JPH11312474A - Metal stud pin for glass sealing - Google Patents
Metal stud pin for glass sealingInfo
- Publication number
- JPH11312474A JPH11312474A JP10119399A JP11939998A JPH11312474A JP H11312474 A JPH11312474 A JP H11312474A JP 10119399 A JP10119399 A JP 10119399A JP 11939998 A JP11939998 A JP 11939998A JP H11312474 A JPH11312474 A JP H11312474A
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- layer
- glass
- sealing
- pin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Electrodes For Cathode-Ray Tubes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、テレビ、ＯＡ機器
等のブラウン管の映像面ガラス（以下「パネル」とい
う）内においてシャドウマスクを支持するために、パネ
ルの内側壁のガラス面に封着するスタッドピンの封着用
酸化皮膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to sealing a glass surface of an inner side wall of a panel for supporting a shadow mask in an image surface glass (hereinafter, referred to as a "panel") of a cathode ray tube of a television, an OA device or the like. The present invention relates to an oxide film for sealing stud pins.
【０００２】[0002]
【従来の技術】このスタッドピン（以下「ピン」とい
う）は、通常Ｆｅ−１８％Ｃｒ−Ｔｉ合金を半筒状に加
工し、脱脂、乾燥後、バレル研磨により加工時に生じた
バリを除去し、封着用酸化皮膜を形成するための酸化熱
処理を施すことにより製造されている。例えば、特開平
７−１９３８６２では、湿潤水素雰囲気中で７００〜１
１００℃に加熱することにより薄い酸化皮膜を形成さ
せ、後続する酸化工程で緻密な酸化皮膜を成長させてい
る。2. Description of the Related Art A stud pin (hereinafter referred to as a "pin") is generally formed by processing a Fe-18% Cr-Ti alloy into a semi-cylindrical shape, degreased and dried, and then removing burrs generated during processing by barrel polishing. It is manufactured by performing an oxidizing heat treatment for forming an oxide film for sealing. For example, in Japanese Patent Application Laid-Open No. 7-193682, 700-1
A thin oxide film is formed by heating to 100 ° C., and a dense oxide film is grown in a subsequent oxidation step.
【０００３】この場合、酸化皮膜付着力を強化するた
め、バレル研磨、洗浄後にサンドブラスト処理を行うこ
ともある。酸化皮膜が形成されたピンを封着したパネル
は、ブラウン管製造工程において、パネル内面に蛍光体
を塗布する工程の直前に、蛍光体塗布面がフッ酸または
フッ酸−硝酸の混酸で酸洗いされる。このとき、ピンも
同時に酸洗いされることになる。In this case, sandblasting may be performed after barrel polishing and cleaning in order to enhance the adhesion of the oxide film. In the cathode ray tube manufacturing process, immediately before the step of applying a phosphor to the inner surface of the panel, the phosphor-coated surface of the panel sealed with the pins having the oxide film formed thereon is washed with hydrofluoric acid or a mixed acid of hydrofluoric acid and nitric acid. You. At this time, the pins are also pickled.
【０００４】従来の酸化皮膜は、最表層がＣｒ2 Ｏ3 主
体のコランダム型酸化物層、ベースメタル側がＳｉＯ2
を主成分とする酸化物層より構成されており、前記コラ
ンダム型酸化物を主体とする２層酸化膜構造となってい
る。（Ｆｅ，Ｍｎ）Ｏ・Ｃｒ2 Ｏ3 を主成分とするスピ
ネル型酸化物層は、形成されている場合でもＭｎＯの含
有量は１５重量％以下でその厚さも１μｍ未満であり、
実質的に形成されていない場合もある。In a conventional oxide film, the outermost layer is a corundum type oxide layer mainly composed of Cr 2 O 3 , and the base metal side is SiO 2.
And a two-layer oxide film structure mainly composed of the corundum-type oxide. The spinel-type oxide layer containing (Fe, Mn) O.Cr 2 O 3 as a main component has a MnO content of 15% by weight or less and a thickness of less than 1 μm even when formed.
In some cases, it is not substantially formed.
【０００５】従来のコランダム型酸化物を主体とする前
記酸化膜は、フッ酸−硝酸の混酸に対して難溶性である
長所があるが、封着時にガラスとの濡れ性が悪い短所が
ある。また、該コランダム型酸化物の表層にスピネル型
酸化物層が形成されていても、前記したようにＭｎＯの
含有量が小さくしかも薄層のものでは、ガラスとの濡れ
性が充分に得られない。The conventional oxide film mainly composed of a corundum oxide has the advantage of being hardly soluble in a mixed acid of hydrofluoric acid and nitric acid, but has the disadvantage of poor wettability with glass at the time of sealing. Further, even if a spinel-type oxide layer is formed on the surface layer of the corundum-type oxide, the content of MnO is small as described above and a thin layer does not provide sufficient wettability with glass. .
