloy electrolytic foil deposited on the cathode surface can be peeled off well and Fe-Ni alloy electrolytic foil can be manufactured by using specific materials and surface roughness Ra. was completed.
すなわち本発明は、Ｎｉ含有率が２０〜５０％のＦｅ
−Ｎｉ合金電解箔を製造するに際し、８０〜１５０ ｇ
／ ＱのＦｅ＋＋イオンと２０−１２０ｇ／ｌのＮｕ
＋＋イオンとを含有する水溶液から成る電解液を使用し
て電流密度を５〜１００Ａ／ｄｍ２とし、９０〜１１０
℃の温度範囲でｐＨを３以下に調整しながら陰極ドラム
として表面粗度Ｒａが０．３〜０，７ＩｊＭであるＴｉ
、 Ｔａ、 Ｎｂ、 Ｔａ−Ｎｂ合金のいずれかを使用
して陰極面にＦｅ −Ｎｉ合金を析出せしめた後に該陰
極面に析出したＦｅ Ｎｉ合金電解箔を剥離すること
を特徴とするＦｅ −Ｎｉ合金電解箔の製造方法に関す
るものである。That is, the present invention provides Fe with a Ni content of 20 to 50%.
-80 to 150 g when manufacturing Ni alloy electrolytic foil
/ Q of Fe++ ions and 20-120 g/l of Nu
Using an electrolyte consisting of an aqueous solution containing ++ ions, the current density was set to 5 to 100 A/dm2, and
Ti having a surface roughness Ra of 0.3 to 0.7IjM as a cathode drum while adjusting the pH to 3 or less in the temperature range of °C.
, Ta, Nb, or Ta-Nb alloy is used to deposit Fe-Ni alloy on the cathode surface, and then the Fe-Ni alloy electrolytic foil deposited on the cathode surface is peeled off. The present invention relates to a method of manufacturing an electrolytic alloy foil.
以下、本発明方法について詳細に説明する。 The method of the present invention will be explained in detail below.
本発明方法は上述したように電解法によりＮｉ含有率が
２０〜５０％と高いＦｅ −Ｎｉ合金電解箔を製造する
方法であって、８０〜１５０ ｇ ／ ＱのＦｅ＋＋イ
オンと２０〜１２０ｇ／ΩのＮｉ＋＋イオンとを含有す
る水溶液から成る電解液を使用する。この電解液は、Ｎ
ｉ＋＋イオンの濃度が２０ ｇ ／ ｆ１未満では電解
法により得られるＦｅ−Ｎｉ合金電解箔中のＮｉ含有率
が２０％未満となって本発明の目的とするＮｉ含有率の
高いＦｅ −Ｎｉ合金電解箔を製造することができず、
また１２０ｇ／Ωを超えると電解法により得られるＦｅ
−Ｎｉ合金電解箔中のＮｉ含有率が５０％を超えて高く
なるため市着応力が高くなって得られるＦｅ −Ｎｉ合
金電解箔に割れが生じたり陰極面に電着する皮膜が電解
中に陰極面から剥がれたりして良好にＦｅ−Ｎｉ合金電
解箔を製造することができないために好ましくないから
である。またＦｅ＋＋イオンの濃度が８０〜１５０ ｇ
／ ｆｌの範囲になければならないのは、電解液中に
おけるＦＣ＋＋イオンとＮｉ＋＋イオンとの和は１００
〜２７０ ｇ ／Ωの範囲内になければならないからで
あって、和が１００ｇ／ｌ未満では電着応力が高くなっ
て陰極面に電着する皮膜を陰極面から良好に剥離するこ
とができなくなるなどの理由により好ましくなく、和が
２７０ ｇ ／Ωを超えると陰極面に結晶が析出しまた
電流効率が低下するなどの理由により好ましくないから
である。As described above, the method of the present invention is a method for producing Fe-Ni alloy electrolytic foil with a high Ni content of 20 to 50% by electrolytic method, and comprises Fe++ ions of 80 to 150 g/Q and 20 to 120 g/Ω. An electrolyte consisting of an aqueous solution containing Ni++ ions is used. This electrolyte is N
If the concentration of i++ ions is less than 20 g/f1, the Ni content in the Fe-Ni alloy electrolytic foil obtained by the electrolytic method will be less than 20%, and the Fe-Ni alloy electrolytic with a high Ni content, which is the objective of the present invention, will not be achieved. Unable to manufacture foil,
Moreover, if it exceeds 120 g/Ω, Fe obtained by electrolytic method
- As the Ni content in the Ni alloy electrolytic foil increases to more than 50%, the adhesion stress increases, resulting in cracks in the Fe -Ni alloy electrolytic foil, and the film electrodeposited on the cathode surface during electrolysis. This is because it is undesirable because it may peel off from the cathode surface, making it impossible to produce a good Fe-Ni alloy electrolytic foil. Also, the concentration of Fe++ ions is 80 to 150 g.
