JPS6376896A - Production of surface-treated steel sheet having excellent seam weldability and corrosion resistance - Google Patents
Production of surface-treated steel sheet having excellent seam weldability and corrosion resistanceInfo
- Publication number
- JPS6376896A JPS6376896A JP61220521A JP22052186A JPS6376896A JP S6376896 A JPS6376896 A JP S6376896A JP 61220521 A JP61220521 A JP 61220521A JP 22052186 A JP22052186 A JP 22052186A JP S6376896 A JPS6376896 A JP S6376896A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- steel sheet
- distribution
- corrosion resistance
- layer
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 42
- 239000010959 steel Substances 0.000 title claims abstract description 42
- 238000005260 corrosion Methods 0.000 title claims abstract description 18
- 230000007797 corrosion Effects 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000007747 plating Methods 0.000 claims abstract description 96
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004381 surface treatment Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 16
- 239000000956 alloy Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000005275 alloying Methods 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 238000004532 chromating Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 58
- 238000009826 distribution Methods 0.000 description 42
- 238000000034 method Methods 0.000 description 18
- 229910017091 Fe-Sn Inorganic materials 0.000 description 9
- 229910017142 Fe—Sn Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000003466 welding Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910001128 Sn alloy Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000009827 uniform distribution Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- -1 aluminum chloride Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はシーム溶接性、耐食性に優れた表面処理鋼板の
製造方法に関するもので、特に缶胴をシーム溶接法で接
合する金属容器用素材としての利用価値が大きい。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing a surface-treated steel sheet with excellent seam weldability and corrosion resistance, and particularly as a material for metal containers in which can bodies are joined by seam welding. has great utility value.
従来電解Ｓｎメッキ鋼板（以下ブリキと称す）、電解ク
ロム酸処理鋼板（以下ＴＦＳ−ＣＴと称す）、又一部に
電解Ｎ１メッキ鋼板（以下ＴＦＳ−ＮＴ ）が知られて
おり、３ピ一ス缶製缶法としてそれぞれハンダ接合、接
着接合、シーム溶接等によって製缶されてきた。Conventionally, electrolytic Sn-plated steel sheets (hereinafter referred to as tinplate), electrolytic chromic acid treated steel sheets (hereinafter referred to as TFS-CT), and some electrolytic N1-plated steel sheets (hereinafter referred to as TFS-NT) are known. Cans have been manufactured by solder joining, adhesive joining, seam welding, etc. as can manufacturing methods.
ブリキは従来製缶用素材として最も広く使用されてきた
が、製缶コスト節減の中でＳｎ”が薄メツキ化され、製
缶法も従来のハンダ付に替シシーム溶接法が採用され始
めたが、Ｓｎメッキ量が片面当９０６２０μｍ厚以下に
なる厚塗下耐食性、シーム溶接性共劣化し、又シーム溶
接缶用素材として一部で使用されているＴＦＳ−ＮＴ
（Ｎ１メッキ鋼板）はシーム溶接性能が実用可能な範囲
ではあるが十分ではなく、又塗装耐食性も強酸性食品等
腐食性が高い内容物の場合不十分であることから、低コ
ストでしかも塗装耐食性、シーム溶接性に優れた製缶用
表面処理銅板が要望されている。Tinplate has traditionally been the most widely used material for can manufacturing, but in order to reduce can manufacturing costs, Sn'' has been made thinner, and seam welding has begun to be used instead of the traditional soldering method for can manufacturing. , TFS-NT, which has a Sn plating amount of less than 90620 μm per side, deteriorates both corrosion resistance and seam weldability, and is also used in some parts as a material for seam welded cans.
(N1 plated steel plate) has seam welding performance that is within a practical range but is not sufficient, and paint corrosion resistance is also insufficient for highly corrosive contents such as strongly acidic foods, so it is low cost and has good paint corrosion resistance. There is a demand for a surface-treated copper plate for can making that has excellent seam weldability.
これに対し本発明者は特開昭６０−７５５８６号等で鋼
板上に微量Ｎｉメッキ被覆を行った後Ｓｎメッキする手
法を発明し、加熱時に形成されるＦｅ−Ｓｎ合金層が微
量のＮｉによって緻密化することから耐食性が向上し、
そして加熱時のＦｅ−Ｓｎ合金化反応が抑制されること
で、シーム溶接性も向上することを知見した。さらに本
発明者はこれらシーム溶接缶用素材としての特性には表
面に存在する金属Ｓｎの分布状態が影響し、金属Ｓｎの
分布状態が均一であるより不均一な凹凸分布を有する方
が特性が良好となることも見い出し、特願昭６１−１６
４７１号にて既に出願した。In response to this, the present inventor invented a method in which a small amount of Ni plating is applied to a steel plate and then Sn plating is applied in JP-A No. 60-75586, etc., and the Fe-Sn alloy layer formed during heating is Corrosion resistance improves due to densification,
It has also been found that seam weldability is also improved by suppressing the Fe-Sn alloying reaction during heating. Furthermore, the inventors have found that the characteristics of these materials for seam-welded cans are affected by the distribution state of metal Sn present on the surface, and that the characteristics are better when the distribution state of metal Sn is uneven and uneven than when the distribution state is uniform. It was also found that it was good, and a patent application was filed in 1986-16.
I have already filed an application under No. 471.
これらは確かに従来の単純な薄Ｓｎメッキ鋼板と比較し
て、シーム溶接性等に効果を有するが、得られる特性が
一定でなくバラツキを持つため、シーム溶接性、耐食性
等特性が安定して良好な築材が望まれていた。このため
本発明者は鋼板上に微量のＮ１メッキ処理を施した後、
Ｓｎメッキを重層被覆する鋼板の特性をさらに改善すべ
くその製造条件の詳細を鋭意検討し、本発明に到達した
のである。These do have an effect on seam weldability, etc. compared to conventional simple thin Sn-plated steel sheets, but the properties obtained are not constant and vary, so seam weldability, corrosion resistance, etc. are not stable. Good construction materials were desired. For this reason, the inventor applied a small amount of N1 plating on the steel plate, and
In order to further improve the characteristics of the steel plate coated with Sn plating in multiple layers, the present invention was achieved by intensively studying the details of the manufacturing conditions.