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、従来
のピンにおける酸化皮膜の前記したガラスとの濡れ性欠
点を解消しようとするものである。SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned drawback of wettability of the oxide film of the conventional pin with the glass.
【０００７】半筒状のピンはパネルにその開放端側の一
部（脚部）が包埋封着され、頭部を含む大半は露出した
状態でブラウン管の製造時に加熱、冷却工程を通過する
ため、この間に膨張、収縮する。そのため、ピン表面に
生成した酸化皮膜とガラスとの濡れ形状によっては、酸
化皮膜に対するガラスの密着力が著しく低下する。酸化
皮膜に対するガラスの密着力が低下した状態でピンがブ
ラウン管に組み込まれて真空引きされると、酸化皮膜と
ガラスが剥離しやすくなる。従来の酸化皮膜の最表層に
形成されるＣｒ2 Ｏ3 主体のコランダム型酸化物層は、
金属酸化物中では比較的溶融温度が高く、ガラスとの濡
れ性が悪い。[0007] The semi-cylindrical pin has a part (leg) on its open end side embedded and sealed in the panel, and most of the part including the head is exposed and goes through a heating and cooling process during the manufacture of a CRT. Therefore, it expands and contracts during this time. Therefore, depending on the wet shape of the oxide film formed on the pin surface and the glass, the adhesion of the glass to the oxide film is significantly reduced. When the pins are assembled in a cathode ray tube and evacuated in a state where the adhesion of the glass to the oxide film is reduced, the oxide film and the glass are easily peeled off. The corundum type oxide layer mainly composed of Cr 2 O 3 formed on the outermost layer of the conventional oxide film is:
In metal oxides, the melting temperature is relatively high and the wettability with glass is poor.
【０００８】また、ピンはその一部が露出した状態で酸
洗いされる。そのため、ピン表面に生成した酸化皮膜の
耐酸性が低いと、酸化皮膜が侵食されるばかりでなく、
ベースメタルに対する酸化皮膜の密着力が著しく低下し
剥離する。シャドウマスク脱着時に剥離したこの酸化皮
膜の微粉がブラウン管内に飛散すると、ブラウン管の表
示欠点となり歩留が低下する。Further, the pins are pickled with a part thereof exposed. Therefore, if the oxide film formed on the pin surface has low acid resistance, not only does the oxide film erode,
The adhesion of the oxide film to the base metal is significantly reduced and peels off. If the fine powder of the oxide film peeled off at the time of attaching and detaching the shadow mask scatters into the cathode ray tube, it becomes a display defect of the cathode ray tube and the yield decreases.
【０００９】[0009]
【課題を解決するための手段】本発明は、このような問
題を解消すべくなされたものであり、ガラスとの濡れ性
にはピン表面に生成する酸化皮膜の最表層にスピネル型
酸化物層が形成されており、かつスピネル型酸化物層中
のＭｎＯの含有量が大きいことが極めて有効であること
を見いだし完成したものである。DISCLOSURE OF THE INVENTION The present invention has been made to solve such a problem, and a spinel type oxide layer is formed on the outermost surface of an oxide film formed on a pin surface in order to improve wettability with glass. Have been formed, and it has been found that it is extremely effective that the content of MnO in the spinel-type oxide layer is large.
【００１０】この知見に基づき、ブラウン管の製造工程
で熱工程を通過するときの酸化皮膜に対するガラスの密
着力低下を抑制するために、溶融温度が低く、ガラスと
の濡れ性が良いＭｎＯ主体の酸化物を最表層に形成し、
該最表層の下層にパネルの酸洗いに使用されるフッ酸−
硝酸の混酸にほとんど溶解しないＣｒ2 Ｏ3 主体の酸化
物を形成することにより、ガラスとの濡れ性に優れ、か
つ耐酸性に優れた酸化皮膜を有するピンを提供する。Based on this finding, in order to suppress a decrease in the adhesion of the glass to the oxide film when passing through the heating step in the cathode ray tube manufacturing process, MnO-based oxidation having a low melting temperature and good wettability with the glass is performed. The thing is formed on the outermost layer,
Hydrofluoric acid used for pickling panels below the outermost layer
A pin having an oxide film excellent in wettability with glass and excellent in acid resistance is provided by forming an oxide mainly composed of Cr 2 O 3 which is hardly dissolved in a mixed acid of nitric acid.