The sum of FC++ ions and Ni++ ions in the electrolyte must be in the range of / fl.
This is because it must be within the range of ~270 g/Ω, and if the sum is less than 100 g/l, the electrodeposition stress becomes high and the film electrodeposited on the cathode surface cannot be peeled off well from the cathode surface. If the sum exceeds 270 g/Ω, crystals will precipitate on the cathode surface and the current efficiency will decrease.
この電解液はＦａＣＩ２．・ｎＨ，ＯとＮｉＣ１，・６
Ｈ２０とを用いて調製することができるが、電解量にお
いてはｐＨを３以下に調整し且つ温度を９０〜１１０℃
の温度範囲に維持することに留意しなければならず、ｐ
Ｈを３以下に調整するのはＰＨが３以上になる場合には
ＨＣｌを添加することによって行えば良い。これはρ１
１が３を超えると２価の鉄イオンが３価の鉄イオンに酸
化して陰極面に電着する皮膜中の水酸化物が増すことに
よって鉄含有量が増加して本発明の目的とする２０％以
上のＮｉ含有量を有するＦｅ−Ｎｉ合金電解箔を製造す
ることができなくなるためであり、温度を９０−１１０
℃の温度範囲に維持するのは温度が９０℃未満では電着
応力が高く且つ陰極面に電着する皮膜中の鉄が脆化する
ために陰極面から剥離することができなくなるので好ま
しくなく、１１０℃を超えると電解液が沸騰して陰極面
に電着するＦｅ −Ｎｉ合金電解箔の表面状態を悪化さ
せるので好ましくないためである。This electrolyte is FaCI2.・nH,O and NiC1,・6
It can be prepared using H20, but the amount of electrolysis requires adjusting the pH to 3 or less and the temperature at 90 to 110°C.
Care must be taken to maintain the temperature range of p
When the pH is 3 or more, H may be adjusted to 3 or less by adding HCl. This is ρ1
When 1 exceeds 3, divalent iron ions are oxidized to trivalent iron ions, and the amount of hydroxide in the film electrodeposited on the cathode surface increases, resulting in an increase in iron content, which is the object of the present invention. This is because it becomes impossible to manufacture Fe-Ni alloy electrolytic foil with a Ni content of 20% or more, and the temperature is set at 90-110%.
It is not preferable to maintain the temperature in the range of 90°C because if the temperature is less than 90°C, the electrodeposition stress will be high and the iron in the film electrodeposited on the cathode surface will become brittle and cannot be peeled off from the cathode surface. This is because if the temperature exceeds 110°C, the electrolytic solution will boil and deteriorate the surface condition of the Fe--Ni alloy electrolytic foil electrodeposited on the cathode surface, which is not preferable.
