JPS59219473A

JPS59219473A - Color etching solution and etching method

Info

Publication number: JPS59219473A
Application number: JP9290483A
Authority: JP
Inventors: Yukihiro Iwashita; 岩下　幸博; Tatsuo Oota; 達雄太田; Kenya Sakamoto; 坂本　研哉; Yutaka Nomura; 豊野村
Original assignee: Nippon Steel Corp
Current assignee: Nippon Steel Corp
Priority date: 1983-05-26
Filing date: 1983-05-26
Publication date: 1984-12-10
Also published as: JPS6339674B2

Abstract

PURPOSE:To subject a steel material to color-coded etching by each structure by treating the steel material with a soln. prepd. by adding a nitric acid to a soln. mixture composed of a picric acid/ethanol soln. and a sodium thiosulfate/citric acid soln. and treating further the material with a soln. mixture composed of said treating soln. and a nital soln., etc. CONSTITUTION:A steel material is immersed for 3-15 seconds in a pretreating soln. prepd. by mixing a soln. A prepd. by dissolving 1-5g a picric acid in 100ml ethanol and a soln. B prepd. by mixing 1-25g sodium thiosulfate and 1-5g a citric acid in 100ml water to 1:1 and adding 1.5-4% a nitric acid to said soln. The material is washed with alcohol and is dried then the material is immersed for 3-20 seconds in a post treating soln. prepd. by mixing 10% the pretreating soln. with a 2% nital soln. or mixing 2-5% a nitric acid with 100ml ethanol to perform etching. The etched material is rinsed and dried. The steel material is color-etched by each structure by the above-mentioned method. The color-coded etching of, for example, ferrite to yellowish white, pearlite to black to pale blue, bainite to gray and martensite to yellow to brown is made possible.

Description

【発明の詳細な説明】本発明は、鋼材の持つ組織を各組織別に色別可能にエッ
チシフし、しかも粒界の現出を自由にコシトロールでき
るカラーエッチシフ液及びその液を用いたエッチ、７り
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a color etch-shifting solution that can etch-shift the structure of a steel material in a manner that allows each structure to be distinguished by color, and also enables the appearance of grain boundaries to be freely controlled, and an etch method using the solution. This is related to the method.

鋼材の性質を支配する要因の一つである組織は、通常、
組織写真、組織測定（面積率、粒径、粒周長等）、組織
別硬度等によって調査される。The structure, which is one of the factors controlling the properties of steel, is usually
It is investigated using microstructure photographs, microstructure measurements (area ratio, grain size, grain circumference, etc.), hardness by structure, etc.

従来は、５チナイタ一ル腐食液にて現出した組織によっ
て前述の諸調査を行っているが、次のような問題点があ
った。即ち、各組織の鮮明度が組織定量・化のための機
械処理能力に一部（フェライト）を除いてイ′１・！に
たないため一旦組緘を写真に撮り、これを人の判１ｔ、
Ｉ［によって組織別にｈ色已別けした１友槻械旧画像処
理で組織定五１化をし、１いた。また、１王来の１昌食
液は粒界が現出するためこれか機械的画像処理を繁！Ａ
１１−にして。Conventionally, the above-mentioned investigations have been carried out based on the structure revealed using a 5-tire corrosive solution, but there were the following problems. In other words, the clarity of each tissue is limited to the mechanical processing capacity for quantifying and quantifying the structure, except for some (ferrite). In order to avoid the damage, I took a photo of the group and printed it in a human size 1t.
I separated the tissue by color using I [1], and used the old image processing method to convert the tissue to 51, and found 1. In addition, since grain boundaries appear in the 1-sho food solution, mechanical image processing is often required. A
Set it to 11-.

