JPH028352A - Heat treatment of metal or alloy - Google Patents
Heat treatment of metal or alloyInfo
- Publication number
- JPH028352A JPH028352A JP2088488A JP2088488A JPH028352A JP H028352 A JPH028352 A JP H028352A JP 2088488 A JP2088488 A JP 2088488A JP 2088488 A JP2088488 A JP 2088488A JP H028352 A JPH028352 A JP H028352A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- heat
- alloy
- acidic
- heat treatment
- 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
- 238000010438 heat treatment Methods 0.000 title claims abstract description 27
- 239000000956 alloy Substances 0.000 title claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000000137 annealing Methods 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 150000004673 fluoride salts Chemical class 0.000 claims description 16
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000005498 polishing Methods 0.000 description 11
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、銅、銅合金、ニッケル又はニッケル・鉄合金
等の条材のコイルをハツチ類で密着させることなく焼鈍
させる場合に好適の金属又は合金の熱処理方法に関する
。[Detailed Description of the Invention] [Industrial Application Field] The present invention is a metal suitable for annealing a coil of strip material such as copper, copper alloy, nickel, or nickel-iron alloy without closely contacting it with a hatch. Or it relates to an alloy heat treatment method.
［従来の技術］
銅（Ｃｕ）、Ｃｕ合金、ニッケル（Ｎ１）又はＮｉ・鉄
（Ｆｅ）合金等の線状又は板状の条材のコイルを密着不
良を発生させることなく焼鈍する技術として、従来、コ
イルを連続して巻き戻しつつ焼鈍する所謂Ａ、Ｐライン
又はＢ、Ａライン等の連続式焼鈍炉により焼鈍するもの
がある。[Prior Art] As a technique for annealing a coil of a linear or plate-like strip material such as copper (Cu), Cu alloy, nickel (N1), or Ni/iron (Fe) alloy without causing adhesion failure, Conventionally, some coils are annealed in a continuous annealing furnace such as the so-called A, P line or B, A line, in which the coil is annealed while being continuously unwound.
しかしなから、析出処理を必要とするＣｕ合金等は析出
のために一定の保持時間を必要とする。However, Cu alloys that require precipitation treatment require a certain holding time for precipitation.
このため、連続式焼鈍法では十分な保持時間をとること
ができないのて、この種のコイルはバッチ式の焼鈍方法
によらさるを得ない。For this reason, since continuous annealing cannot provide a sufficient holding time, this type of coil cannot be subjected to batch annealing.
この場合に、コイルをバッチ式の焼鈍炉により焼鈍しよ
うとすると、コイル状に巻かれた条材の接触面にて相互
に密着してしまい、条材の表面不良が発生する。In this case, if an attempt is made to anneal the coil in a batch-type annealing furnace, the contact surfaces of the coiled strips will come into close contact with each other, resulting in surface defects in the strips.
そこで、Ｓｉを−（Ｓ ｉ Ｏ）。−型の化合物として
含有する油を灯油で薄めた油液をコイルの全長にわたっ
てその表面に塗布し、条材同士が直接的に接触しないよ
うにしている。Therefore, Si is -(S i O). An oil solution made by diluting oil containing -type compounds with kerosene is applied to the surface of the coil along its entire length, so that the strips do not come into direct contact with each other.
［発明が解決しようとする課題］
しかしながら、Ｓｉオイルを塗布したＣｕ合金等のコイ
ルを焼鈍するとＳｉが酸化されてＳｉＯ２が生成し、こ
れがＣｕ合金コイルの表面にイ（着する。そして、バッ
チ焼鈍後に、酸化スケール除去のためにコイル表面を研
磨すると、コイル表面に付着した５ｉ０２が研磨砥石の
かかりを悪化させ、研磨能力を阻害する。これにより、
生産性が著しく低下すると共に、研磨量が減少するため
、加熱ふくれの原因となる条材表面のがぶさり状欠陥を
除去することができないので製品品質も劣化させてしま
う。[Problems to be Solved by the Invention] However, when a coil made of Cu alloy or the like coated with Si oil is annealed, Si is oxidized and SiO2 is generated, which is deposited on the surface of the Cu alloy coil. Later, when the coil surface is polished to remove oxide scale, the 5i02 adhering to the coil surface worsens the grip of the polishing wheel and impedes the polishing ability.