このようにして調製した電解液を使用して電解を行うに
際し、電流密度は５〜１００Ａ／ｄｍ”に維持すること
が必要であり、電流密度が５ Ａ／ｄｍ２未満では陰極
面でＮｉの析出が優先的に起こって電着応力が高くなり
クラックが生じて箔として剥離できなくなると共に生産
性も低くなり、１００Ａ／ｄｍ２を超えると電流効率が
低下して著しい場合には箔の表面状態が悪化するために
好ましくないからである。When performing electrolysis using the electrolyte solution prepared in this way, it is necessary to maintain the current density at 5 to 100 A/dm2, and if the current density is less than 5 A/dm2, Ni will precipitate on the cathode surface. occurs preferentially, the electrodeposition stress increases, cracks occur, and the foil cannot be peeled off, and productivity also decreases.If it exceeds 100A/dm2, the current efficiency decreases, and if it is significant, the surface condition of the foil deteriorates. This is because it is not desirable to do so.
そして使用する陰極面としては、電着した金属に対する
剥離性の良い金属であるＴｉ、 Ｔａ、 Ｎｂ、 Ｔａ
−Ｎｂ合金のいずれかを雨月した陰極ドラムを使用する
ことが必要であるが、単にこのような剥離性の良い金属
製の陰極ドラムを使用しただけでは陰極面に析出せしめ
たＦｅ−Ｎｉ合金電解箔を剥離することはできず、その
表面粗度Ｒａが０．３〜０．７ｐの範囲内になければな
らないのである。これは表面粗度Ｒａが０．３ｐ未満で
は陰極面に析出する皮膜が目的の厚さに到達する前に陰
極面から部分的に剥離し著しい場合には全体的に剥離し
てしまうので好ましくなく１表面粗度Ｒａが０．７ＩＪ
ｆａを超えると陰極面に電着する皮膜が陰極面に密着し
て箔として陰極面から剥離することが困難となり著しい
場合には陰極面から剥離することが全くできなくなる現
象が生じるために好ましくないからである。The cathode surface used is made of Ti, Ta, Nb, Ta, which are metals with good peelability for electrodeposited metals.
- It is necessary to use a cathode drum coated with one of the Nb alloys, but simply using such a cathode drum made of a metal with good releasability will result in Fe-Ni alloy deposited on the cathode surface. The electrolytic foil cannot be peeled off, and its surface roughness Ra must be within the range of 0.3 to 0.7p. This is undesirable because if the surface roughness Ra is less than 0.3p, the film deposited on the cathode surface will partially peel off from the cathode surface before reaching the desired thickness, and if it is severe, it will peel off entirely. 1Surface roughness Ra is 0.7IJ
If fa is exceeded, the film electrodeposited on the cathode surface adheres closely to the cathode surface, making it difficult to peel off from the cathode surface as a foil, and in severe cases, it is not preferable because it becomes impossible to peel it off from the cathode surface at all. It is from.
このように、８０〜１５０ｇ／ｌのＦｅ＋＋イオンと２
０〜１２０ｇ／ｕのＮｉ”イオンとを含有する水溶液か
ら成る電解液を使用して電流密度を５〜１００Ａ／ｄｍ
”とし、９０〜１１０℃の温度範囲でｐＨを３以下に調
整しながら陰極ドラムとして表面粗度Ｒａが０．３〜０
．７声であるＴｉ、 Ｔａ、 Ｎｂ、 Ｔａ−Ｎｂ合金
のいずれかを使用して電解を行うと、陰極面にＮｉ含有
率が２０〜５０％のＦｅ−Ｎｉ合金電解箔が析出するの
でこの陰極面に析出したＦｅ −Ｎｉ合金電解箔を剥離
すればＮｉ含有率が２０”ｒ５０％と高いＦｅ −Ｎｉ
合金電解箔を良好に連続的に製造することができるので
ある。In this way, 80-150 g/l of Fe++ ions and 2
Using an electrolyte consisting of an aqueous solution containing 0 to 120 g/u of Ni" ions, the current density is 5 to 100 A/dm.
