JPH05157723A - Method for inspecting defect of insulation coating - Google Patents
Method for inspecting defect of insulation coatingInfo
- Publication number
- JPH05157723A JPH05157723A JP32219591A JP32219591A JPH05157723A JP H05157723 A JPH05157723 A JP H05157723A JP 32219591 A JP32219591 A JP 32219591A JP 32219591 A JP32219591 A JP 32219591A JP H05157723 A JPH05157723 A JP H05157723A
- Authority
- JP
- Japan
- Prior art keywords
- defect
- metal material
- inspected
- solution
- insulation coating
- 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.)
- Withdrawn
Links
Landscapes
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属材料の表面に形成さ
れている絶縁皮膜の欠陥検査方法に関する。近年、塗装
技術と機器の進歩により薄く、且つ、均一に塗装するこ
とができるようになった。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for inspecting defects in an insulating film formed on the surface of a metallic material. In recent years, the progress of coating technology and equipment has made it possible to coat thinly and uniformly.
【０００２】また、アルミニウム(Al)やチタン(Ti)のよ
うな弁作用金属(Valve-metal) については、この金属を
電解液に浸漬して陽極とし、電解酸化を行うことによっ
て、金属面上に絶縁性の酸化皮膜を形成することができ
る。For valve-acting metals such as aluminum (Al) and titanium (Ti), these metals are immersed in an electrolytic solution to form an anode, and electrolytic oxidation is performed to form a metal on the metal surface. An insulating oxide film can be formed on.
【０００３】こゝで、塗装や電解酸化による酸化皮膜形
成の目的は金属面の保護, 耐蝕性の向上, 電気絶縁など
色々あるが、塗膜や酸化皮膜にピンホールなどの欠陥が
ないことが必要である。Here, the purpose of forming an oxide film by painting or electrolytic oxidation is to protect a metal surface, improve corrosion resistance, electrical insulation, etc., but there are no defects such as pinholes in the paint film or oxide film. is necessary.
【０００４】そのため、絶縁皮膜の欠陥検査は品質管理
のために不可欠な工程である。Therefore, the defect inspection of the insulating film is an essential step for quality control.
【０００５】[0005]
【従来の技術】絶縁皮膜の欠陥検出法としては下地金属
により各種の方法が用いられている。例えば、多孔性ア
ルミニウム酸化皮膜（通称アルマイト皮膜) を備えたAl
材料については、 メチルレッドやコンゴーレッドなどの染料をトリエ
タノールアミンの水溶液中に浸漬し、材料片を陽極とし
て電圧を印加し、電気泳動により皮膜の欠陥部に染料が
電着してスポット状に着色することにより検出する電着
法。 材料片を陰極、また銅(Cu)板を陽極とし、その間に
塩化バリウム(BaCl2) とフェノールフタレインの混合水
溶液を湿らせた濾紙を挟んだ状態で電流を通じ、欠陥部
がピンクに変色するのを利用して検出するエレクトログ
ラフ(Electrograph)法。 CuなどAlより貴な金属イオンを含む水溶液中に材料
片を浸漬し、欠陥部に貴の金属を析出させる方法( 金属
析出法) 。 Alを陽極, 純鉛(Pb)を陰極とし、材料片を蟻酸の水
溶液に浸漬した状態で電圧を印加し、通過電気量により
欠陥を定量的に測定する蟻酸浴電解法。 などがある。2. Description of the Related Art Various methods for detecting defects in an insulating film are used depending on the underlying metal. For example, Al with a porous aluminum oxide film (commonly called alumite film)
As for the material, dye such as methyl red or Congo red is dipped in an aqueous solution of triethanolamine, voltage is applied with the piece of material as an anode, and the dye is electrodeposited on the defective part of the film by electrophoresis to form spots. An electrodeposition method that detects by coloring. A defect piece turns pink by passing an electric current while sandwiching a piece of material as a cathode and a copper (Cu) plate as an anode, and sandwiching a filter paper moistened with a mixed aqueous solution of barium chloride (BaCl 2 ) and phenolphthalein between them. An electrograph method of detecting by using the. A method in which a piece of material is immersed in an aqueous solution containing a metal ion that is more precious than Al such as Cu to deposit the precious metal on the defect (metal deposition method). A formic acid bath electrolysis method in which Al is used as an anode and pure lead (Pb) is used as a cathode, and a voltage is applied while the piece of material is immersed in an aqueous solution of formic acid, and defects are quantitatively measured by the amount of passing electricity. and so on.
【０００６】また、下地が鉄(Fe)の場合は、フェリシア
ンイオン[Fe(CN)6 3+] とフェロシアンイオン[Fe(C
N)6 4+] を含む混合溶液中に材料片を浸漬し、皮膜に欠
陥が存在した場合にこの溶液がFeの表面に到達し、青色
の発色反応を生ずるのを利用して検出が行われている。When the base is iron (Fe), ferricyan ion [Fe (CN) 6 3+ ] and ferrocyan ion [Fe (C
When a piece of material is dipped in a mixed solution containing (N) 6 4+ ] and the film has defects, this solution reaches the surface of Fe and causes a blue color reaction to be detected. It is being appreciated.
【０００７】然し、このような方法は検出反応がそのま
ゝ維持できないことが問題である。すなわち、電着法に
おいては欠陥部に電着した染料が試験の終わるまでに再
び溶媒に溶解するため欠陥部の数や面積を正確に読み取
ることが難しい。However, such a method has a problem that the detection reaction cannot be maintained as it is. That is, in the electrodeposition method, it is difficult to accurately read the number and area of defective portions because the dye electrodeposited on the defective portions dissolves in the solvent again by the end of the test.
【０００８】また、エレクトログラフ法においては水の
電気分解を伴うために印加電圧によっては金属面で生成
物が分極し、感度が低下すると云う問題がある。Further, in the electrographic method, there is a problem that the product is polarized on the metal surface depending on the applied voltage due to the electrolysis of water and the sensitivity is lowered.
【０００９】[0009]
【発明が解決しようとする課題】絶縁皮膜に存在するピ
ンホールなどの欠陥検査法としては金属により各種の方
法が用いられているが、先に記したように検出反応がそ
のまゝ試験後まで維持できないことが問題である。Various methods are used for inspecting defects such as pinholes existing in the insulating film, depending on the metal, but as described above, the detection reaction is performed until after that test. The problem is that it cannot be maintained.
【００１０】そこで、検出反応が試験後まで維持でき、
安定性のよい方法を実用化することが課題である。Therefore, the detection reaction can be maintained until after the test,
The challenge is to put a method with good stability into practical use.
【００１１】[0011]
【課題を解決するための手段】上記の課題は非水系有機
溶媒中に芳香族スルホン酸塩よりなる支持電解質と電解
酸化により導電性高分子重合体を形成するヘテロ芳香族
系物質とを加えて溶解したものを検査溶液とし、この溶
液中に絶縁皮膜の欠陥検査を行う被検査金属材料を浸漬
して陽極とし、対極との間に電圧を加えて電解を行い、
被検査金属材料の欠陥部にヘテロ芳香族系の物質よりな
る導電性高分子重合体を析出せしめ、この析出量より欠
陥部の検出と定量を行うことを特徴として絶縁皮膜の欠
陥検査方法を構成することにより解決することができ
る。Means for Solving the Problems The above-mentioned problems are caused by adding a supporting electrolyte composed of an aromatic sulfonate and a heteroaromatic substance forming a conductive polymer by electrolytic oxidation in a non-aqueous organic solvent. The dissolved solution is used as an inspection solution, the metal material to be inspected for defect inspection of the insulating film is immersed in this solution as an anode, and voltage is applied between the counter electrode and electrolysis,
A method for inspecting defects in insulating films is characterized by depositing a conductive high-molecular polymer made of a heteroaromatic substance on the defect part of the metal material to be inspected, and detecting and quantifying the defect part from the deposited amount. It can be solved by doing.