〔問題点を解決するための手段・作用〕本発明表面処理
鋼板は鋼板底面に片面当９２〜１００ ｍｌ／ｍ２のＮ
１を不連続な島状に被覆した後、引き続き片面当’）
２００〜２０００ ｍｇ／ｍ２のＳｎメッキを施こし、
さらにＳｎメッキ層融点以上での加熱処理を施こした後
、電解クロメート処理を施すものであり、本発明の一イ
ンドは、鋼板表面に形成する片面当シ２〜１００ｍｇ７
ｍ２のＮ１層を不均一な島状に被覆する点にある。この
ように本発明はＮｉを下地メッキする薄Ｓｎメッキ鋼板
の最適な製造方法を提供するものであり、本発明と同量
のＮ１を連続な均一層として被覆する場合と比較し、シ
ーム溶接性、耐食性等特性が安定して良好となる。本発
明？さらに詳しく説明する。[Means/effects for solving the problem] The surface-treated steel sheet of the present invention is coated with 92 to 100 ml/m2 of N per one side on the bottom surface of the steel sheet.
After coating 1 in a discontinuous island shape, continue to apply on one side')
Apply Sn plating of 200 to 2000 mg/m2,
Furthermore, after heat treatment is performed at a temperature higher than the melting point of the Sn plating layer, electrolytic chromate treatment is performed.
The point is that the N1 layer of m2 is coated in a non-uniform island shape. As described above, the present invention provides an optimal manufacturing method for a thin Sn-plated steel sheet with Ni underplating, and has improved seam weldability compared to the case of coating the same amount of N1 as a continuous uniform layer as in the present invention. , properties such as corrosion resistance become stable and good. Invention? I will explain in more detail.
溶接缶用素材として使用される片面当り ２００〜２０
００ｍｇ／ｍ２のＳｎメッキ鋼板に要求される特性で最
も重要なのは、シーム溶接性でらシ、そして塗膜下目等
の耐食性である。これら特性には、Ｆｅ、ｙ’ｓｎ界面
に形成されるＦｅ−Ｓｎ合金層又金属Ｓｎ層等の構造、
形態、分布が大きく影響することが知られでいる。この
ためＳｎメッキを施す前に片面当り２〜１００〜７ｍ２
のＮｉメッキ処理を施す手法が考案され、このＮｉメッ
キ前処理によってＦｅ／Ｓｎ界面に形成されるＦｅ−Ｓ
ｎ合金層が緻密化し、耐食性の向上、さらに塗装焼付等
加熱工程でのＦｅ−Ｓｎ合金化反応が抑制されることで
シーム溶接性向上に寄与する金属Ｓｎの確保が同−Ｓｎ
メッキ層の場合に容易となるのである。200 to 20 per side used as material for welded cans
The most important characteristics required for a 00 mg/m2 Sn-plated steel sheet are seam weldability and corrosion resistance of the underside of the coating. These characteristics include the structure of the Fe-Sn alloy layer or metal Sn layer formed at the Fe, y'sn interface,
It is known that morphology and distribution have a large influence. For this reason, before applying Sn plating, 2 to 100 to 7 m2 per side
A method of performing Ni plating treatment was devised, and the Fe-S formed at the Fe/Sn interface by this Ni plating pretreatment was devised.
The n-alloy layer becomes denser, improving corrosion resistance, and suppressing the Fe-Sn alloying reaction during heating processes such as paint baking, thereby securing the metal Sn that contributes to improving seam weldability.
This becomes easy in the case of a plated layer.
このように溶接缶用薄Ｓｎメッキ鋼板の特性はＮｉメッ
キ前処理によって確かに向上し、さらに本発明者が％願
昭６０−２４７４９号、特願昭６１−１６４７１号で既
に出願したようにＳｎメッキ層の分布状態を不均一な凹
凸分布とすることで特性はより向上する。そしてこのよ
うなＳｎメッキ層の凹凸分布状態を安定して得るため藤
本らは「鉄と鋼Ｊ （Ｖｏｌ ７２． Ａ５５４４５）
でＮ１メッキ処理前にアルカリ浴中で陽極処理を施す必
要があることを報告し、さらに一般的にはＳｎメッキ後
のフラックス処理条件の影響も大きいことが知られてい
る。しかしこのような対策を取っても安定した特性を得
ることはできず、本発明者は鋼板上に施こす微量のＮｉ
メッキ処理に着目して研究を行ない、Ｎｉの分布状態と
不連続な島状とすることで、溶接缶用素材としての特性
を安定して満足できることを見い出したのである。In this way, the properties of thin Sn-plated steel sheets for welded cans are certainly improved by Ni plating pretreatment, and furthermore, as the present inventor has already filed in Patent Application No. 60-24749 and Japanese Patent Application No. 61-16471, Sn Characteristics are further improved by making the distribution state of the plating layer uneven. In order to stably obtain such an uneven distribution state of the Sn plating layer, Fujimoto et al.
reported that it is necessary to perform anodization in an alkaline bath before N1 plating, and it is generally known that the flux treatment conditions after Sn plating have a large influence. However, even if such measures were taken, stable characteristics could not be obtained, and the inventor decided to
They conducted research focusing on the plating process and found that by making the Ni distribution state discontinuous and island-like, the properties as a material for welded cans could be stably satisfied.
シーム溶接缶用薄Ｓｎメッキ鋼板に要求される特性は、
シーム溶接性、耐食性であるが、前述したようにこれら
特性には緻密で耐食性に優れたＦｅ−Ｓｎ合金屓の形成
及び本発明者が特願昭６１−１６４７１号で既に知見し
たような凹凸分布と有するＳｎメッキ層形態の影響が大
きく、これにはＮ１メッキ処理時のＮｉ分布状態が大き
く影響することを本発明者は知見した。鋼板上に片面当
り２〜１００ ｍｇ７ｍ のＮｉを被覆する際、この
Ｎｉを均一に連続して被覆する場合と不均一な島状に被
覆する場合では、Ｆｅ／Ｓｎ’界面に形成されるＦｅ−
Ｓｎ合金層の形成状況そしてＳｎメッキ層の分布状況が
大きく異なｐ、Ｎｉを不均一な島状に分布させると緻密
で耐食性に優れたＦａ−Ｓｎ合金層、及び凹凸分布を持
つＳｎメッキ層が、製造工程中のａｎメッキ処理条件、
Ｓｎメッキ後の溶融加熱処理条件等の若干の変動が有り
ても安定して形成され、その結果シーム溶接缶用素材と
しての特性が安定して優れたものになる。次にこのＮｉ
メッキ層の不均一な島状分布状態及びＮｉ分布状態がＳ
ｎメッキ層の凹凸分布等に大きく影響する理由について
さらに詳しく説明する。The characteristics required for thin Sn-plated steel sheets for seam welded cans are:
Seam weldability and corrosion resistance are important, but as mentioned above, these characteristics include the formation of a dense Fe-Sn alloy layer with excellent corrosion resistance and the unevenness distribution as already discovered by the inventor in Japanese Patent Application No. 16471/1983. The inventor of the present invention found that the form of the Sn plating layer has a large influence on the shape of the Sn plating layer, and that the state of Ni distribution during the N1 plating treatment has a large effect on this. When coating a steel plate with 2 to 100 mg/7m of Ni per side, the Fe-
The formation conditions of the Sn alloy layer and the distribution conditions of the Sn plating layer are greatly different. When p and Ni are distributed in an uneven island shape, a dense Fa-Sn alloy layer with excellent corrosion resistance and a Sn plating layer with an uneven distribution are formed. , an plating treatment conditions during the manufacturing process,
Even if there are slight variations in the melting heat treatment conditions after Sn plating, it is stably formed, and as a result, the properties as a material for seam welded cans are stable and excellent. Next, this Ni
The non-uniform island-like distribution state of the plating layer and the Ni distribution state are S
The reason why this greatly affects the unevenness distribution of the n-plated layer will be explained in more detail.