Product quality is also degraded because productivity is significantly reduced and the amount of polishing is reduced, making it impossible to remove bulge-like defects on the surface of the strip that cause heating blisters.
なお、従来、研磨処理に先立ち、コイルを硫酸水溶液又
は硫酸と過酸化水素との混合溶液により処理しているが
、コイル表面のＳ ＩＯ２を十分に除去することは困難
である。Conventionally, prior to polishing, the coil is treated with an aqueous sulfuric acid solution or a mixed solution of sulfuric acid and hydrogen peroxide, but it is difficult to sufficiently remove SIO2 from the surface of the coil.
このため、従来、Ｓｉオイル中のＳｉ含有量を低下させ
てコイルに塗布するが、又はＳｉオイルを塗布せずにコ
イルを焼鈍処理している。For this reason, conventionally, the Si content of Si oil is reduced and applied to the coil, or the coil is annealed without applying Si oil.
しかしながら、このようにＳｉ含有量が低い場合は、焼
鈍過程てコイルの条材間の密着が生じゃすく、条材と条
材との間て局所的に密着して歩留を低下させる要因にな
っている。また、密着が生じていない部分においても、
コイル条材の表面に局所的に大量のＳｉ酸化物が残存し
てしまう。However, when the Si content is low like this, the adhesion between the coil strips becomes weak during the annealing process, causing local adhesion between the strips and reducing the yield. It has become. Also, even in areas where there is no close contact,
A large amount of Si oxide locally remains on the surface of the coil strip.
特に、近時、Ｃｕ、Ｃｕ合金、Ｎｉ又はＮｉＦｅ合金等
のコイルをバッチ炉により焼鈍する場合に、生産性の向
上を図るために、コイルの広幅化及び３１〜ンがら８ト
ンまての嚇重の増加が促進されている。このため、Ｓｉ
オイルの塗りむらが発生しやすく、また焼鈍時の熱膨張
によりコイルの巻き締りか起きやすくなっている。従っ
て、このようなＳｉオイルの塗りむら、コイルの巻き締
り及びコイル重量増加により、増々コイル条材間の密着
が生しやすい状況下にある。また、Ｓｉオイル中のＳｉ
の濃度については厳しい管理が必要である。このため、
熱処理工程が煩雑化するという難点がある。In particular, recently, when annealing coils of Cu, Cu alloy, Ni or NiFe alloy, etc. in a batch furnace, in order to improve productivity, the width of the coil has been increased and Weight gain is promoted. For this reason, Si
It is easy for the oil to become unevenly coated, and the coil is likely to tighten due to thermal expansion during annealing. Therefore, due to the uneven coating of Si oil, the tight winding of the coil, and the increase in coil weight, it is increasingly likely that the coil strips will come into close contact with each other. In addition, Si in Si oil
Strict control is required regarding the concentration of For this reason,
There is a drawback that the heat treatment process becomes complicated.
本発明はかかる問題点に鑑みてなされたものであって、
熱処理による被熱処理材相互間の密着を確実に防止する
ことができると共に、Ｓｉ酸化物が付着していないコイ
ルを研磨工程に供給することができる金属又は合金の熱
処理方法を提供することを目的とする。The present invention has been made in view of such problems, and includes:
It is an object of the present invention to provide a method for heat treatment of metals or alloys that can reliably prevent adhesion between materials to be heat treated due to heat treatment and can supply a coil to a polishing process to which no Si oxide is attached. do.
［課題を解決するための手段］
本発明に係る金属又は合金の熱処理方法においては、２
重量％以上のＳｉを含有する油液を被熱処理材の表面に
塗布した後、被熱処理材を熱処理する。次いで、この熱
処理により生じたＳｉ酸化物を酸性フッ化塩を含有する
水溶液により処理して除去する。[Means for Solving the Problems] In the method for heat treatment of metal or alloy according to the present invention, 2
After applying an oil solution containing at least % by weight of Si to the surface of the heat-treated material, the heat-treated material is heat-treated. Next, the Si oxide produced by this heat treatment is removed by treatment with an aqueous solution containing an acidic fluoride salt.