【００１１】すなわち、本発明はベースメタルが重量％
で、Ｃｒ: １７．０〜２０．０％、Ｓｉ: ０．２０〜
０．８０％、Ｍｎ: ０．６０％以下、Ａｌ: ０．４０％
以下、Ｔｉ: ０．７０％以下のＦｅ−１８％Ｃｒ−Ｔｉ
合金であり、その表面に封着用酸化皮膜を有し、該酸化
皮膜の最表層がＭｎをＭｎＯ換算で１８重量％以上含ん
でいることを特徴とするガラス封着用金属製スタッドピ
ンを提供する。That is, in the present invention, the base metal is
And Cr: 17.0-20.0%, Si: 0.20
0.80%, Mn: 0.60% or less, Al: 0.40%
Hereinafter, Ti: Fe-18% Cr-Ti of 0.70% or less
A metal stud pin for sealing glass, which is an alloy, has an oxide film for sealing on the surface thereof, and the outermost layer of the oxide film contains Mn in an amount of 18% by weight or more in terms of MnO.
【００１２】また、前記封着用酸化皮膜が３層構造であ
り、その最表層が（Ｆｅ，Ｍｎ）Ｏ・Ｃｒ2 Ｏ3 を主成
分とする厚さ１〜２μｍのスピネル型酸化物層である上
記のガラス封着用金属製スタッドピンを提供する。The sealing oxide film has a three-layer structure, and the outermost layer is a spinel oxide layer having a thickness of 1 to 2 μm and containing (Fe, Mn) O.Cr 2 O 3 as a main component. A metal stud pin for sealing glass is provided.
【００１３】また、前記封着用酸化皮膜の中間層がＣｒ
2 Ｏ3 を主成分とする厚さ１〜２μｍのコランダム型酸
化物層であり、前記封着用酸化皮膜のベースメタルに最
も近い層が厚さ１〜２μｍのＳｉＯ2 を主成分とする酸
化物層である上記のガラス封着用金属製スタッドピンを
提供する。The intermediate layer of the sealing oxide film is made of Cr.
1 to 2 μm thick corundum oxide layer mainly composed of 2 O 3 , wherein the layer closest to the base metal of the sealing oxide film is an oxide mainly composed of 1 to 2 μm thick SiO 2 . There is provided a metal stud pin for sealing glass as described above, which is a layer.
【００１４】本発明のガラス封着用ピンは、その目的を
達成するため、酸化熱処理時の酸化炉内雰囲気温度、酸
化処理条件、湿潤水素量、湿潤水素の露点等の処理条件
を制御してガラス封着用酸化皮膜を生成させることがで
きる。また、酸化熱処理前にブラスティング処理を施す
こともできる。In order to achieve the object, the glass sealing pin of the present invention controls the glass atmosphere by controlling the processing conditions such as the atmospheric temperature in the oxidation furnace, the oxidation processing conditions, the amount of wet hydrogen, and the dew point of the wet hydrogen. An oxide film for sealing can be formed. Further, a blasting treatment can be performed before the oxidation heat treatment.
【００１５】[0015]
【発明の実施の形態】本発明において、ガラスに封着す
るピンの封着用酸化皮膜は、ピン素材であるベースメタ
ルを湿潤雰囲気等の弱酸化雰囲気において、１１００〜
１２００℃で３０〜１２０分加熱する酸化処理により形
成できる。ベースメタルとしては、重量％で、Ｃｒ: １
７．０〜２０．０％、Ｓｉ: ０．２０〜０．８０％、Ｍ
ｎ: ０．６０％以下、Ａｌ: ０．４０％以下、Ｔｉ:
０．７０％以下、残部がＦｅのＦｅ−１８％Ｃｒ−Ｔｉ
合金を使用する。この合金は一般に４３０Ｔｉ合金とし
て知られているもので、ピン素材の特性と使用実績を有
している。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an oxide film for sealing a pin to be sealed to glass is obtained by heating a base metal as a pin material in a weakly oxidizing atmosphere such as a wet atmosphere.
It can be formed by an oxidation treatment of heating at 1200 ° C. for 30 to 120 minutes. As base metal, Cr: 1
7.0 to 20.0%, Si: 0.20 to 0.80%, M
n: 0.60% or less, Al: 0.40% or less, Ti:
0.70% or less, the balance being Fe-18% Cr-Ti
Use alloy. This alloy is generally known as a 430Ti alloy and has the properties and performance of pin materials.