いた。このため、多大の労力と時間を要し、多大の処理
イをな、１７やしていた。更には、鋼材の成分、加工形
態等により＋＋ｉ：：ｌ　Ａ’ｉｉｋの一部（バーライ
１〜、ベーナイト、マルデシ１〕・イト）が肉眼でも刊
別Ｌ　！＋ｌｌ；いものかル）す、ＩＡ’）えて実行し
た場合の積度＋ｔ＝　Ｙ・−管必−要な。）１″４査に
も！ｆｉｌｌ限か牛していた３、ホラｃ明ば、上記の如
き１ｉ［来技術の間Ｆｑ点をｊ４１に）・ノｒ決」るの
ではなく、根本的な改革を前提に室料のフェライト、バ
ーライ１−、ベーライト、フルデシ１ｊイト等の竹ｈ［
０哉を組織別に色別ムＪ能なＪ−ツ１ジグ液の開発と、
それによるエツヂシジカ法の開発を目的に各（・ｆ！誠
楽をもとに莫大な実験、ｉｒ’Ｑ　ＩＩを車、ねた結星
なされたもので、その特徴とするところは、１エタノー
ル１００　ｍｌにピクリ、／肖ンを１〜５ｙの古１］合
でｍ丹Ｉ　したＡ７夜、水１０〇−にグλ乱醒Ｊトリウ
ムｊ６〜２５２とクエ′Ｊ酸１〜５Ｉの７；すＩＴｒで
溶解したＢ液、Ａ液とＢ液を１：１で混合しまた後、硝
酸を１．５〜４チの割合で添加混合（−またｈｉ」処理
液と、２襲１゛イタール液に前記前処理液を１０％の割
合で混合するか、又はエタノ−１ｂ　１００　ｍｌ、に
（１１′１１４＜２〜５ψ・の割合で混侶したイ夛処理
液からなることを特徴とするカラ・−１ツチしヅ′）ｉ
、２４タノール１０〇−にしクリル酸を１−−一５ｙの
割合で溶解したＡ液、水１００　ｍｅに５プ似酸Ｊ−ト
リウム１〜２５　？　トクエ：Ｊ　ｍ　！　−□　５　
ｇ　（ｊ）　Ｗ’１合”ｅ　ｉ８　汗！’、　ｌ、　ｆ
、−Ｂ液、Ａ液とＲ・故をｔｒｉで混合した後、硝酸を
】５〜・４％の割合で添加混合した前処理液に鋼材を３
〜１５秒浸漬後、アＩＬ　］−ルで洗浄し、乾燥した後
、２φナイタ〜！し液に前記前処理液を１０％の割合で
混合するか、又はエタ）　　１１／１００　ｍｌに硝酸
２−５％の割合で混合した後処理液の何れかに３−２（
）秒浸漬後、水洗し、乾燥することを特’ｄ’、　：ｔ
−ず４〕′ｓ−・−ｊチシタプｊ゛法にある。there was. This requires a great deal of effort and time, and a great deal of processing time. Furthermore, depending on the composition of the steel material, processing form, etc., some parts of ++i::l A'iik (barai 1~, bainite, mardesi 1] and ito) can be seen with the naked eye by publication L! +ll; IA') Accumulation degree when executed with +t= Y・-tube required. ) 1" Even in the 4th inspection! I was worried about filling 3. Now, rather than deciding on 1i [during the next technology to set Fq point to j41) as above, I decided to make a fundamental decision. Based on the premise of reform, bamboo h[
Developing a J-T1 jig liquid that can be used to color-code 0ya by tissue,
With the aim of developing the Etsujishika method, a huge amount of experimentation was carried out based on Seiraku, ir'Q II was used as a car, and the special feature was that 1 ethanol 100 On the night of A7, on Wednesday 100-100-100-100-100-day, the mixture of 1 to 5 years of old 1 to 5 years was mixed with 1 to 5 years of acid. B solution dissolved in ITr, A solution and B solution were mixed in a ratio of 1:1, and then nitric acid was added and mixed at a ratio of 1.5 to 4 h (-mata hi" treatment solution and 2-stroke 1" ital solution). 10% of the pretreatment liquid or mixed with 100 ml of ethanol-1b at a ratio of (11′114<2 to 5ψ・).・-1tsuchishizu')i
, 24tanol 100- and acrylic acid dissolved in a ratio of 1-5y. Toque: Jm! −□ 5
g (j) W'1 go"e i8 sweat!', l, f
, - After mixing B solution, A solution, and R solution in tri, add nitric acid at a ratio of 5 to 4% and add steel material to the mixed pretreatment solution.
After soaking for ~15 seconds, wash with AIL] and dry, then soak for 2φ night~! Add 3-2(
) After soaking for seconds, wash with water and dry.
It is in the method.

本発明のカラー　エッチ、°・夕液がどのような反応磯
１１乍から鉢４月の谷組織別にか（もＩ叶明な色別を提
供するのか定かでないが、千オイシＩＬ酸ｙトリウムと
クエシ酸が少なくとも１１１１記したｊＩｌｉ月の四つ
のｉｌ’（ｉ　Ｉｉ↑１（を色別することと粒界の現出
が後処理液の硝酸濃度と浸漬時間によって左右されるこ
との発見がＱｊ６　ｍＮで、この発見をもとに重ねる実
験で」二記した４１１成液が最も鮮明にかつｌｆ）現性
よ＜　ａｆｒれもが何れの場所においＣも當に同等のカ
ラーエッチ、７ジをネオことｋ　イｉｆに認したもので
ある。What kind of reaction does the color etch of the present invention have with thorium IL acid and thorium IL acid? The color classification of the four il' (i Ii↑1) described by quesic acid at least 1111 and the discovery that the appearance of grain boundaries is influenced by the nitric acid concentration of the post-treatment solution and the immersion time are Qj6 mN, and in repeated experiments based on this discovery, the liquid 411 mentioned above was the clearest and the most vivid. Neo, also known as k-iif, approved this.