Ｎｉメッキ層の不均一な島状分布であるが、これには様
々な分布状況が有シ、その例を第１図。Although the Ni plating layer has a non-uniform island-like distribution, there are various distribution situations, examples of which are shown in Fig. 1.
第２図に示す。第１図は素地鋼板１上に連続したＮ１層
を有するが、その分布が不均一な凹凸状をなす場合であ
シ、この場合Ｎ１層凹部の最低厚をｈｍｉｎ及び凸部の
最大厚を一８Ｘとした時ｈｍａＸ≧”ｍ１ｎの関係を持
つことが必須となり’ ｈｍａ工≧０．００２μｍの範
囲を満足する必要がある。さらにＮｉメッキ厚が０．０
０１μｍ以上である領域が鋼板表面の面積率にして少な
くとも９０チ以下であることが本発明の要件であシ、又
下限は特に規定しないが、１０チ以上が望ましい。これ
はこの範囲を満足しなければ、本発明の意義が失われ、
例えば最適なＳｎメッキ層凹凸分布を得ることが困難と
なるからである。Shown in Figure 2. Fig. 1 shows a case where a continuous N1 layer is formed on the base steel plate 1, but its distribution is uneven, and in this case, the minimum thickness of the concave portion of the N1 layer is hmin, and the maximum thickness of the convex portion is equal to When set to 8X, it is essential to have the relationship hmaX≧"m1n, and it is necessary to satisfy the range of hmaX≧0.002μm. Furthermore, the Ni plating thickness is 0.0
It is a requirement of the present invention that the area having a diameter of 0.01 μm or more is at least 90 inches or less in terms of area ratio of the surface of the steel sheet, and although the lower limit is not particularly specified, it is preferably 10 inches or more. If this range is not satisfied, the meaning of the present invention will be lost,
This is because, for example, it becomes difficult to obtain an optimal Sn plating layer unevenness distribution.
次に第２図はＮｉ層が完全に不連続とな、９ 、Ｎｉが
付着せず素地鋼板１０表面が部分的に露出している場合
であり、この場合素地鋼板１の露出部には酸化Ｆ・皮膜
が存在していても良い。この様にＮｉ層が完全に不連続
な島状を呈する時にもＮ１が付着している部分の最大Ｎ
ｉ厚ｈｍ□は０．００２μｍ以上である必要があシ、又
Ｎ１の鋼板表面被覆率は鋼板表面面積率として少なくと
も９０チ以下であることが好ましい。又下限は特に限定
しないが、１０チ以上であることが望ましい。限定理由
は第１図の場合と全く同様である。ここではＮｉメッキ
層の不均一な島状分布例として以上の２例について述べ
たが、第１図の例と第２図の例が混在する場合等様々な
分布状態が考えられ、一般的な概念である不均一な島状
のＮ１メッキ分布を持つ場合全てが本発明範囲に含まれ
るものである。なおこのようなＮ１の不均一な島状分布
状態はＥＰＭＡ （Ｅｌｅｃｔｒｏｎ Ｐｒｏｂｅｄ
Ｍｉｃｒ。Next, Fig. 2 shows a case where the Ni layer is completely discontinuous, 9, and the surface of the base steel plate 10 is partially exposed without any Ni adhering.In this case, the exposed portion of the base steel plate 1 has oxidized F. A film may be present. In this way, even when the Ni layer has a completely discontinuous island shape, the maximum N of the part where N1 is attached is
The i thickness hm□ must be 0.002 μm or more, and the steel plate surface coverage ratio of N1 is preferably at least 90 inches or less as a steel plate surface area ratio. The lower limit is not particularly limited, but is preferably 10 inches or more. The reason for the limitation is exactly the same as in the case of FIG. Here, the above two examples of non-uniform island-like distribution of the Ni plating layer were described, but various distribution states can be considered, such as a case where the example in Figure 1 and the example in Figure 2 coexist. All cases having a conceptually non-uniform island-like N1 plating distribution are included within the scope of the present invention. It should be noted that this non-uniform island-like distribution state of N1 is known as EPMA (Electron Probed
Micr.
Ａｎａｌｙｓｅｒ又はＡＥＳ （Ａｕｇｅｒ Ｅｌｅｃ
ｔｒｏｎＳｐ＠ｃｔｒｏｓｃｏｐｙ ）等の手法で確認
できる。そしてこのような不均一な島状Ｎｉメッキ分布
とすることで、シーム溶接缶用素材としての薄Ｓｎメッ
キ銅板の特性が向上する理由は次のように考えられる。Analyser or AES (Auger Elec
This can be confirmed using methods such as tronSp@ctroscopy). The reason why such a non-uniform island-like Ni plating distribution improves the properties of the thin Sn-plated copper plate as a material for seam-welded cans is considered as follows.