【００１６】上記の各金属は、Ｆｅ−１８％Ｃｒ−Ｔｉ
合金の有効必須成分として含有されており、最表層に所
望のＭｎＯ系の酸化皮膜を前記酸化処理により形成する
には、Ｍｎは０．２重量％以上、特に０．４〜０．５重
量％含まれているのが望ましい。なお、基本組成がガラ
ス封着用のＦｅ−１８％Ｃｒ−Ｔｉ合金であれば、前記
した金属以外にＮｉ、Ｃなどの微量成分を他の鋼材と同
じように含んでいても支障ない。Each of the above metals is Fe-18% Cr-Ti
In order to form a desired MnO-based oxide film on the outermost layer by the above oxidation treatment, Mn is contained in an amount of 0.2% by weight or more, particularly 0.4 to 0.5% by weight, which is contained as an effective essential component of the alloy. Preferably it is included. In addition, if the basic composition is an Fe-18% Cr-Ti alloy for sealing glass, other than the above-mentioned metals, trace components such as Ni and C may be contained similarly to other steel materials.
【００１７】前記した熱処理条件でこのＦｅ−１８％Ｃ
ｒ−Ｔｉ合金を酸化熱処理すると、図１に示すような酸
化皮膜が表面に形成される。図１において、１はピンの
ベースメタル、２〜４は該ベースメタルの表面に形成さ
れた３層構造の封着用酸化皮膜で、２は（Ｆｅ，Ｍｎ）
Ｏ・Ｃｒ2 Ｏ3 を主成分とするスピネル型酸化物層から
なるＭｎＯ系の最表層、３はＣｒ2 Ｏ3 を主成分とする
コランダム型酸化物層からなる中間層、４はベースメタ
ル１に最も近い層でＳｉＯ2 を主成分とする酸化物層か
らなる最下層である。Under the above heat treatment conditions, the Fe-18% C
When the r-Ti alloy is subjected to an oxidizing heat treatment, an oxide film as shown in FIG. 1 is formed on the surface. In FIG. 1, 1 is a base metal of a pin, 2 to 4 are oxide films for sealing having a three-layer structure formed on the surface of the base metal, and 2 is (Fe, Mn).
The outermost layer of MnO system comprising a spinel-type oxide layer to the O · Cr 2 O 3 as a main component, the intermediate layer 3 is made of corundum oxide layer mainly composed of Cr 2 O 3, 4 base metal 1 And a lowermost layer composed of an oxide layer containing SiO 2 as a main component.
【００１８】ガラスとの密着力が大きく、ガラスとの濡
れ性に優れかつ酸洗浄時の耐酸性に優れたピンを得るた
めには、ガラスに対する濡れ性がよい前記ＭｎＯ系酸化
皮膜と混酸に対して難溶解性のＣｒ2 Ｏ3 系酸化皮膜
を、ピンの表面全体を覆うように酸化熱処理で均一に形
成させることが重要である。In order to obtain a pin having a large adhesion to glass, excellent wettability with glass, and excellent acid resistance at the time of acid washing, it is necessary to use a mixed acid with the MnO-based oxide film having good wettability with glass. It is important to uniformly form a hardly soluble Cr 2 O 3 -based oxide film by oxidizing heat treatment so as to cover the entire surface of the pin.
【００１９】このような観点から、図１に示すような構
成の酸化皮膜は、ガラスとの濡れ性、耐酸性に優れた効
果を生ずる。そして、酸化皮膜が所期の効果を発揮する
ためには、後述するように最表層２のＭｎ（ＭｎＯ換
算）の含有量が１８重量％以上でなければならないが、
皮膜の厚さも充分に配慮する必要がある。特に、最表層
２の（Ｆｅ，Ｍｎ）Ｏ・Ｃｒ2 Ｏ3 を主成分とする酸化
皮膜は、ガラスとの濡れ性に密接に関係するので大切で
あり、その厚さは１〜２μｍが好ましい。最表層２の厚
さが１μｍ未満であると、ガラスとの濡れ性が充分に得
られなくなり、また２μｍを超えると耐酸性が悪くな
る。From such a viewpoint, the oxide film having the structure as shown in FIG. 1 produces an effect excellent in wettability with glass and acid resistance. In order for the oxide film to exhibit the desired effect, the content of Mn (in terms of MnO) of the outermost layer 2 must be 18% by weight or more as described later.
Careful consideration must also be given to the thickness of the film. In particular, the oxide film mainly composed of (Fe, Mn) O · Cr 2 O 3 in the outermost layer 2 is so closely related to wettability between glass are important, its thickness is preferably 1~2μm . When the thickness of the outermost layer 2 is less than 1 μm, sufficient wettability with glass cannot be obtained, and when it exceeds 2 μm, acid resistance deteriorates.