次に本発明を実施例に基いてＨ￥　ｉｌｌに説明する。Next, the present invention will be explained based on examples.

（１′）　　エツチシジ液の（古成前処理液Ａ液：ヒクリル酸３ｙ／エタノール１００ｍｇ１容赦Ｂ散：チメ硫酸ずトリウム５７、クエシ酸３　’ｊ／Ｈ
２０１００ｄ溶７＆Ａ液とＢ液を１−１で混合後、硝酸２％を添加した液後処理液硝酸５ゴ／エタノール１ｏｕｄ溶液（］）　　供試鋼材表　　１ υ♀　処理方法前処理液に５秒間浸漬後、鋼材を取り出１−、メチルア
ルコールでａ滌後、送風乾燥（好ましくは４０℃以下）
を行い、欠（・で後処理液に５秒間浸漬後、鋼拐ンハＺ
り出して、流動水で洗滌後、送風乾燥（望まｌ〜くけ４
０℃以下）した各鋼１１］を５〜・１０分でカラー撮影
した。(1') Etsuchishiji's solution (pre-treatment liquid A: 3y hyacrylic acid/100mg ethanol 1 merciless B powder: 57% trithium thimesulfate, 3'j/H quesic acid
20100d solution 7 & After mixing solutions A and B at a ratio of 1-1, 2% nitric acid was added to the solution Post-treatment solution Nitric acid 5g/ethanol 1oud solution (]) Table of test steel materials 1 υ♀ Treatment method Add 5 to the pre-treatment liquid After immersing for a second, take out the steel material, rinse with methyl alcohol, and dry with air (preferably below 40°C).
After immersing in the post-treatment liquid for 5 seconds,
Take it out, wash it with flowing water, and dry it with air (preferably 1 to 4
Each steel 11] was photographed in color for 5 to 10 minutes.

己　処理結果表　　２体）測定結果本１ケ１］ば、供試鋼の上記発色にもとづいて、硬度に
ついては超微小硬度６Ｆ、面積率については接械的画像
処理によってｇｊ定算出したものである。Treatment result table 2 Body) Measurement result book 1 1] Based on the above color development of the test steel, the hardness is ultra-micro hardness 6F, and the area ratio is gj constant calculated by mechanical image processing. It is.

表　３本実施例におけるＡ、Ｂ１０各鋼材のエッチシタ特性を
まとめると次のようになり、これ等を配慮して実用的な
カラーエッチシフが実現するのは、本発明が限定する液
の構成範囲とエッチシフ方法であり、これを外れると欠
配する各特性は実用性の低下を招（。Table 3 The etch characteristics of steel materials A and B10 in this example are summarized as follows, and taking these into consideration, practical color etch shift can be achieved within the composition range of the liquid defined by the present invention. This is the etch shift method, and if you deviate from this method, each characteristic that is missing will lead to a decline in practicality (.

ａ、　　（ＯＪが低くて加工歪の大きいもの程色が出難
い。a, (The lower the OJ and the greater the processing distortion, the harder it is to produce color.

ｂ、　ヂオ硫酸すトリウムの濃度が高い程、色は【農く
なるが汚れが出やすい。b. The higher the concentration of thorium diosulfate, the darker the color, but the easier it is to stain.

Ｃ２処理（前・後共）の時間が２０秒を超えると表面の
肌が荒れ始める。When the time of C2 treatment (both before and after) exceeds 20 seconds, the surface skin begins to become rough.

ｄ、液温が高くなると（３０〜４０℃）表面の肌が荒れ
始める。d. When the liquid temperature becomes high (30 to 40°C), the surface skin starts to become rough.

Ｃ６硝酸の濃度によってパーライトの色彩が黒色から淡
青色の間で変化する。The color of pearlite changes from black to pale blue depending on the concentration of C6 nitric acid.

１８粒界は後処理液の硝酸濃度がρくなるが、浸漬時間
が長（なると現出がみられる。18 grain boundaries appear when the nitric acid concentration of the post-treatment liquid becomes ρ, but the immersion time is longer (the longer the immersion time is), the more they appear.