また、本発明をコイル状の被熱処理材の焼鈍処理に適用
した場合は、被熱処理材の表面に２重量％以上のＳｉを
含有する油液を塗布した後、３００乃至７００°Ｃの温
度て焼鈍し、次いで、１０ｇ／ｌ以上の酸性フッ化塩を
含有する水溶液により焼鈍時に発生したＳｉ酸化物を除
去する。In addition, when the present invention is applied to annealing a coil-shaped material to be heat treated, after applying an oil solution containing 2% by weight or more of Si to the surface of the material to be heat treated, the material is annealed at a temperature of 300 to 700°C. Annealing is performed, and then Si oxide generated during annealing is removed using an aqueous solution containing 10 g/l or more of an acidic fluoride salt.
［作用］
本発明においては、２重量％以上の十分高い濃度のＳｉ
を含有する油液を塗布した後、金属又は合金の被熱処理
材を熱処理するから、被熱処理材か熱処理中に局所的に
密着してしまうことか回避される。[Function] In the present invention, a sufficiently high concentration of Si of 2% by weight or more is used.
Since the metal or alloy material to be heat treated is heat-treated after applying the oil containing the oil, it is possible to avoid local contact between the material and the material to be heat-treated during the heat treatment.
また、熱処理後には、酸性フッ化塩を含有する水溶液に
より被熱処理材を処理し、熱処理により被熱処理材の表
面に生成したＳ１酸化物を除去する。これにより、例え
は、本発明をコイルの熱処理に適用した場合は、後工程
のスケール除去の研磨工程にＳｉ酸化物か付着していな
い清浄なコイルを供給することかできる。Further, after the heat treatment, the material to be heat treated is treated with an aqueous solution containing an acidic fluoride salt, and the S1 oxide generated on the surface of the material to be heat treated by the heat treatment is removed. As a result, for example, when the present invention is applied to heat treatment of a coil, a clean coil with no Si oxide attached can be supplied to the subsequent polishing step for removing scale.
［実施例］ 以下、本発明の実施例について詳細に説明する。[Example] Examples of the present invention will be described in detail below.
先ず、Ｃｕ、Ｃｕ合、金、Ｎｉ又はＮｉ−Ｆｅ合金等の
被熱処理材の線状又は板状の条材をコイルに巻き取る際
に、この条材の表面にＳｉ濃度が２乃至１０重量％のＳ
ｉ含有オイルを均一に塗布する。First, when winding a linear or plate-shaped strip of heat-treated material such as Cu, Cu alloy, gold, Ni, or Ni-Fe alloy into a coil, the surface of the strip has a Si concentration of 2 to 10% by weight. %S
Apply i-containing oil evenly.
次いで、バッチ炉に被熱処理材を装入し、３００乃至７
００℃に加熱して被熱処理材を焼鈍する。Next, the material to be heat treated is charged into a batch furnace and heated to 300 to 7
The material to be heat treated is annealed by heating to 00°C.
そうすると、条材の表面のＳｉオイルがＳｉ酸化物にな
り、そのまま残存するので、条材同士の局所的な密着は
回避される。In this case, the Si oil on the surface of the strip becomes Si oxide and remains as it is, so that local adhesion between the strips is avoided.
Ｓｉオイル中のＳｉ濃度は２重量％である。The Si concentration in the Si oil is 2% by weight.
Ｓｉ濃度が２重量％未満の場合は、後工程の研磨工程に
て研磨のかかり方は良好であるが、焼鈍時の密着不良を
十分に防止することはできず、５００乃至７００℃とい
う比較的高温の焼鈍処理により局所的な密着が発生して
しまう。このため、Ｓｉ濃度は２重量％以上にする。If the Si concentration is less than 2% by weight, the polishing will be good in the subsequent polishing process, but poor adhesion during annealing cannot be sufficiently prevented, and the Local adhesion occurs due to high temperature annealing treatment. Therefore, the Si concentration is set to 2% by weight or more.
このＳｉ濃度は１０重量％以下にすることが好ましい。This Si concentration is preferably 10% by weight or less.