すなわちこのよりなＮ１メッキ前処理層分有する薄Ｓｎ
メッキ鋼板の製造プロセスを考え、それに伴うメッキ断
面構造の変化をモデル図で示すと第３図に示す如くであ
る。第３図はＮｉメッキ層が本発明例の不均一島状分布
を呈する場合（この場合第２図で示した例）及び従来の
連続した均一分布を持つ場合両者を比較して示すが、本
発明のようにＮｉが、不均一な島状に存在する場合は、
Ｎｉが厚く存在する部分及びＮ１が少ないが、もしくは
存在しない部分でのＳｎメッキ層溶融処理に於けるＦ・
−Ｓｎ合金層（この場合Ｆ＠−Ｎｉ−８ｎ三元合金とな
る）の生成挙動が異なり、Ｎ１が厚く存在する部分では
合金化スピードが速く、Ｆ・−ａｎ合金生成が速いと共
に合金量も多くなるのに対し、Ｎｉが少ないか、もしく
は存在しない部分ではＦｅ−Ｓｎ合金生成が遅れ、合金
量が少なくなるため結果として生成したＦｅ−Ｓｎ合金
層の分布状態は最初にＮｉが島状に存在した分布状況と
対応した凹凸分布を持つようになる。そして一般に学会
等で公知な如く、Ｆｅ−Ｓｎ合金上とＦｅ−Ｓｎ合金層
が薄いか、もしくは存在しない部分の間で溶融したＳｎ
の濡れ性が異なるため、Ｓｎメッキ層溶融加熱処理の初
期の段階で溶融Ｓｎの濡れ性の相違に基き、Ｓｎメッキ
層も第３図のに示すように、最初にＮｉが島状に存在し
た分布状況と対応した凹凸分布を安定して持つようにな
るのである。In other words, this thin Sn layer with a thicker N1 plating pretreatment layer
Considering the manufacturing process of plated steel sheets, the changes in the plated cross-sectional structure accompanying the process are illustrated in a model diagram as shown in FIG. 3. FIG. 3 shows a comparison between a case where the Ni plating layer exhibits a non-uniform island-like distribution according to the present invention (in this case, the example shown in FIG. 2) and a case where the Ni plating layer has a conventional continuous uniform distribution. When Ni exists in a non-uniform island shape as in the invention,
F・ during Sn plating layer melting treatment in areas where Ni is thick and areas where N1 is small or absent.
The formation behavior of the -Sn alloy layer (in this case, it becomes a F@-Ni-8n ternary alloy) is different, and the alloying speed is faster in the part where N1 is thicker, and the F・-an alloy formation is faster and the amount of alloy is also smaller. On the other hand, in areas where there is little or no Ni, Fe-Sn alloy formation is delayed, and the amount of alloy decreases, so the distribution state of the resulting Fe-Sn alloy layer is such that Ni initially forms islands. It comes to have an uneven distribution that corresponds to the existing distribution situation. As is generally known in academic societies, Sn melts between the Fe-Sn alloy and the areas where the Fe-Sn alloy layer is thin or absent.
Due to the difference in the wettability of molten Sn at the initial stage of the Sn plating layer melting heat treatment, the Sn plating layer also initially had Ni present in the form of islands, as shown in Figure 3. This results in a stable unevenness distribution that corresponds to the distribution situation.
これに対し、Ｎｉを連続な均一分布となるよう被覆した
場合は鋼板表面で均一にＦ＠−Ｓｎ合金が生成し成長す
るため、鋼板表面の局部的な溶融Ｓｎ濡れ性の差が小さ
いため、Ｓｎメッキ層溶融加熱処理終了後のＳｎメッキ
層分布状態は基本的に第３図■に示すような均一な分布
を呈し、Ｓｎメッキ処理後のフラックス牽伸の変化で、
第３図のに示すような凹凸分布を有するＳｎメッキ層に
なったシ、又第３図の、■の状態が混存するよりなＳｎ
メッキ層となったりして、結果的にシーム溶接性、耐食
性等特性が不安定になるのである。On the other hand, when Ni is coated with a continuous and uniform distribution, F@-Sn alloy forms and grows uniformly on the steel plate surface, so the difference in local molten Sn wettability on the steel plate surface is small. The distribution state of the Sn plating layer after the Sn plating layer melting heat treatment basically exhibits a uniform distribution as shown in Figure 3 (■), and due to the change in flux drafting after the Sn plating treatment,
The Sn plating layer has a roughness distribution as shown in Fig. 3, and the Sn plating layer has the unevenness distribution as shown in Fig. 3.
As a result, properties such as seam weldability and corrosion resistance become unstable.
このようにＮｉメッキ層の分布状態が最終製品としての
Ｆ＠−Ｓｎ合金層、及びＳｎメッキ層の構造に大きく影
響することが、本発明者の研究によって判明し、Ｎｉを
不均一な島状分布とすることで初めて溶接缶用素材とし
ての薄Ｓｎメッキ鋼板の特性を安定して向上させること
が可能となったものである。The inventor's research has revealed that the distribution state of the Ni plating layer greatly affects the structure of the F@-Sn alloy layer and the Sn plating layer as the final product. This distribution makes it possible for the first time to stably improve the properties of a thin Sn-plated steel sheet as a material for welded cans.
引き続き本発明製造方法について限定理由と共にさらに
説明する。本発明は通常の方法で表面清浄化した鋼板を
メッキ原板として使用するが、その使用する原板、又表
面清浄化処理について何ら限定するものでなく、底面清
浄化時に硫酸等の酸洗処理浴、又力性ソーダ等脱脂処理
浴中でＩＰＩ極電解する手法も含まれる。引き続き片面
当シ２〜１００■／ｒｎ のＮｉを前述したような不
均一な島状に被覆するが、Ｎ１メッキ処理浴としては一
般的なワット浴等の硫酸浴が使用でき、処理浴組成、電
解電流密度等電解条件の調整で本発明のポイントとなる
不均一島状のＮｉメッキ分布を得ることができる。なお
本発明にはこのようなＮ１メッキ分布を得られる手法で
あれば、電気メツキ法によらず、無電解メッキ法等の手
法も当然包含されるものであり、又Ｎｉメッキ後に陽極
電解処理を施す場合も含まれる。Subsequently, the manufacturing method of the present invention will be further explained along with the reasons for the limitations. In the present invention, a steel plate whose surface has been cleaned by a conventional method is used as a plating base plate, but there are no limitations on the base plate used or the surface cleaning treatment. It also includes a method of IPI electrode electrolysis in a degreasing treatment bath such as hydric soda. Subsequently, one side is coated with Ni at a rate of 2 to 100 μ/rn in a non-uniform island shape as described above. As the N1 plating bath, a general sulfuric acid bath such as a Watts bath can be used, and the treatment bath composition is By adjusting electrolytic conditions such as electrolytic current density, it is possible to obtain a non-uniform island-like Ni plating distribution, which is the key point of the present invention. Note that the present invention naturally includes methods such as electroless plating other than electroplating as long as such a N1 plating distribution can be obtained, and also includes anodic electrolytic treatment after Ni plating. This also includes cases where it is applied.