又、処理液は作成快ガスの発生を伴なうことがあるので
作成後１５分程度経過してから使用することが＆Ｊまし
く、又、作成後６時間以上を経ると沈ｌｉ・ｕ物が発生
し、反応は変化か生ずることがあるので、鏑尚な変質防
止剤を用いない場合は６時間を超える保イｒは避けるこ
とが望まし℃・。In addition, since the processing liquid may be accompanied by the generation of gas, it is best to use it approximately 15 minutes after preparation, and if more than 6 hours have passed after preparation, it may cause precipitation It is desirable to avoid holding the product for more than 6 hours unless a suitable deterioration inhibitor is used, as this may cause changes in the reaction.

本発明によると、既述の説明から明白なように６１４利
の各組織を組織別に鮮明に色別できることから、そのま
まカラー！ｉｌＪ織写↓工を得ることができ、又、調査
目的により粒界の現出を自由にコシドロー；１．ｉ目止
であり、その上腐食”Ｊ、７Ｊルから直接組織Δ１測の
ための劣は曲面像処理が１１能で多大の労ツバ時向、処
理費が節減できるばかりでなく、耕イト１１拐の開発速
度を大ｒｌｊに促進する等工業上もたらす効果は太きい
。According to the present invention, as is clear from the above description, each of the 614 tissues can be clearly distinguished by color, so it can be colored as it is! It is possible to obtain an ilJ texture, and also to freely express the appearance of grain boundaries according to the purpose of investigation; 1. In addition, it is possible to directly measure the structure Δ1 from the corrosion "J, 7J" curved surface image processing, which not only saves a lot of labor time and processing costs, but also reduces the amount of tilling. It has great industrial effects, such as greatly accelerating the development speed of microorganisms.

Claims

【特許請求の範囲】１　エタノール１００ｒｎｌにヒクリシ酸を１〜５７０
割合で溶解したＡ液、水１００−にチオ硫酸ナトリウム
１〜２５？とクエシ酸１〜５りの割合で溶解したＢ液、
Ａ液とＢ液を１：１で混合した後、硝酸を１．５〜４％
の割合で添加混合した前処理液と、２％ナイタール液に
前記前処理液を１０襲の割合で混合するか、又はエタノ
ール１００−に硝酸２〜５嘱の割合で混合した後夕１上
埋液からなることを特徴とするカラーエッチシフ液。２　エタノール１００　ｍｅにヒクリシ酸を１〜５１０
割合で溶解したＡ液、水１００−にチオ硫酸ナトリウム
１〜２５１とクエシ酸１〜５７０割合で溶月了したＢ液
、Ａ液とＢ液を１；ｌで混合した後、硝１１−乏を１．
５〜４％の割合で添加混合した前処理液に鋼材を３〜１
５秒浸漬後、アルコールで洗浄し、乾燥した後、２％ナ
イタール液に前記処理液を１０％の割合で混合するか、
又はエタノール１００−に硝酸２〜５チの割合で混合し
た後処理液の何れかに３〜２０秒浸漬後、水洗し、乾燥
することを特徴とするエッチ、７タ方法。[Claims] 1. 1 to 570 hyclisic acid in 100 rnl of ethanol
A solution dissolved in a ratio of 1 to 25 parts sodium thiosulfate to 100 parts of water. and B solution dissolved in a ratio of 1 to 5 parts of quesic acid,
After mixing liquid A and liquid B at a ratio of 1:1, add 1.5 to 4% nitric acid.
The pre-treatment liquid was added and mixed at a ratio of 2% nital solution and the pre-treatment liquid was mixed at a ratio of 10 parts, or the pre-treatment liquid was mixed at a ratio of 100 parts of ethanol and 2 to 5 parts of nitric acid, and then the pre-treatment liquid was mixed with 2% nital solution at a ratio of 2 to 5 parts of nitric acid. A color etch schiff liquid characterized by consisting of a liquid. 2 Add 1 to 510 hyclisic acid to 100 me of ethanol.
Solution A was dissolved in a ratio of 100% of sodium thiosulfate and 1 to 570% of sodium thiosulfate was dissolved in 1 to 570% of water. After mixing solutions A and B in a ratio of 1:1, 1.
Add 3-1% of steel material to the pre-treatment liquid added and mixed at a ratio of 5-4%.
After 5 seconds of immersion, washing with alcohol and drying, the treatment solution is mixed with a 2% nital solution at a ratio of 10%, or
Or, an etch method characterized by immersing for 3 to 20 seconds in a post-treatment liquid prepared by mixing 2 to 5 parts of nitric acid to 100 parts of ethanol, followed by washing with water and drying.