Ｓｉ濃度を１０重量％を超えて高くしても、焼鈍時の密
着防止効果は１０重量％以下の場合と同等である。また
、Ｓｉ濃度を高めると、処理コス１〜が高くなると共に
、後工程のＳｉ酸化物除去工程において酸性フッ化塩水
溶液を劣化させてしまう。このため、Ｓｉオイル中のＳ
ｉ凛度は１０重量％以下にすることか好ましい。Even if the Si concentration is increased to more than 10% by weight, the effect of preventing adhesion during annealing is the same as when the Si concentration is 10% by weight or less. Moreover, when the Si concentration is increased, the processing cost 1~ increases and the acidic fluoride salt aqueous solution is deteriorated in the Si oxide removal step in the subsequent step. For this reason, S in Si oil
It is preferable that the degree of coolness is 10% by weight or less.
そして、熱処理後に酸性フッ化塩を含有する水溶液によ
り被熱処理材を処理して、焼鈍により被熱処理材の表面
に生じたＳ１酸化物を除去する。After the heat treatment, the material to be heat treated is treated with an aqueous solution containing an acidic fluoride salt to remove S1 oxides generated on the surface of the material to be heat treated by annealing.
このような酸性フッ化塩としては、酸性フッ化アンモン
、酸性フッ化カリウム又は酸性フッ化すＩ・リウム等が
ある。例えは、酸性フッ化アンモンＮＨ４Ｆ・ＨＦは下
記化学式によりＳｉ酸化物Ｓ ｉ ０２と反応して化合
物になる。Examples of such acidic fluoride salts include acidic ammonium fluoride, acidic potassium fluoride, and acidic lithium fluoride. For example, acidic ammonium fluoride NH4F.HF reacts with Si oxide S i 02 to form a compound according to the following chemical formula.
Ｎ Ｈ４Ｆ Ｉ−Ｉ Ｐ ’Ｎ ）−１４Ｆ ＋ Ｉ
−Ｉ Ｆ（水中で酸性フッ化アンモンが分解）
Ｓ ｉ ０２−１−４ Ｉ（Ｆ−＞Ｓ ｉ Ｆ４−１−
２８２０（Ｓｉ酸化物と反応）
Ｓ ｉ ｒ”４−１−２Ｎ８４Ｆ→（ＮＨ４）２ＳｉＦ
６（錯塩の生成）
この場合に、常温において酸性フッ化塩ＭＦ！−（Ｆ（
但し、ＭはＮＨ３、Ｎａ、に等）の水溶液中に１０秒間
浸漬することによりＳｉ酸化物を完全に除去しようとす
ると、水溶液中の酸性フッ化塩の含有量を１０ｇ ／（
１以上にすることが必要である。N H4F I-I P'N )-14F + I
-IF (Acidic ammonium fluoride decomposes in water) S i 02-1-4 I (F->S i F4-1-
2820 (Reacts with Si oxide) Si r"4-1-2N84F→(NH4)2SiF
6 (Formation of complex salt) In this case, acidic fluoride salt MF! −(F(
However, if you try to completely remove Si oxide by immersing it in an aqueous solution of NH3, Na, etc. for 10 seconds, the content of acidic fluoride salt in the aqueous solution will be 10g/(
It is necessary to set it to 1 or more.
次に、本発明方法により実際にコイルを製造した実施例
についてその比較例と共に説明する。Next, examples in which coils were actually manufactured by the method of the present invention will be described together with comparative examples.
実施例１
銅合金コイルを、冷間圧延機により上り前圧延した後、
リワインダに巻き取る際に、Ｓｉ濃度が１．５乃至１０
重量％のＳｉオイルを灯油で薄めた液をコイル表面に塗
布した。次いで、バッチ式雰囲気ガス焼鈍炉にコイルを
装入し、５００°Ｃに２時間加熱して焼鈍した。次いで
、１乃至２重量％の酸性フッ化アンモンと、２０乃至３
０重重量の硫酸と、残部水とからなる混合水溶液により
コイルを酸洗することによって、コイル表面に被膜とし
て残存している５ｉ０２を除去した。その後、コイル表
面を研磨した後、上り圧延してコイル製品を製造した。Example 1 After pre-rolling a copper alloy coil with a cold rolling mill,
When winding up in a rewinder, the Si concentration is 1.5 to 10.
A solution prepared by diluting % by weight of Si oil with kerosene was applied to the coil surface. Next, the coil was placed in a batch atmosphere gas annealing furnace and annealed by heating to 500°C for 2 hours. Next, 1 to 2% by weight of acidic ammonium fluoride and 20 to 3% by weight of acidic ammonium fluoride.