また、ＮＩメッキ後加熱処理により鋼中に拡散させても
よい。ここで平均したＮｉメッキ量を片面当り２〜１０
０■／ｍ２と限定したのはＮｉ ｉがこれ以上に増加す
るとＮｉメッキ分布分不均−な島状とすることが困難と
なシ、特性が低下するからでち）、又Ｎ１量の下限は平
均被覆量として片面当り２ｍｙ、Ｚｎ とする。これ
はＮ１メッキ前処理によるＦｅ−４ｎ合金層の緻密化等
耐食性向上効果等を推持するためであシ片面当シ５ｍｇ
／ｍ２以上が好ましい。なおＮｉ中にＺｎ、Ｆｅ、Ｐ、
Ｂの一種又は二種以上が重量％として２０％以下含有し
た場合も本発明に含むものとする。Alternatively, it may be diffused into steel by heat treatment after NI plating. Here, the average Ni plating amount is 2 to 10 per side.
The reason why it is limited to 0/m2 is because if Ni increases more than this, it becomes difficult to make the Ni plating distribution into an uneven island shape, and the properties deteriorate), and the lower limit of the N1 amount. The average coating amount of Zn is 2 my per side. This is to maintain the effect of improving corrosion resistance such as densification of the Fe-4n alloy layer due to N1 plating pre-treatment.
/m2 or more is preferable. In addition, Zn, Fe, P,
The present invention also includes cases where one or more B types are contained in an amount of 20% or less by weight.
次にＳｎメッキ被覆を施こすが、手法としては電気メツ
キ法が最も合理的であシ、通常のＳｎメッキ処理法がそ
のま−ま適用できる。Ｓｎメッキ量として片面尚シ２０
０〜２０００ ｍｇ７ｍ２と限定したのはＳｎ量が限定
値以上に増大しても本発明の効果は飽和し、コストアッ
プとなるからであシ、又下限はシーム溶接性、耐食性の
面から片面当シ２００■／ｍ２以上とした。なおＳｎメ
ッキ量は鋼板の表／裏で相違する差厚メッキとしても良
い。Next, a Sn plating coating is applied, and the most rational method is electroplating, and a normal Sn plating method can be applied as is. The amount of Sn plating is 20 on one side.
The reason why the Sn amount is limited to 0 to 2000 mg7m2 is that even if the Sn amount increases beyond the limit value, the effect of the present invention will be saturated and the cost will increase. 200 μ/m2 or more. Note that the amount of Sn plating may be plated with a different thickness on the front and back sides of the steel plate.
本発明はＳｎメッキ後水洗しそのまま、又は一般に使用
されるフェノールスルフォン酸を主体とするフラックス
又は塩化アルモニウム等塩化物を主体とする７ラツクス
等に浸漬し、乾燥後Ｓｎメッキ層溶融加熱処理が施され
る。７ラツクス処理を施すか又は施さず直接Ｓｎメッキ
層溶融加熱処理を施すかは状況に応じて適時選択でき、
又フラックス浴濃度を通常のぶシき製造時にｔ史用され
る濃度の１／２〜１／３に調整して実施することもでき
る。Ｓｎメッキ層溶融加熱処理の方法は一般的な抵抗加
熱法、高周波誘導加熱法が利用でき、その雰凹気として
不活性ガス中で実施することもできる。又このＳｎメッ
キ層溶融加熱時にＦｅ／Ｓｎ界面に形成されるＦｅ−Ｓ
ｎ合金の平均被覆量は合金中のＳｎ量として被覆する全
Ｓｎｉの１／３程度以下に抑制することが望ましい。In the present invention, after Sn plating, the Sn plating layer is washed with water and then immersed in a commonly used flux mainly composed of phenolsulfonic acid or 7 lux mainly composed of chlorides such as aluminum chloride, dried, and then subjected to heat treatment to melt the Sn plating layer. be done. Depending on the situation, you can choose whether to apply the 7lux treatment or not and directly apply the melting heat treatment to the Sn plating layer.
It is also possible to adjust the concentration of the flux bath to 1/2 to 1/3 of the concentration used in the production of ordinary bushings. For the Sn plating layer melting heat treatment, a general resistance heating method or a high frequency induction heating method can be used, and it can also be carried out in an inert gas atmosphere. Also, Fe-S formed at the Fe/Sn interface during melting and heating of this Sn plating layer.
It is desirable that the average coating amount of the n-alloy is suppressed to about 1/3 or less of the total Sn to be coated as the amount of Sn in the alloy.
本発明による不均一島状Ｎｉメッキを施し、引き続きＳ
ｎメッキ処理、Ｓｎメッキ層溶融加熱処理を飾すことで
、薄Ｓｎメッキ鋼板のメッキ層状態と溶接缶用素材とし
て最も好ましい状態にコントロールすることが可能とな
シ、本発明者が既に出願した特願昭６１−１６４７１号
に示す状態を容易に安定して保つことが可能となる。Apply non-uniform island-like Ni plating according to the present invention, and then apply S
The present inventor has already filed an application that it is possible to control the state of the plating layer of a thin Sn-plated steel sheet to the most preferable state as a material for welded cans by performing n plating treatment and Sn plating layer melting heat treatment. It becomes possible to easily and stably maintain the state shown in Japanese Patent Application No. 61-16471.
本発明は塗装後使用されることが多く、最表面に不動態
化処理としてクロメート処理２施すが、これはＴＦＳ−
ＣＴのクロメート処理として工業的に実施されている方
法で十分であシ、一般にはアニオンを添加しない無水ク
ロム酸浴中、又は硫酸イオン、フッ素イオン等を少量添
加した無水クロム酸浴中等でのカソード還元処理が適用
できる。又本発明に於いても学会等で公知でちるクロメ
ート被覆層中の共析アニオンを低減、除去する各種手法
を適用可能であることは言うまでもない。すなわち本発
明のクロメート被覆はクロム水利酸化物のみで構成され
てもよくまた金属クロムとクロム水利酸化物から構成さ
れてもよい。このクロメート被覆量としては金属クロム
換算で３〜３０ｍｇ７ｍ２の範囲が好ましい。The present invention is often used after painting, and chromate treatment 2 is applied to the outermost surface as passivation treatment, but this is TFS-
An industrially practiced method for chromate treatment of CT is sufficient; generally, the cathode is treated in an anhydrous chromic acid bath without the addition of anions, or in an anhydrous chromic acid bath to which a small amount of sulfate ions, fluorine ions, etc. are added. Reduction processing can be applied. It goes without saying that various methods for reducing and removing eutectoid anions in the chromate coating layer, which are known in academic societies, can also be applied to the present invention. That is, the chromate coating of the present invention may be composed only of chromium hydration oxide, or may be composed of metallic chromium and chromium hydration oxide. The amount of chromate coated is preferably in the range of 3 to 30 mg7m2 in terms of metallic chromium.