【００２０】また、中間層３は酸化皮膜、正確には封着
用酸化皮膜の耐酸性を向上させる効果があり、膜厚は１
μｍ以上が望ましい。一方、この中間層の膜厚を厚くす
ると、酸化皮膜の耐酸性は向上するが、酸化皮膜の密着
性が悪化するので、２μｍ以下に抑えるのがよい。The intermediate layer 3 has the effect of improving the acid resistance of the oxide film, more precisely, the oxide film for sealing.
μm or more is desirable. On the other hand, when the thickness of the intermediate layer is increased, the acid resistance of the oxide film is improved, but the adhesion of the oxide film is deteriorated. Therefore, the thickness is preferably suppressed to 2 μm or less.
【００２１】ＳｉＯ2 を主成分とする最下層４は、ベー
スメタルと酸化皮膜の密着性を向上させる効果があり、
膜厚は通常１〜２μｍが望ましい。１μｍ未満になると
密着性が充分に得られなくなり、２μｍを超えると主成
分のＳｉＯ2 が酸に溶解しやすいので、ベースメタルと
の接着性は向上するが、耐酸性が悪化する。The lowermost layer 4 mainly composed of SiO 2 has an effect of improving the adhesion between the base metal and the oxide film.
Usually, the film thickness is desirably 1-2 μm. If it is less than 1 μm, sufficient adhesion cannot be obtained, and if it exceeds 2 μm, the main component SiO 2 is easily dissolved in acid, so that the adhesion to the base metal is improved, but the acid resistance is deteriorated.
【００２２】したがって、封着用酸化皮膜全体の膜厚は
これら３層が加算されるので約３〜６μｍとなる。な
お、酸化皮膜を構成するこれら３層の各層界または層界
部は、通常必ずしも明確に分離しないで両方の酸化物が
混在していることが多い。中間層３と最表層２とは、比
較的はっきりと層分離しているが、中間層３、最下層４
およびベースメタル１との各界部は、この混在部が目立
つ傾向にある。このときの各層は、混在部の中間で画定
する。また、各酸化皮膜層はできるだけ均一に形成する
が、膜厚分布がある場合には、その平均膜厚とする。さ
らに、ピンの熱処理により通常アンカーリングと呼ばれ
る、Ａｌ2 Ｏ3 、ＴｉＯ2 からなる内部酸化層が、最下
層４よりベースメタル側２０μｍの範囲に存在するが、
この内部酸化層は封着用酸化皮膜とは異なるものとして
扱う。Accordingly, the total thickness of the sealing oxide film is about 3 to 6 μm because these three layers are added. In addition, each layer boundary or layer boundary portion of these three layers constituting the oxide film is usually not always clearly separated and both oxides are often mixed. The middle layer 3 and the outermost layer 2 are relatively clearly separated from each other.
In each boundary with the base metal 1, the mixed portion tends to be conspicuous. Each layer at this time is defined in the middle of the mixed portion. Each oxide film layer is formed as uniformly as possible. If there is a film thickness distribution, the average film thickness is used. Further, an internal oxide layer made of Al 2 O 3 and TiO 2 , which is usually called an anchor ring due to the heat treatment of the pin, exists in a range of 20 μm from the lowermost layer 4 to the base metal side.
This internal oxide layer is treated as different from the oxide film for sealing.
【００２３】次に、最表層２のＭｎの含有量について説
明する。ガラスとの濡れ性を確保するためには、最表層
中のＭｎの含有量をＭｎＯ換算で１８重量％以上にす
る。最表層２は、前記したように（Ｆｅ，Ｍｎ）Ｏ・Ｃ
ｒ2 Ｏ3 を主成分とするスピネル型酸化物層からなって
いるので、Ｍｎは実質的にＭｎＯとして含有されてい
る。したがって、ＭｎＯの含有量として算定してほとん
ど問題ないが、ＭｎＯ以外の形態でＭｎが含まれている
場合にはすべてＭｎＯに換算し、換算後のＭｎの全含有
量を便宜的にＭｎＯ量とする。Next, the content of Mn in the outermost layer 2 will be described. In order to ensure wettability with glass, the content of Mn in the outermost layer is set to 18% by weight or more in terms of MnO. As described above, the outermost layer 2 is made of (Fe, Mn) O.C
Mn is substantially contained as MnO because it is composed of a spinel-type oxide layer containing r 2 O 3 as a main component. Therefore, there is almost no problem in calculating the content of MnO, but when Mn is contained in a form other than MnO, all of the MnO is converted to MnO, and the converted Mn content is conveniently referred to as the MnO amount. I do.