", and the surface roughness Ra is 0.3 to 0 as a cathode drum while adjusting the pH to 3 or less in the temperature range of 90 to 110 ° C.
．． When electrolysis is performed using any of the 7-tone Ti, Ta, Nb, and Ta-Nb alloys, Fe-Ni alloy electrolytic foil with a Ni content of 20 to 50% is deposited on the cathode surface. When the Fe-Ni alloy electrolytic foil deposited on the surface is peeled off, Fe-Ni with a high Ni content of 20"r50% is obtained.
The alloy electrolytic foil can be produced continuously and efficiently.
以下に実施例について説明する。 Examples will be described below.
先ず、下表に示す混合割合でＦｅＣｌ２・ｎＨ２ＯとＮ
ｉＣｌ２・６Ｈ２０と更に必要に応じて添加したＨＣｌ
とＮＨ４ＯＨ，とを用いて電解液を調製した。なお、Ｈ
ＣｌとＮＨ，ＯＨとはＦｅＣ４・ｎＨ，ＯとＮｉＣｌ２
・６Ｈ２０とで第１表に記載した混合割合で調製した電
解液ＩＱに第１表に記載した量だけ添加したものである
。First, FeCl2.nH2O and N were mixed at the mixing ratio shown in the table below.
iCl2・6H20 and HCl added as necessary
An electrolytic solution was prepared using NH4OH and NH4OH. In addition, H
Cl and NH, OH are FeC4・nH, O and NiCl2
・6H20 was added in the amount shown in Table 1 to electrolytic solution IQ prepared at the mixing ratio shown in Table 1.
以下余白
第１表
上記第１表に示した電解液を使用してＦｅ−Ｎｉ合金箔
を電解法により製造した結果の実施例を第２表に、また
比較例を第３表にそれぞれ示す。Below is a blank Table 1. Examples of the results of manufacturing Fe--Ni alloy foil by an electrolytic method using the electrolytes shown in Table 1 above are shown in Table 2, and Table 3 shows comparative examples.
第２表
第３表
上記第２表及び第３表において、成否の欄における各部
は次の通りである。Table 2 Table 3 In Tables 2 and 3 above, each part in the success/failure column is as follows.
０ｆｒＪの製造可能
・ 箔を剥離できない
Δ 箔が電着中で剥離した
ム 箔の表面状態が不良
× 箔にならなかった
上記第２表及び第３表の実施例及び比較例から８０〜１
５０ｇＩＱのＦｅ＋＋イオンと２０〜１２０ｇ／ｌのＮ
ｘ ＋＋イオンとを含有する水溶液から成る電解液を
使用して電流密度を５〜１００Ａ／ｄａｉ”とし、９０
〜１１０℃の温度範囲でｐＨを３以下に調整しながら陰
極ドラムとして表面粗度Ｒａが０．３〜０．７．ｎであ
るＴｉ、 Ｔａ、 Ｎｂ。Possible to manufacture 0frJ・Foil cannot be peeled Δ Foil peeled off during electrodeposition Foil surface condition is poor
50gIQ Fe++ ions and 20-120g/l N
Using an electrolyte consisting of an aqueous solution containing
While adjusting the pH to 3 or less in the temperature range of ~110°C, the surface roughness Ra is 0.3~0.7. n Ti, Ta, Nb.