その理由は、３■／ｍ２以下では耐食性、塗料の密着性
が不十分であり、また３ ０ ｍｇ７ｍ 以上では溶接
性が低下するからである。The reason for this is that if it is less than 3 cm/m2, corrosion resistance and paint adhesion will be insufficient, and if it is more than 30 mg/m2, weldability will deteriorate.
次に本発明の実施例について説明する。 Next, examples of the present invention will be described.
実施例１
通常の条件で表面清浄化した鋼板両面に■に示す処理浴
中で各種条件にて片面当シ平均量として片面当９２〜１
２０■／ｍ２のＮｉメッキ処理を施し、処理浴組成、−
１さらに電解電流密度等電解条件を変更することで、Ｎ
１メッキ層状態を本発明の不均一島状分布及び比較例と
しての連続な均一分布に作シ分けた。このＮ１メッキ層
状態はＡＥＳ 、 ＥＰＭＡで調査し、第−表にＮｉ分
布状態を不均一島状分布及び連続均一分布と分類し、さ
らにＮｉメッキ層最大厚、及びＮ１メッキ厚が０、００
１ Ａｍ以上である領域の面積率で示した。Example 1 An average amount of 92 to 1 per side was applied to both sides of a steel plate whose surface was cleaned under normal conditions under various conditions in the treatment bath shown in (■).
Ni plating treatment was performed at a rate of 20μ/m2, and the treatment bath composition was -
1 Furthermore, by changing electrolytic conditions such as electrolytic current density, N
The state of one plating layer was divided into a non-uniform island-like distribution according to the present invention and a continuous uniform distribution as a comparative example. The state of this N1 plating layer was investigated using AES and EPMA, and the Ni distribution state was classified into non-uniform island-like distribution and continuous uniform distribution in Table 1, and the maximum thickness of the Ni plating layer and the N1 plating thickness were 0 and 0.
It is expressed as the area ratio of the area of 1 Am or more.
なお本発明要件はＮｉメッキ層最大厚が０．００２μｍ
以上又Ｎｉメッキ厚が０．００１μｍ以上である領域が
鋼板表面の面積率として９０％以下でおることである。Note that the present invention requires that the maximum thickness of the Ni plating layer be 0.002 μm.
As mentioned above, the area ratio of the area of the steel sheet surface where the Ni plating thickness is 0.001 μm or more is 90% or less.
引き続き■に示す処理浴中で片面当シ被覆量として８０
０及び１０００ｍｇ／ｍ のＳｎメッキ処理後■に示し
たフラックス溶液中へ浸漬、乾燥し、抵抗加熱法を用い
て大気雰囲気中でＳｎメッキ層溶融加熱処理を施した。Subsequently, in the treatment bath shown in ■, the coating amount per one side was 80%.
After Sn plating at 0 and 1000 mg/m 2 , it was immersed in the flux solution shown in (3), dried, and subjected to a heat treatment for melting the Sn plating layer in the air using a resistance heating method.
Ｓｎメッキ層溶融加熱処理条件は、溶融加熱処理時にＦ
ｅ／Ｓｎ界面に形成されるＦｅ −８ｎ合金中のＳｎ量
が全Ｓｎメッキ量の１／３となるような条件で実施した
。The Sn plating layer melt heat treatment conditions are F during the melt heat treatment.
The test was carried out under conditions such that the amount of Sn in the Fe-8n alloy formed at the e/Sn interface was 1/3 of the total amount of Sn plating.
そして■に示す条件で電解クロメート処理を施し、金属
クロム換算で片面当シ１２〜１７７ｎ９／ｍ２のクロメ
ート被膜層を形成し供試料とした。Then, electrolytic chromate treatment was performed under the conditions shown in (2) to form a chromate coating layer with a thickness of 12 to 177 n9/m2 on one side in terms of metal chromium, which was used as a sample.
浴温５０℃
浴Ｐ）Ｉ：１．８〜４．０
陰極電流密度＝５〜５０Ａ／ｄｍ２
浴温：４０〜５０℃
陰極電流密度： ２０ Ａ／ｄｍ２
■ ［フェノールスルフォン酸 ＝ １〜２ ｊ；ｌ／
ｌ ］浴温４５℃ ゛
浴温：４０〜６０℃
陰極電流密度： ５〜９ Ｑ Ａ／ｄｍ２実施例２
実施例１に於いてＳｎメッキ処理浴として■に替え■の
条件とし、又Ｓｎメッキ処理後の７ラツクス処理を省略
し、水洗のみとした実施例であり、その他項目は実施例
１と同じ
浴温：４０〜５０℃
陰極電流密度： ２０〜４０ Ａ／ｄｍ２比較例
実施例１に於いてＮｉメッキ処理を全て省略した比較例
でその他項目は実施例１と同じそして本発明実施例及び
比較列は製造チャンスごとの特性のバラツキ範囲を確認
するため、全く同一の製造条件で２回の試作を行ない、
それぞれ特性を同一チャンスで評価し、２回の製造チャ
ンスのバラツキを考慮して総合評価した。Bath temperature 50°C Bath P) I: 1.8 to 4.0 Cathode current density = 5 to 50 A/dm2 Bath temperature: 40 to 50°C Cathode current density: 20 A/dm2 ■ [phenol sulfonic acid = 1 to 2 j ;l/
l ] Bath temperature: 45°C Bath temperature: 40 to 60°C Cathode current density: 5 to 9 Q A/dm2 Example 2 In Example 1, the Sn plating treatment bath was replaced with ■ and conditions were changed to ■, and Sn plating was also performed. This is an example in which the 7 lux treatment after treatment was omitted and only water washing was performed, and other items were the same as in Example 1. Bath temperature: 40 to 50°C Cathode current density: 20 to 40 A/dm2 Comparative example Example 1 This is a comparative example in which the Ni plating process was completely omitted, and the other items were the same as in Example 1.The inventive example and comparison column were conducted twice under exactly the same manufacturing conditions in order to confirm the range of variation in characteristics for each manufacturing chance. We made a prototype of
The characteristics of each were evaluated in the same chance, and a comprehensive evaluation was made taking into account the dispersion between the two manufacturing chances.