By pickling the coil with a mixed aqueous solution consisting of 0 weight sulfuric acid and the remainder water, 5i02 remaining as a film on the coil surface was removed. Thereafter, the surface of the coil was polished and then rolled to produce a coil product.
下記第１表はＳｉオイル中のＳｉの濃度及び酸性フッ化
アンモン水溶液処理の有無と、焼鈍処理時の密着不良発
生の有無及びめっき加熱フクレ試験結果との関係を示す
。Table 1 below shows the relationship between the concentration of Si in Si oil, the presence or absence of acidic ammonium fluoride aqueous solution treatment, the occurrence of poor adhesion during annealing treatment, and the results of the plating heating blistering test.
この第１表から明らかなように、ＳｉオイルのＳｉ濃度
が２重量％以−ヒてあって、酸性フッ化アンモン処理を
施したものは、焼鈍時に密着不良は発生せず、めっき加
熱フクレも生しなかった。As is clear from Table 1, when the Si oil has a Si concentration of 2% by weight or more and is treated with acidic ammonium fluoride, poor adhesion does not occur during annealing, and no blistering occurs when the plating is heated. It didn't survive.
実施例２
厚さが３５１ｎｌＩｌであって、下記第２表に組成を示
す金属又は合金の条材の表面にＳｉ濃度が１．５及び５
０重量％のＳｉオイルを含む油液を滴下しつつ、この条
材をコイルに巻き取った。このコイルは幅か４７０＋ｎ
ｍ、重さが６トンであり、直径が５００ｍｍのスプール
に前記条材を巻き取ったものである。但し、条材の表面
粗さはＲｍａｘて １．０乃至１．３ノ１ｍである。Example 2 Si concentration was 1.5 and 5 on the surface of a metal or alloy strip having a thickness of 351nlIl and whose composition is shown in Table 2 below.
The strip was wound into a coil while an oil solution containing 0% by weight Si oil was dropped. The width of this coil is 470+n
The strip material was wound onto a spool with a diameter of 500 mm and a weight of 6 tons. However, the surface roughness of the strip material is Rmax of 1.0 to 1.3 m.
そして、この：１イルを下記第３表に示す焼鈍条件（加
熱温度、加熱時間）により焼鈍した。その結果、各材料
のコイルについて密着不良の発生の有無を調査し、その
結果を下記第３表に併せて示す。この第３表に示すよう
に、油中のＳｉ濃度が５重量％の場合には密着不良が全
く発生しなかった。Then, this :1 tile was annealed under the annealing conditions (heating temperature, heating time) shown in Table 3 below. As a result, the presence or absence of poor adhesion was investigated for the coils made of each material, and the results are also shown in Table 3 below. As shown in Table 3, no poor adhesion occurred when the Si concentration in the oil was 5% by weight.
この第２表に示す材料のコイルのうち、密着不良が発生
しなかったコイル（Ｓｉ濃度５重量％）について、その
コイルを巻きほときつつ、酸性フッ化アンモン（フッ化
水素アンモニウム）を下記第４表に示す組成で含有する
液温２０℃の水溶液中に通した。なお、一部の水溶液に
は硫酸を１０体積％て添加した。その結果、下記第４表
に条材表面の５ｉＯＸの除去状況を示すように、酸性フ
ッ化アンモンを１５ｇ／々含有する水溶液により処理し
た場合は、Ｓ １０ ｘを完全に除去することがてきた
。Among the coils made of the materials shown in Table 2, for the coils (Si concentration 5% by weight) that did not cause poor adhesion, the coils were unwound and acidic ammonium fluoride (ammonium hydrogen fluoride) was applied as described below. It was passed through an aqueous solution containing the composition shown in Table 4 and having a liquid temperature of 20°C. Note that 10% by volume of sulfuric acid was added to some of the aqueous solutions. As a result, as shown in Table 4 below showing the removal status of 5iOX on the surface of the strip, when treated with an aqueous solution containing 15 g/each of acidic ammonium fluoride, S 10 x was completely removed. .
第 ４ 表
このように、本実施例においては、３００乃至７００℃
で焼鈍する際のコイルの密着不良を防止することかでき
ると共に、密着防止材として生成させたＳｉ酸化物を容
易に除去することができる。Table 4 As shown, in this example, the temperature
It is possible to prevent poor adhesion of the coil during annealing, and it is also possible to easily remove Si oxide produced as an adhesion prevention material.
なお、本実施例は焼鈍炉としてＤＸガス炉を使用した場
合のものであるか、Ｃｕ又はＣｕ基合金を焼鈍する場合
は電気炉を使用してもよい。In this example, a DX gas furnace is used as the annealing furnace, or an electric furnace may be used when annealing Cu or a Cu-based alloy.
また、電気炉により焼鈍したコイルのＳｉ酸化物を除去
するためには、硫酸を含む水溶液を使用した方か有効に
Ｓｉ酸化物を除去することができる。これは、硫酸を含
む水溶液を使用することにより、Ｓｉ酸化物の除去と同
時に、焼鈍時に生成したＣｕの酸化物も併行して除去さ
れるからである。Further, in order to remove Si oxide from a coil annealed in an electric furnace, the Si oxide can be effectively removed by using an aqueous solution containing sulfuric acid. This is because by using an aqueous solution containing sulfuric acid, the Si oxide is removed and the Cu oxide generated during annealing is also removed simultaneously.
更にまた、本実施例は、酸性フッ化アンモン（ＮＨ４Ｆ
、ＨＦ）を使用したものであるが、硫酸を使用しない場
合は酸性フッ化ナトリウムＮａＦ・ＨＦ又は酸性フッ化
カリウムＫＦ ＨＦを使用してもよく、Ｓｉ酸化物の除
去については同様の効果を得ることができる。Furthermore, in this example, acidic ammonium fluoride (NH4F
, HF), but if sulfuric acid is not used, acidic sodium fluoride (NaF.HF) or acidic potassium fluoride (KF.HF) may be used, and the same effect can be obtained for the removal of Si oxide. be able to.
［発明の効果］
本発明によれば、所定濃度のＳｉを含有するＳｉオイル
を塗布した後熱処理するから、熱処理中にＳｉ酸化物が
生成し、このＳｉ酸化物により被熱処理材間の密着不良
を防止することかでき、歩留を著しく向上させることが
できる。[Effects of the Invention] According to the present invention, since heat treatment is performed after applying Si oil containing a predetermined concentration of Si, Si oxide is generated during the heat treatment, and this Si oxide causes poor adhesion between the materials to be heat treated. This can significantly improve the yield.
また、酸性フッ化塩水溶液により前記Ｓｉ酸化物を除去
するから、Ｓｉ酸化物を有しない清浄なコイルが得られ
る。従って、後工程の被熱処理材の研磨工程においては
、被熱処理材表面のＳｉ酸化物により研磨能力が損われ
ることなく研磨することができる。このため、被熱処理
材の表面の全域に亘って均一に表面欠陥を除去するのに
十分な研磨量を確保することができるから、後工程にお
けるめっき加熱フクレを防止することができると共に、
研磨速度を高めることができるので生産性が向上する。Furthermore, since the Si oxide is removed using the acidic fluoride salt aqueous solution, a clean coil free of Si oxide can be obtained. Therefore, in the subsequent step of polishing the heat-treated material, polishing can be performed without the polishing ability being impaired by the Si oxide on the surface of the heat-treated material. Therefore, it is possible to ensure a sufficient amount of polishing to uniformly remove surface defects over the entire surface of the material to be heat-treated, so it is possible to prevent blistering of the plating when heated in the subsequent process, and
Productivity is improved because the polishing rate can be increased.
Claims (10)
のＳｉを含有する油液を塗布し、次いで、前記被熱処理
材を熱処理した後、酸性フッ化塩を含有する水溶液によ
り被熱処理材の表面のＳｉ酸化物を除去することを特徴
とする金属又は合金の熱処理方法。(1) Apply an oil solution containing 2% by weight or more of Si to the surface of a metal or alloy material to be heat treated, then heat treat the material, and then heat treat it with an aqueous solution containing an acidic fluoride salt. A method for heat treating a metal or alloy, the method comprising removing Si oxide on the surface of the material.
ケル・鉄合金から選択されたものであることを特徴とす
る請求項１に記載の金属又は合金の熱処理方法。(2) The method for heat treating a metal or alloy according to claim 1, wherein the material to be heat treated is selected from copper, copper alloy, nickel, and nickel/iron alloy.
を特徴とする請求項２に記載の金属又は合金の熱処理方
法。(3) The method for heat treating a metal or alloy according to claim 2, wherein the material to be heat treated is a linear or plate-shaped strip.
を特徴とする請求項３に記載の金属又は合金の熱処理方
法。(4) The method for heat treating a metal or alloy according to claim 3, wherein the material to be heat treated is wound into a coil.
とを特徴とする請求項１に記載の金属又は合金の熱処理
方法。(5) The method for heat treating a metal or alloy according to claim 1, wherein the Si content of the oil liquid is 10% by weight or less.
以上の酸性フッ化塩を含有することを特徴とする請求項
１に記載の金属又は合金の熱処理方法。(6) The aqueous solution containing the acidic fluoride salt is 10 g/l.
The method for heat treating a metal or alloy according to claim 1, characterized in that the method contains the above acidic fluoride salt.
とを特徴とする請求項６に記載の金属又は合金の熱処理
方法。(7) The method for heat treating a metal or alloy according to claim 6, wherein the acidic fluoride salt is acidic ammonium fluoride.
ことを特徴とする請求項６に記載の金属又は合金の熱処
理方法。(8) The method for heat treating a metal or alloy according to claim 6, wherein the acidic fluoride salt is acidic sodium fluoride.
とを特徴とする請求項６に記載の金属又は合金の熱処理
方法。(9) The method for heat treating a metal or alloy according to claim 6, wherein the acidic fluoride salt is acidic potassium fluoride.
を含有する油液を塗布し、３００乃至７００℃の温度で
焼鈍した後、この焼鈍材の表面に生成したＳｉ酸化物を
１０ｇ／ｌ以上の酸性フッ化塩を含有する水溶液により
除去することを特徴とする金属又は合金の熱処理方法。(10) 2% by weight or more of Si in the coiled heat-treated material
After applying an oil solution containing 300 to 700 ° C. and annealing at a temperature of 300 to 700 ° C., the Si oxide generated on the surface of the annealed material is removed with an aqueous solution containing 10 g / l or more of acidic fluoride salt. Characteristic heat treatment method for metals or alloys.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63020884A JP2578462B2 (en) | 1988-01-29 | 1988-01-29 | Heat treatment method for metal or alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63020884A JP2578462B2 (en) | 1988-01-29 | 1988-01-29 | Heat treatment method for metal or alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH028352A true JPH028352A (en) | 1990-01-11 |
| JP2578462B2 JP2578462B2 (en) | 1997-02-05 |
Family
ID=12039624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63020884A Expired - Fee Related JP2578462B2 (en) | 1988-01-29 | 1988-01-29 | Heat treatment method for metal or alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2578462B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5798680A (en) * | 1980-12-12 | 1982-06-18 | Sanshin Kagaku Kogyo Kk | Corrosion inhibiting agent for stainless steel |
| JPS6086242A (en) * | 1983-10-19 | 1985-05-15 | Kawasaki Steel Corp | Single surface coated one directional silicon steel plate and preparation thereof |
| JPS6148584A (en) * | 1984-08-10 | 1986-03-10 | C Uyemura & Co Ltd | Scale remover |
| JPS6169977A (en) * | 1984-09-12 | 1986-04-10 | Kawasaki Steel Corp | Production of electrical steel sheet having film to prevent seizure of steel sheet during strain relief annealing |
-
1988
- 1988-01-29 JP JP63020884A patent/JP2578462B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5798680A (en) * | 1980-12-12 | 1982-06-18 | Sanshin Kagaku Kogyo Kk | Corrosion inhibiting agent for stainless steel |
| JPS6086242A (en) * | 1983-10-19 | 1985-05-15 | Kawasaki Steel Corp | Single surface coated one directional silicon steel plate and preparation thereof |
| JPS6148584A (en) * | 1984-08-10 | 1986-03-10 | C Uyemura & Co Ltd | Scale remover |
| JPS6169977A (en) * | 1984-09-12 | 1986-04-10 | Kawasaki Steel Corp | Production of electrical steel sheet having film to prevent seizure of steel sheet during strain relief annealing |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2578462B2 (en) | 1997-02-05 |
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