【００１２】[0012]
【作用】発明者等は感度および再現性が良く、且つ下地
金属の材質を選ばない検出法として芳香族系の単量体が
酸化重合反応によって導電性高分子重合体になる反応を
検出反応として使用するものである。The present inventors have found that the sensitivity and reproducibility are good, and that the detection reaction does not depend on the material of the underlying metal, and the reaction in which the aromatic monomer becomes a conductive polymer by an oxidative polymerization reaction is used as the detection reaction. Is what you use.
【００１３】すなわち、図１に示すように被検査金属材
料１を対極２と共にヘテロ芳香族系単量体を含む検査溶
液３の中に浸漬し、被検査金属材料１を直流電源４の陽
極に結線して一定の電圧を加えて電解を行い、欠陥部５
で生ずる酸化重合反応により導電性高分子重合体６が析
出するのを利用し、この析出位置と析出量を測定するこ
とにより欠陥の検出を行うものである。That is, as shown in FIG. 1, the metal material 1 to be inspected is dipped in an inspection solution 3 containing a heteroaromatic monomer together with a counter electrode 2, and the metal material 1 to be inspected is used as an anode of a DC power source 4. Connect the wires and apply a certain voltage to electrolyze,
By utilizing the fact that the conductive high-molecular polymer 6 is deposited by the oxidative polymerization reaction that occurs in (1), the defect is detected by measuring the deposition position and the deposition amount.
【００１４】このような検出法を用いれば、析出物が導
電性であるため析出が阻害されることがなく、ヘテロ芳
香族系単量体は低い酸化還元電位を有するために比較的
低い電圧印加により感度が高く、また再現性の優れた欠
陥検査を行うことができる。When such a detection method is used, since the precipitate is conductive, the precipitation is not hindered, and since the heteroaromatic monomer has a low redox potential, a relatively low voltage is applied. Thus, it is possible to perform defect inspection with high sensitivity and excellent reproducibility.
【００１５】そのためには、 検査溶液の液抵抗が低いこと、 導電性高分子重合体の電導性の良いこと、 などが必要である。For that purpose, it is necessary that the test solution has a low resistance and that the conductive high-molecular polymer has a good electric conductivity.
【００１６】この観点から発明者等は検査溶液としては
アセトニトリル，炭酸プロピレン，N,N-ジメチルホルム
アミド, メタノールなどの非水系溶媒を使用し、電導性
をもたせる支持電解質として芳香族スルホン酸のテトラ
エチルアンモニウム塩とテトラブチルアンモニウム塩を
選んだ。From this point of view, the inventors have used a non-aqueous solvent such as acetonitrile, propylene carbonate, N, N-dimethylformamide, and methanol as a test solution, and use tetraethylammonium of aromatic sulfonic acid as a supporting electrolyte having conductivity. Salt and tetrabutylammonium salt were chosen.
【００１７】こゝで、芳香族スルホン酸としてはベンゼ
ンスルホン酸,p-トルエンスルホン酸, ナフタレンスル
ホン酸などの使用が適当である。また、液中に溶解して
おり、低い酸化還元電位をもち電解重合により導電性高
分子となる物質としてはヘテロ芳香族系の材料例えばピ
ロール, チオフェン, フランなどを選定した。Here, it is suitable to use benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc. as the aromatic sulfonic acid. Heteroaromatic materials such as pyrrole, thiophene, and furan were selected as substances that are dissolved in the liquid and have a low redox potential to become conductive polymers by electrolytic polymerization.
【００１８】このような液組成を使用すると２〜５Ｖの
電圧印加により欠陥部に導電性の高分子重合体の成長が
生ずるので、この成長物を光学顕微鏡で観察するか、Ｘ
線マイクロアナライザなどで分析することにより欠陥の
位置と量を測定することができる。When such a liquid composition is used, a conductive high-molecular polymer grows in the defect portion when a voltage of 2 to 5 V is applied. Therefore, the growth product is observed by an optical microscope or X
The position and amount of defects can be measured by analyzing with a line micro analyzer.
【００１９】[0019]
実施例１：溶媒としてアセトニトリルを用い、支持電解
質としてp-トルエンスルホン酸テトラエチルアンモニウ
ムを用い0.1 Ｍ溶液を作り、ヘテロ芳香族系物質として
ピロールを0.1 Ｍ添加して検査溶液とした。Example 1 Acetonitrile was used as a solvent, tetraethylammonium p-toluenesulfonate was used as a supporting electrolyte to prepare a 0.1 M solution, and 0.1 M of pyrrole was added as a heteroaromatic substance to give a test solution.
【００２０】また、被検査金属材料としては大きさが１
×２cmのAl板を0.1 ％の硼酸アンモン溶液を用いて電解
酸化を行い、厚さ約0.5 μm のAl酸化皮膜をつけたもの
を使用した。The size of the metal material to be inspected is 1
An x 2 cm Al plate was electrolytically oxidized using a 0.1% ammonium borate solution and provided with an Al oxide film having a thickness of about 0.5 μm.
【００２１】検査方法としては、検査溶液30cc中にステ
ンレス板を対極として３Ｖの電圧を印加し30分放置し
た。時間経過後にAl板を取り出して表面を観察すると点
状にポリピロールが生成しており、色が深い黒色である
ために検出は容易に行うことができた。 実施例２：溶媒としてアセトニトリルを用い、支持電解
質としてナフタレンスルホン酸テトラエチルアンモニウ
ムを用い0.1 Ｍ溶液を作り、ヘテロ芳香族系物質として
ピロールを0.1 Ｍ添加して検査溶液とした。As a test method, a voltage of 3 V was applied to 30 cc of the test solution with a stainless steel plate as a counter electrode, and the test solution was allowed to stand for 30 minutes. When the Al plate was taken out after a lapse of time and the surface was observed, polypyrrole was formed in dots, and the detection was easy because the color was deep black. Example 2: A 0.1 M solution was prepared using acetonitrile as a solvent and tetraethylammonium naphthalenesulfonate as a supporting electrolyte, and 0.1 M of pyrrole was added as a heteroaromatic substance to prepare a test solution.
【００２２】また、被検査金属材料としては大きさが１
×２cmのCu板に10μm の厚さにエポキシ系塗料を塗布し
たものを使用した。検査方法としては、検査溶液30cc中
にステンレス板を対極として３Ｖの電圧を印加し30分放
置した。The size of the metal material to be inspected is 1
A 2 cm × 2 cm Cu plate coated with an epoxy paint to a thickness of 10 μm was used. As an inspection method, a voltage of 3 V was applied to 30 cc of the inspection solution with a stainless steel plate as a counter electrode and left for 30 minutes.
【００２３】時間経過後にCu板を取り出して表面を観察
すると線状または点状にポリピロールが生成しており、
色が深い黒色であるために検出は容易に行うことができ
た。After a lapse of time, when the Cu plate was taken out and the surface was observed, polypyrrole was formed in a linear or dot shape,
The detection was easy because of the deep black color.
【００２４】[0024]
【発明の効果】電解重合反応を利用して欠陥部に導電性
高分子を成長させる本発明の使用により再現性と安定性
が良く、また簡便に欠陥検査を行うことができる。EFFECTS OF THE INVENTION The use of the present invention in which a conductive polymer is grown in a defective portion by utilizing an electrolytic polymerization reaction has good reproducibility and stability, and a defect inspection can be performed easily.
【図１】本発明の原理図である。FIG. 1 is a principle diagram of the present invention.
１ 被検査金属材料 ３ 検査溶液 ５ 欠陥部 ６ 導電性高分子重合体 1 Metal material to be inspected 3 Inspection solution 5 Defect part 6 Conductive polymer
Claims (2)
よりなる支持電解質と電解酸化により導電性高分子重合
体を形成するヘテロ芳香族系物質とを加えて溶解したも
のを検査溶液とし、該溶液中に絶縁皮膜の欠陥検査を行
う被検査金属材料を浸漬して陽極とし、対極との間に電
圧を加えて電解を行い、該被検査金属材料の欠陥部に前
記ヘテロ芳香族系の物質よりなる導電性高分子重合体を
析出せしめ、該析出量より欠陥部の検出と定量を行うこ
とを特徴とする絶縁皮膜の欠陥検査方法。1. A test solution is prepared by adding a supporting electrolyte made of an aromatic sulfonate and a heteroaromatic substance forming a conductive high-molecular polymer by electrolytic oxidation to a non-aqueous organic solvent and dissolving the solution. A metal material to be inspected for defect inspection of an insulating film is immersed in the solution to form an anode, a voltage is applied between the metal and a counter electrode to perform electrolysis, and a defect portion of the metal material to be inspected is made of the heteroaromatic system. A method for inspecting a defect of an insulating film, which comprises depositing a conductive high-molecular polymer made of a substance, and detecting and quantifying a defect portion from the deposited amount.
炭酸プロピレン，N,N-ジメチルホルムアミドまたはメタ
ノールであり、芳香族スルホン酸塩がベンゼンスルホン
酸,p- トルエンスルホン酸またはナフタレンスルホン酸
のテトラエチルアンモニウム塩またはテトラブチルアン
モニウム塩であり、ヘテロ芳香族系物質がピロール, チ
オフェンまたはフランであることを特徴とする請求項１
記載の絶縁皮膜の欠陥検査方法。2. The non-aqueous organic solvent is acetonitrile,
Propylene carbonate, N, N-dimethylformamide or methanol, wherein the aromatic sulfonate is benzene sulfonic acid, p-toluene sulfonic acid or naphthalene sulfonic acid tetraethylammonium salt or tetrabutylammonium salt, and a heteroaromatic substance Is pyrrole, thiophene or furan.
Insulation film defect inspection method described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32219591A JPH05157723A (en) | 1991-12-06 | 1991-12-06 | Method for inspecting defect of insulation coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32219591A JPH05157723A (en) | 1991-12-06 | 1991-12-06 | Method for inspecting defect of insulation coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05157723A true JPH05157723A (en) | 1993-06-25 |
Family
ID=18141012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32219591A Withdrawn JPH05157723A (en) | 1991-12-06 | 1991-12-06 | Method for inspecting defect of insulation coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05157723A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101509867B1 (en) * | 2011-12-26 | 2015-04-07 | 닛산 지도우샤 가부시키가이샤 | Inspecting method and inspecting system |
| KR20150107712A (en) * | 2012-10-19 | 2015-09-23 | 프리에토 배터리, 인크. | Detection of defects in solid-polymer coatings |
| KR20200027595A (en) * | 2018-09-04 | 2020-03-13 | 주식회사 디엠에스 | Apparatus for detecting pin hole |
-
1991
- 1991-12-06 JP JP32219591A patent/JPH05157723A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101509867B1 (en) * | 2011-12-26 | 2015-04-07 | 닛산 지도우샤 가부시키가이샤 | Inspecting method and inspecting system |
| KR20150107712A (en) * | 2012-10-19 | 2015-09-23 | 프리에토 배터리, 인크. | Detection of defects in solid-polymer coatings |
| KR20200027595A (en) * | 2018-09-04 | 2020-03-13 | 주식회사 디엠에스 | Apparatus for detecting pin hole |
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