Ｔａ−Ｎｂ合金のいずれかを使用して陰極面にＦｅ −
Ｎｉ合金を析出せしめた後に該陰極面に析出したＦｅ
−Ｎｉ合金電解箔を剥離する本発明に係るＦｅ −Ｎｉ
合金電解箔の製造方法によれば、Ｎｉ含有率が２０〜５
０％と高いＦｅ−Ｎｉ合金電解箔を良好に製造すること
ができるのに対し、比較例１〜４のように電解液のＦｅ
＋＋イオン及びＮｉ＋＋イオンの含有量、特にＮｉ＋＋
イオンの含有量が多すぎて本発明法の範囲を逸脱してい
る場合には箔の製造が不可能であり、比較例５〜７のよ
うに電流密度が小さすぎて本発明法の範囲を逸脱してい
る場合には箔の製造が不可能でありまた比較例８〜１０
のように電流密度が大きすぎて本発明法の範囲を逸脱し
ている場合には箔の表面状態が不良となり、比較例１１
〜１３のように陰極板の表面粗度Ｒａが小さすぎて本発
明法の範囲を逸脱している場合には箔が電着中で剥離し
て好ましくなくまた比較例１４及び１５のように表面粗
度Ｒａが大きすぎて本発明法の範囲を逸脱している場合
には箔を陰極板の表面から剥にできないために箔の製造
が不可能であり、更に比較例１６及び１７のように陰極
板の表面粗度Ｒａが本発明法の範囲を逸脱していると共
に陰極ドラムの陰極面が本発明法の対象とする剥離性の
良い金属に該当しない５ｔｌＳ４３０であっても同様で
あり、比較例１８〜２０のように電解液のＰＨが高すぎ
て本発明法の範囲を逸脱している場合には箔にならず比
較例２１及び２２のように電解液のＰＨが低すぎて本発
明法の範囲を逸脱している場合には箔の表面状態が不良
となって好ましくなく、比較例２３〜２５のように電解
液の液温か高すぎて本発明法の範囲を逸脱している場合
には箔の表面状態が不良となって好ましくなく比較例２
６及び２７のように電解液の液温か低すぎて本発明法の
範囲を逸脱している場合には箔にならず、比較例２８〜
３２のように陰極ドラムの陰極面が本発明法の対象とす
る剥離性の良い金属に該当しない金属であると箔が陰極
面から剥離できなかったり箔が電着途中で剥離したりし
て良好な合金箔を製造できないことが判る。Fe − on the cathode surface using either Ta-Nb alloy
Fe deposited on the cathode surface after depositing the Ni alloy
-Fe-Ni according to the present invention peeling off Ni alloy electrolytic foil
According to the method for manufacturing alloy electrolytic foil, the Ni content is 20 to 5
While Fe-Ni alloy electrolytic foil with a high Fe-Ni content of 0% can be successfully manufactured, as in Comparative Examples 1 to 4, Fe-Ni alloy electrolytic foil with a high
++ ion and Ni++ ion content, especially Ni++
If the ion content is too high and falls outside the scope of the method of the present invention, it is impossible to manufacture the foil, and as in Comparative Examples 5 to 7, the current density is too low and falls outside the scope of the method of the present invention. If it deviates, it is impossible to manufacture the foil, and Comparative Examples 8 to 10
If the current density is too high and is out of the range of the method of the present invention, as in Comparative Example 11, the surface condition of the foil will be poor.
If the surface roughness Ra of the cathode plate is too small and is outside the scope of the method of the present invention, as shown in Comparative Examples 14 and 13, the foil may peel off during electrodeposition, which is undesirable. If the roughness Ra is too large and is out of the range of the method of the present invention, the foil cannot be peeled off from the surface of the cathode plate, making it impossible to manufacture the foil. The same applies even if the surface roughness Ra of the cathode plate is outside the range of the method of the present invention and the cathode surface of the cathode drum is 5tlS430, which does not fall under the metal with good releasability targeted by the method of the present invention. As in Examples 18 to 20, when the pH of the electrolytic solution is too high and is outside the range of the method of the present invention, no foil is formed, as in Comparative Examples 21 and 22, when the pH of the electrolytic solution is too low and the method of the present invention If it deviates from the range of the method, the surface condition of the foil becomes poor, which is undesirable, and if the temperature of the electrolyte is too high as in Comparative Examples 23 to 25, it deviates from the range of the method of the present invention. In Comparative Example 2, the surface condition of the foil becomes poor and undesirable.
In cases where the temperature of the electrolytic solution is too low and deviates from the range of the method of the present invention, as in Comparative Examples 28 to 27, the foil does not form.
If the cathode surface of the cathode drum is made of a metal that does not fall under the category of metals with good releasability targeted by the method of the present invention, as in No. 32, the foil may not be peeled from the cathode surface or the foil may peel off during electrodeposition. It can be seen that it is not possible to produce alloy foils that are
以上詳述した本発明に係るＦｅ−Ｎｉ合金電解箔の製造
方法は、８０〜１５０ ｇ ／ ＱのＦｅ＋＋イオンと
２０〜１２０ｇ／ΩのＮｉ＋＋イオンとを含有する水溶
液から成る電解液を使用して電流密度を５〜１００Ａ／
ｄｍ２とし、９０〜１１０℃の温度範囲でＨＣｌを添加
することによってＰＨを３以下に調整しながら陰極ドラ
ムとして表面粗度Ｒａが０．３〜０．７７ａであるＴｉ
、丁ａ、 Ｎｂ。The method for manufacturing Fe-Ni alloy electrolytic foil according to the present invention described in detail above uses an electrolytic solution consisting of an aqueous solution containing 80 to 150 g/Q of Fe++ ions and 20 to 120 g/Ω of Ni++ ions. Current density 5-100A/
dm2, and the surface roughness Ra is 0.3 to 0.77a as a cathode drum while adjusting the pH to 3 or less by adding HCl at a temperature range of 90 to 110 °C.
, Ding a, Nb.
Ｔａ−Ｎｂ合金のいずれかを使用して陰極面にＦｅ −
Ｎｉ合金を析出せしめた後に該陰極面に析出したＦｅ＝
Ｎｉ合金電解箔を剥離することにより従来電解法により
製造することが不可能であったＮｉ含有率が２０〜５０
％と高いＦｅ −Ｎｉ合金電解箔を製造することを可能
とした画期的な方法であり、Ｎｉ含有率が高いことに起
因した高強度で靭性に優れていて高透磁率材料であるＮ
ｉの含有率が２０〜５′０％と高いＦｅ −Ｎｉ合金箔
を電解により連続的に製造することができるために従来
極薄鉄箔では不充分であった特性を改善した紙やプラス
チックとの複合材として例えば地図、ゲーム盤、フロッ
ピーディスクケース。Fe − on the cathode surface using either Ta-Nb alloy
Fe deposited on the cathode surface after depositing the Ni alloy=
By peeling off the Ni alloy electrolytic foil, the Ni content, which was impossible to produce by conventional electrolytic methods, can be reduced to 20 to 50.
This is an epoch-making method that makes it possible to manufacture Fe-Ni alloy electrolytic foil with a high Ni content.
Fe-Ni alloy foil with a high i content of 20 to 5'0% can be produced continuously by electrolysis, making it possible to produce paper and plastic with improved properties that were previously unsatisfactory with ultra-thin iron foil. Examples of composite materials include maps, game boards, and floppy disk cases.
Claims (1)
を製造するに際し、８０〜１５０ｇ／ｌのＦｅ＾＋＾＋
イオンと２０〜１２０ｇ／ｌのＮｉ＾＋＾＋イオンとを
含有する水溶液から成る電解液を使用して電流密度を５
〜１００Ａ／ｄｍ＾２とし、９０〜１１０℃の温度範囲
でｐＨを３以下に調整しながら陰極ドラムとして表面粗
度Ｒａが０．３〜０．７μｍであるＴｉ、Ｔａ、Ｎｂ、
Ｔａ−Ｎｂ合金のいずれかを使用して陰極面にＦｅ−Ｎ
ｉ合金を析出せしめた後に該陰極面に析出したＦｅ−Ｎ
ｉ合金電解箔を剥離することを特徴とするＦｅ−Ｎｉ合
金電解箔の製造方法。 ２ ８０〜１５０ｇ／ｌのＦｅ＾＋＾＋イオンと２０〜
１２０ｇ／ｌのＮｉ＾＋＾＋イオンとを含有する水溶液
から成る電解液をＦｅＣｌ＿２・ｎＨ＿２ＯとＮｉＣｌ
＿２・６Ｈ＿２Ｏとを用いて調製する特許請求の範囲第
１項に記載のＦｅ−Ｎｉ合金電解箔の製造方法。 ３ 電解液のｐＨをＨＣｌを添加することによつて３以
下に調整する特許請求の範囲第１項又は第２項に記載の
Ｆｅ−Ｎｉ合金電解箔の製造方法。[Claims] 1. When producing Fe-Ni alloy electrolytic foil with a Ni content of 20 to 50%, 80 to 150 g/l of Fe^+^+
ions and an aqueous solution containing 20 to 120 g/l of Ni^+^+ ions at a current density of 5.
Ti, Ta, Nb, which has a surface roughness Ra of 0.3 to 0.7 μm as a cathode drum while adjusting the pH to 3 or less in the temperature range of 90 to 110 ° C.
Fe-N on the cathode surface using either Ta-Nb alloy
Fe-N deposited on the cathode surface after depositing the i alloy
A method for producing an Fe-Ni alloy electrolytic foil, which comprises peeling off the i-alloy electrolytic foil. 2 80~150g/l of Fe^+^+ ions and 20~
An electrolytic solution consisting of an aqueous solution containing 120 g/l of Ni^+^+ ions was mixed with FeCl_2・nH_2O and NiCl
The method for producing an Fe-Ni alloy electrolytic foil according to claim 1, wherein the Fe-Ni alloy electrolytic foil is prepared using _2.6H_2O. 3. The method for producing an Fe-Ni alloy electrolytic foil according to claim 1 or 2, wherein the pH of the electrolytic solution is adjusted to 3 or less by adding HCl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26187687A JPH01104792A (en) | 1987-10-19 | 1987-10-19 | Production of electrolytic fe-ni alloy foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26187687A JPH01104792A (en) | 1987-10-19 | 1987-10-19 | Production of electrolytic fe-ni alloy foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01104792A true JPH01104792A (en) | 1989-04-21 |
Family
ID=17367988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26187687A Pending JPH01104792A (en) | 1987-10-19 | 1987-10-19 | Production of electrolytic fe-ni alloy foil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01104792A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6503348B1 (en) | 1997-09-03 | 2003-01-07 | Ballard Power Systems Ag | Method of making a metal membrane foil made of a palladium alloy for hydrogen separation |
| JPWO2011001932A1 (en) * | 2009-06-29 | 2012-12-13 | 日立金属株式会社 | Method for producing aluminum foil |
| WO2022014669A1 (en) * | 2020-07-16 | 2022-01-20 | 東洋鋼鈑株式会社 | Electrolytic iron foil |
| JPWO2022014668A1 (en) * | 2020-07-16 | 2022-01-20 |
-
1987
- 1987-10-19 JP JP26187687A patent/JPH01104792A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6503348B1 (en) | 1997-09-03 | 2003-01-07 | Ballard Power Systems Ag | Method of making a metal membrane foil made of a palladium alloy for hydrogen separation |
| JPWO2011001932A1 (en) * | 2009-06-29 | 2012-12-13 | 日立金属株式会社 | Method for producing aluminum foil |
| JP5403053B2 (en) * | 2009-06-29 | 2014-01-29 | 日立金属株式会社 | Method for producing aluminum foil |
| WO2022014669A1 (en) * | 2020-07-16 | 2022-01-20 | 東洋鋼鈑株式会社 | Electrolytic iron foil |
| JPWO2022014668A1 (en) * | 2020-07-16 | 2022-01-20 | ||
| JPWO2022014669A1 (en) * | 2020-07-16 | 2022-01-20 | ||
| WO2022014668A1 (en) * | 2020-07-16 | 2022-01-20 | 東洋鋼鈑株式会社 | Electrolytic iron foil |
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