【００２４】ＭｎＯ量が１８重量％より少なくなると、
ガラスとの濡れ性が相対的に低下し、所望の封着が得ら
れなくなる。一方、最表層２のＭｎＯ量を増加させる
と、ガラスとの濡れ性は向上するが、耐酸性が悪化する
ので、ＭｎＯ量は３０重量％以下に抑えるのが望まし
い。ガラスとの濡れ性と耐酸性が両立し特に好ましい範
囲は、２１〜２７重量％である。なお、ここでＭｎＯ量
は最表層２の膜厚方向および膜面方向における分布が均
一でないときは、その平均含有量として算定する。When the amount of MnO is less than 18% by weight,
The wettability with glass relatively decreases, and the desired sealing cannot be obtained. On the other hand, when the amount of MnO in the outermost layer 2 is increased, the wettability with glass is improved, but the acid resistance is deteriorated. Therefore, the amount of MnO is desirably suppressed to 30% by weight or less. A particularly preferred range for achieving both wettability with glass and acid resistance is 21 to 27% by weight. Here, when the distribution of the outermost layer 2 in the thickness direction and the film surface direction is not uniform, the MnO amount is calculated as an average content thereof.
【００２５】ピンの耐酸性向上については、ベースメタ
ル中のＣｒ量の増量によりベースメタル自体の耐食性を
向上させ、混酸への溶解に起因する耐酸性の劣化を防止
することも考えられる。しかし、Ｃｒ量を増加させると
熱膨張係数が大きくなり、封着材としての機能が果たせ
なくなる。With respect to the improvement of the acid resistance of the pin, it is conceivable to improve the corrosion resistance of the base metal itself by increasing the amount of Cr in the base metal and prevent the deterioration of the acid resistance due to dissolution in the mixed acid. However, when the Cr content is increased, the coefficient of thermal expansion increases, and the function as a sealing material cannot be achieved.
【００２６】また、Ｓｉ無添加の鋼材を使用することに
より、混酸に溶解するＳｉＯ2 層をなくすことも考えら
れる。しかし、ＳｉＯ2 層が存在しないと、中間層３の
Ｃｒ2 Ｏ3 層とベースメタルとの密着力が低下し、酸化
熱処理の段階で健全な酸化皮膜が形成されにくくなる。
素材中のＭｎ量を低減して、最表層にＭｎＯ層が形成さ
れるのを抑制し中間層３を表層に出せば、耐酸性は向上
するが、ガラスとの濡れ性が悪くなる。このように、素
材の組成を変更することにはいろいろな制約が加わる。It is also conceivable to eliminate the SiO 2 layer dissolved in the mixed acid by using a steel material without Si. However, if the SiO 2 layer does not exist, the adhesion between the Cr 2 O 3 layer of the intermediate layer 3 and the base metal decreases, and it becomes difficult to form a sound oxide film in the oxidation heat treatment stage.
If the amount of Mn in the material is reduced to suppress the formation of the MnO layer on the outermost layer and the intermediate layer 3 is exposed to the surface, the acid resistance is improved, but the wettability with glass is deteriorated. As described above, changing the composition of the material has various restrictions.
【００２７】本発明は、その点ピン素材の組成を変更す
ることなく、酸化熱処理条件を制御することで、ガラス
との濡れ性、耐酸性に優れた封着用酸化皮膜をピン表面
に形成できる。According to the present invention, by controlling the oxidation heat treatment conditions without changing the composition of the pin material, an oxide film for sealing excellent in wettability with glass and acid resistance can be formed on the pin surface.
【００２８】[0028]
【実施例】（実施例）Ｆｅ−１８％Ｃｒ−Ｔｉ鋼材（重
量％で、Ｃｒ：１８．４、Ｓｉ：０、４４、Ｍｎ：０．
４７、Ａｌ：０．３９、Ｔｉ：０．４６）をピンに加工
し、酸化熱処理に供した。酸化熱処理には湿潤水素雰囲
気で加熱した後、炉冷する条件を採用した。この酸化熱
処理したピン表面をＳＥＭ−ＥＤＸで加速電圧を１５ｋ
Ｖに設定して分析したところ、前記した３層の封着用酸
化皮膜が形成されており、その最表層のＭｎＯの含有量
は約２３重量％であった。また、膜厚は１．５μｍであ
った。EXAMPLES (Examples) Fe-18% Cr-Ti steel (Cr: 18.4, Si: 0, 44, Mn: 0.
47, Al: 0.39, Ti: 0.46) were processed into pins and subjected to oxidative heat treatment. For the oxidizing heat treatment, conditions of heating in a wet hydrogen atmosphere and then cooling in a furnace were employed. The surface of the pin subjected to the oxidizing heat treatment is accelerated by SEM-EDX to an accelerating voltage of 15 k.
When the analysis was carried out at V, the three oxide films for sealing were formed, and the MnO content of the outermost layer was about 23% by weight. The film thickness was 1.5 μm.
【００２９】このピンについて、パネルガラスとの濡れ
性および耐酸性を調査した。ガラスとの濡れ性試験とし
て、１０８０℃、１１４０℃に加熱した電気炉に酸化熱
処理されたピンを入れ、ピン頭部に一定量、一定形状の
パネルガラスを乗せ、ガラスとピンとの濡れ角度を測定
した。その結果を表１に示す。The pin was examined for wettability with panel glass and acid resistance. As a test for wettability with glass, put the pin that has been oxidized and heat-treated in an electric furnace heated to 1080 ° C and 1140 ° C, put a fixed amount of a panel glass of a fixed shape on the pin head, and measure the wetting angle between the glass and the pin. did. Table 1 shows the results.
【００３０】耐酸性試験として２０℃の６％フッ酸＋６
％硝酸の水溶液にピンを浸漬した。浸漬前後にピンの重
量を測定し、次式に従って重量減少率を求めた結果を表
２に示す。As an acid resistance test, 6% hydrofluoric acid at 20 ° C. + 6
The pins were immersed in an aqueous solution of 10% nitric acid. The weight of the pin was measured before and after immersion, and the weight loss rate was determined according to the following equation.
【００３１】重量減少率＝（浸漬後の減少重量）／（浸
漬前のピン重量）×１００ （比較例）実施例と同じＦｅ−１８重量％Ｃｒ−Ｔｉ鋼
材からなり、その封着用酸化皮膜が、Ｃｒ2 Ｏ3 を主成
分とするコランダム型酸化物層とＳｉＯ2 を主成分とす
る酸化物層の実質的に２層からなる従来のピンについて
も、実施例と同様なガラスとの濡れ性試験および耐酸性
試験を行った。その結果をそれぞれ表１、表２に示す。
なお、このピンの前記コランダム型酸化物層の表層には
１μｍ以下の極く薄い（Ｆｅ，Ｍｎ）Ｏ・Ｃｒ2 Ｏ3 を
主成分とするスピネル型酸化物層が形成されているが、
そのＭｎＯの含有量は約９重量％であった。Weight reduction rate = (reduced weight after immersion) / (pin weight before immersion) × 100 (Comparative Example) It is made of the same Fe-18% by weight Cr—Ti steel material as in the example, and the oxide film for sealing is used. A conventional pin consisting of substantially two layers, a corundum oxide layer mainly composed of Cr 2 O 3 and an oxide layer mainly composed of SiO 2, has the same wettability with glass as in the embodiment. A test and an acid resistance test were performed. The results are shown in Tables 1 and 2, respectively.
A very thin spinel-type oxide layer mainly composed of (Fe, Mn) O.Cr 2 O 3 of 1 μm or less is formed on the surface of the corundum-type oxide layer of this pin.
The MnO content was about 9% by weight.
【００３２】表１、表２の調査結果から明らかなよう
に、本発明のピンは従来のピンに比べて特に１１４０℃
におけるガラスとの濡れ性が優れる。そして、耐酸性は
いずれの場合も同等である。As is clear from the results of the investigations in Tables 1 and 2, the pin of the present invention was particularly 1140 ° C.
Has excellent wettability with glass. The acid resistance is the same in each case.
【００３３】このことから最表層に（Ｆｅ，Ｍｎ）Ｏ・
Ｃｒ2 Ｏ3 を主成分とする酸化物層を形成することによ
り、耐酸性を維持したままで、パネルガラスとの濡れ性
が飛躍的に向上することが確認された。From this, (Fe, Mn) O.
It was confirmed that by forming an oxide layer containing Cr 2 O 3 as a main component, the wettability with the panel glass was dramatically improved while maintaining the acid resistance.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【発明の効果】以上に説明したように、本発明において
はピンの表面に酸化熱処理により形成する封着用酸化皮
膜の最表層を、（Ｆｅ，Ｍｎ）Ｏ・Ｃｒ2 Ｏ3 を主成分
とする酸化物層とし、そのＭｎＯ含有量を１８重量％以
上にすることにより、耐酸性を維持したままで、パネル
ガラスとの濡れ性を向上させることができる。これによ
りピン封着強度の大きいパネルガラスを得ることができ
る。しかも、前記酸化物層を酸化熱処理時の処理条件を
制御することにより形成できるので、ベースメタル素材
の成分を特に変える必要がない。As described above, in the present invention, the outermost layer of the sealing oxide film formed on the surface of the pin by the oxidizing heat treatment is mainly composed of (Fe, Mn) O.Cr 2 O 3. By setting the MnO content of the oxide layer to 18% by weight or more, the wettability with the panel glass can be improved while maintaining the acid resistance. As a result, a panel glass having a high pin sealing strength can be obtained. In addition, since the oxide layer can be formed by controlling the processing conditions during the oxidation heat treatment, there is no need to particularly change the components of the base metal material.
【図１】Ｆｅ−１８％Ｃｒ−Ｔｉ合金を湿潤水素雰囲気
中で酸化熱処理したときに生成する封着用酸化皮膜層の
断面図。FIG. 1 is a cross-sectional view of a sealing oxide film layer formed when an Fe-18% Cr—Ti alloy is subjected to an oxidizing heat treatment in a wet hydrogen atmosphere.
１：ベースメタル ２：最表層 ３：中間層 ４：最下層 1: base metal 2: outermost layer 3: middle layer 4: lowermost layer
Claims (4)
用酸化皮膜を有し、該酸化皮膜の最表層がＭｎをＭｎＯ
換算で１８重量％以上含んでいることを特徴とするガラ
ス封着用金属製スタッドピン。1. The base metal is 1% to 20.0% by weight: Cr: 17.0 to 20.0%, Si: 0.20 to 0.80%, Mn: 0.60% or less, Al: 0.40% or less, Ti: 0.70% or less Fe-18% Cr-Ti alloy having an oxide film for sealing on the surface thereof, and the outermost layer of the oxide film is formed of Mn by MnO
A metal stud pin for sealing glass, comprising at least 18% by weight in conversion.
の最表層が（Ｆｅ，Ｍｎ）Ｏ・Ｃｒ2 Ｏ3 を主成分とす
る厚さ１〜２μｍのスピネル型酸化物層である請求項１
記載のガラス封着用金属製スタッドピン。2. The oxide film for sealing has a three-layer structure, and the outermost layer is a spinel oxide layer having a thickness of 1 to 2 μm and containing (Fe, Mn) O.Cr 2 O 3 as a main component. Claim 1
A metal stud pin for sealing glass as described.
を主成分とする厚さ１〜２μｍのコランダム型酸化物層
であり、前記封着用酸化皮膜のベースメタルに最も近い
層が厚さ１〜２μｍのＳｉＯ2 を主成分とする酸化物層
である請求項２記載のガラス封着用金属製スタッドピ
ン。3. The sealing oxide film according to claim 1, wherein the intermediate layer is Cr 2 O 3.
And a layer closest to the base metal of the oxide film for sealing is an oxide layer having a thickness of 1 to 2 μm and containing SiO 2 as a main component. The metal stud pin for sealing glass according to claim 2.
で１８〜３０重量％である請求項１、２または３記載の
ガラス封着用金属製スタッドピン。4. The metal stud pin for sealing glass according to claim 1, wherein the content of Mn in the outermost layer is 18 to 30% by weight in terms of MnO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10119399A JPH11312474A (en) | 1998-04-28 | 1998-04-28 | Metal stud pin for glass sealing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10119399A JPH11312474A (en) | 1998-04-28 | 1998-04-28 | Metal stud pin for glass sealing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11312474A true JPH11312474A (en) | 1999-11-09 |
Family
ID=14760541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10119399A Pending JPH11312474A (en) | 1998-04-28 | 1998-04-28 | Metal stud pin for glass sealing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11312474A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005248191A (en) * | 2004-03-01 | 2005-09-15 | Sumitomo Metal Ind Ltd | Ferritic stainless steel sheet having superior seizure resistance, and manufacturing method therefor |
| JP2005248190A (en) * | 2004-03-01 | 2005-09-15 | Sumitomo Metal Ind Ltd | Ferritic stainless steel sheet having superior seizure resistance for component of automotive exhaust gas system, and manufacturing method therefor |
-
1998
- 1998-04-28 JP JP10119399A patent/JPH11312474A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005248191A (en) * | 2004-03-01 | 2005-09-15 | Sumitomo Metal Ind Ltd | Ferritic stainless steel sheet having superior seizure resistance, and manufacturing method therefor |
| JP2005248190A (en) * | 2004-03-01 | 2005-09-15 | Sumitomo Metal Ind Ltd | Ferritic stainless steel sheet having superior seizure resistance for component of automotive exhaust gas system, and manufacturing method therefor |
| JP4519482B2 (en) * | 2004-03-01 | 2010-08-04 | 新日鐵住金ステンレス株式会社 | Ferritic stainless steel sheet for automobile exhaust system having excellent seizure resistance and method for producing the same |
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