なお従来例として片面当シのＳｎメッキ量が２８００■
／ｍのす２５ぶシきを同時に評価した。評価試験は下記
の（４）、φ）２項目について実施し、その結果を第１
表に示した。As a conventional example, the amount of Sn plating on one side is 2800■
/m was evaluated at the same time. The evaluation test was conducted on the following two items (4) and φ), and the results were
Shown in the table.
（４） シーム溶接性テスト
各試片を缶胴に成形した後、製缶用シーム溶接機と使用
して、缶胴接合部のラップ幅０．４調、加圧力４５ｋｇ
ｆ、製缶速度４５ ｍｐｍの条件で、溶接２次電流と変
化させることによって調査した。(4) Seam weldability test After forming each specimen into a can body, use a seam welder for can making to weld the can body joint at a lap width of 0.4 and a pressure of 45 kg.
The investigation was conducted by changing the welding secondary current under the conditions of f and can making speed of 45 mpm.
そして評価は良好な溶接が可能な溶接２次電流範囲で表
示した。The evaluation was expressed in the welding secondary current range that allowed good welding.
適正溶接２次電流の下限値は溶接部の強度の下限で、又
上限値はスプラ、シュ発生の上限で決定したが溶接部の
強度は衝撃テスト及び溶接部にＶ形のノツチを入れペン
、チで引きさく引きさきテストにより判定し、シーム溶
接部の外観は目視で散シの有無等よシ判定した。なおシ
ーム溶接性テストに供した試片は全て電気エアーオーブ
ン中で２１０℃、２０分の生焼を行った。The lower limit value of the appropriate secondary welding current was determined by the lower limit of the strength of the welded part, and the upper limit value was determined by the upper limit of the generation of splash and spark. The appearance of the seam weld was visually determined by checking the presence or absence of scattering. All specimens used in the seam weldability test were baked in an electric air oven at 210°C for 20 minutes.
（Ｂ） 耐冷膜下錆性テスト
各試片１／Ｃ１Ｒ缶用エポキシーフェノール塗料を片面
当Ｆ） ５５ ｍｇ／ ｄｍ ロールコートし、２０
５℃で１０分間焼付し、さらに１９０℃で１０分間追焼
処理した。そしてカッターナイフを用いて塗膜にスクラ
ッチを入れ、エリクセン試験機で５ヨのエリクセン加工
を施し供試サンプルとした。供試サンプルは５ ％ Ｎ
＆Ｃｔを用いた塩水噴霧を１時間行った後２５℃、相対
湿度８５％の恒温、恒湿試験機中に１４日間保定し、ス
クラッチ部から発錆状況を目視評価した。判定は◎糸錆
発生なし、○発生小、Δやや大、Ｘ大とした。(B) Cold film rust resistance test Each specimen was coated with epoxy phenol paint for 1/C1R can on one side at 55 mg/dm, and 20
Baking was performed at 5°C for 10 minutes, and additional baking was performed at 190°C for 10 minutes. Then, a scratch was made on the coating film using a cutter knife, and Erichsen processing of 5 degrees was performed using an Erichsen tester to prepare a test sample. The test sample was 5% N
After spraying salt water using &Ct for 1 hour, it was kept in a constant temperature and humidity tester at 25° C. and 85% relative humidity for 14 days, and the state of rust development was visually evaluated from the scratched portion. The evaluation was as follows: ◎ No thread rust occurred, ○ Small occurrence, Δ Slightly large, and X Large.
以上の試験結果は第１表工り明らかなように本発明実施
例に於いて本発明限定範囲を満足するものは、２回の製
造チャンス共得られた特性は安定しておシ、製造チャン
スごとのバラツキが少ない優れた特性が得られるのに対
し、本発明限定範囲を満足しないもの及び比較例は２回
の製造チャンスのうち少なくとも１回は得られる特性が
不十分であシ、劣っていることが判る。As is clear from the above test results in the first table work, in the examples of the present invention that satisfy the limited range of the present invention, the characteristics obtained in both the two manufacturing chances are stable. In contrast, the products that do not satisfy the limited range of the present invention and the comparative examples have insufficient properties in at least one of the two manufacturing chances, and are inferior. I know that there is.
本発明は鋼板上にＮ１メッキ前処理を施した、片面当シ
のＳｎメッキ量が２００〜２０００ ｍｇ／ｍ２の薄Ｓ
ｎメッキ鋼板の特性を銅板上のＮ１メッキ層を不均一な
島状分布となすよう施すことで安定かつ優れたものとす
る製造方法を提供するものである。そして本発明によっ
てシーム溶接性等特性を製造チャンスごとのバラツキが
ない安定して優れたものとすることができ、≠２５ぶシ
きに替る低コスト、高性能な素材を市場に提供すること
ができる。The present invention is a thin S plate with a Sn plating amount of 200 to 2000 mg/m2 on one side, which has been subjected to N1 plating pretreatment on a steel plate.
The present invention provides a manufacturing method that makes the characteristics of an N-plated steel sheet stable and excellent by applying an N1 plating layer on a copper plate so as to have a non-uniform island-like distribution. In addition, the present invention makes it possible to make seam weldability and other properties stable and excellent without variations depending on manufacturing opportunities, and to provide the market with a low-cost, high-performance material that can replace ≠25 bushings. can.
第１図、第２図は本発明法による不均−Ｎｉメッキ被覆
分布を示す模写図、第３図は本発明及び従来例のメッキ
断面モデル図を示す。
１・・・素地鋼板
第１図
第２図FIGS. 1 and 2 are schematic diagrams showing the uneven Ni plating coating distribution according to the method of the present invention, and FIG. 3 is a cross-sectional model diagram of the plating according to the present invention and a conventional example. 1...Base steel plate Figure 1 Figure 2
Claims (1)
キ被覆を施こし、引き続き片面当り２００〜２０００ｍ
ｇ／ｍ＾２のＳｎメッキ被覆を施こし、さらにＳｎメッ
キ層融点以上での加熱処理を施こした後、電解クロメー
ト処理を施こすことを特徴としたシーム溶接性、耐食性
に優れた表面処理鋼板の製造方法。[Claims] A non-uniform island-shaped Ni plating coating with an average coating amount of 2 to 100 mg/m^2 per side is applied to the surface of a steel plate, followed by a coating of 200 to 2000 m per side.
A surface treatment with excellent seam weldability and corrosion resistance, characterized by applying a Sn plating coating of g/m^2, further performing a heat treatment above the melting point of the Sn plating layer, and then applying electrolytic chromate treatment. Method of manufacturing steel plates.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61220521A JPS6376896A (en) | 1986-09-18 | 1986-09-18 | Production of surface-treated steel sheet having excellent seam weldability and corrosion resistance |
| DE87104231T DE3788178T2 (en) | 1986-09-18 | 1987-03-23 | Process for the production of a multi-coated steel strip with excellent corrosion resistance and weldability as well as usable for containers. |
| EP87104231A EP0260374B1 (en) | 1986-09-18 | 1987-03-23 | Process for producing a multilayer-coated strip having excellent corrosion resistance and weldability and useful for containers |
| CA000532926A CA1331962C (en) | 1986-09-18 | 1987-03-25 | Process for producing a multilayer-coated steel strip having excellent corrosion resistance and weldability and useful for containers |
| AU70712/87A AU573122B2 (en) | 1986-09-18 | 1987-03-27 | Electroplated tin-nickel on steel strip |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61220521A JPS6376896A (en) | 1986-09-18 | 1986-09-18 | Production of surface-treated steel sheet having excellent seam weldability and corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6376896A true JPS6376896A (en) | 1988-04-07 |
| JPH0214438B2 JPH0214438B2 (en) | 1990-04-09 |
Family
ID=16752317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61220521A Granted JPS6376896A (en) | 1986-09-18 | 1986-09-18 | Production of surface-treated steel sheet having excellent seam weldability and corrosion resistance |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0260374B1 (en) |
| JP (1) | JPS6376896A (en) |
| AU (1) | AU573122B2 (en) |
| CA (1) | CA1331962C (en) |
| DE (1) | DE3788178T2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63247393A (en) * | 1987-04-01 | 1988-10-14 | Nkk Corp | Production of surface treated steel sheet |
| JPH05177764A (en) * | 1991-12-27 | 1993-07-20 | Nkk Corp | Laminated steel plate for welded can and production thereof |
| JP2006274324A (en) * | 2005-03-28 | 2006-10-12 | Jfe Steel Kk | Method for manufacturing tin coated steel plate for welded can and method for measuring welding characteristic of tin coated steel plate for welded can |
| CN105177641A (en) * | 2015-10-27 | 2015-12-23 | 姜少群 | Nickel-plated steel shell |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2877957B2 (en) * | 1993-10-22 | 1999-04-05 | 東洋鋼鈑株式会社 | Surface treated steel sheet for battery case and battery case |
| CN104790002B (en) * | 2015-03-13 | 2017-04-12 | 武汉钢铁(集团)公司 | Production method of wear-resistant double composite plated tie for packaging hardware products |
| CN115175466B (en) * | 2022-07-04 | 2023-06-06 | 江苏富乐华半导体科技股份有限公司 | Welding method for improving electroplated tin-nickel alloy on surface of ceramic copper-clad substrate |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54142135A (en) * | 1978-04-28 | 1979-11-06 | Nippon Kokan Kk <Nkk> | Tin-plated steel plate and its manufacture |
| JPS56130487A (en) * | 1980-03-18 | 1981-10-13 | Toyo Kohan Co Ltd | After-treatment for extra-thin tin-plated steel sheet for welding |
| SE451976B (en) * | 1980-06-03 | 1987-11-09 | Nippon Steel Corp | STRABBAND WITH COATING LAYER AND CONTAINER MANUFACTURED FROM A CLEAR STALBAND |
| JPS5828356B2 (en) * | 1980-12-29 | 1983-06-15 | 新日本製鐵株式会社 | Chrome-plated steel sheet with excellent weldability |
| US4442181A (en) * | 1981-04-23 | 1984-04-10 | Nippon Steel Corporation | Steel strip having differentiated multilayer coatings and being useful for manufacturing of cans |
| US4511631A (en) * | 1984-04-13 | 1985-04-16 | Toyo Kohan Co., Ltd. | Metallic chromium-nickel-hydrated chromium oxide-coated tin free steel and process for the production thereof |
| JPS60258499A (en) * | 1984-06-04 | 1985-12-20 | Kawasaki Steel Corp | Manufacture of surface-treated steel plate for resistance welding |
| JPS61130500A (en) * | 1984-11-29 | 1986-06-18 | Kawasaki Steel Corp | Production of sn/cr two-layered plated steel plate |
-
1986
- 1986-09-18 JP JP61220521A patent/JPS6376896A/en active Granted
-
1987
- 1987-03-23 DE DE87104231T patent/DE3788178T2/en not_active Expired - Lifetime
- 1987-03-23 EP EP87104231A patent/EP0260374B1/en not_active Expired - Lifetime
- 1987-03-25 CA CA000532926A patent/CA1331962C/en not_active Expired - Lifetime
- 1987-03-27 AU AU70712/87A patent/AU573122B2/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63247393A (en) * | 1987-04-01 | 1988-10-14 | Nkk Corp | Production of surface treated steel sheet |
| JPH05177764A (en) * | 1991-12-27 | 1993-07-20 | Nkk Corp | Laminated steel plate for welded can and production thereof |
| JP2006274324A (en) * | 2005-03-28 | 2006-10-12 | Jfe Steel Kk | Method for manufacturing tin coated steel plate for welded can and method for measuring welding characteristic of tin coated steel plate for welded can |
| CN105177641A (en) * | 2015-10-27 | 2015-12-23 | 姜少群 | Nickel-plated steel shell |
Also Published As
| Publication number | Publication date |
|---|---|
| AU7071287A (en) | 1988-03-24 |
| EP0260374B1 (en) | 1993-11-18 |
| JPH0214438B2 (en) | 1990-04-09 |
| AU573122B2 (en) | 1988-05-26 |
| CA1331962C (en) | 1994-09-13 |
| DE3788178D1 (en) | 1993-12-23 |
| EP0260374A2 (en) | 1988-03-23 |
| DE3788178T2 (en) | 1994-03-10 |
| EP0260374A3 (en) | 1989-09-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |