JPS62188752A - Soft glass sealing alloy - Google Patents

Soft glass sealing alloy

Info

Publication number
JPS62188752A
JPS62188752A JP3659187A JP3659187A JPS62188752A JP S62188752 A JPS62188752 A JP S62188752A JP 3659187 A JP3659187 A JP 3659187A JP 3659187 A JP3659187 A JP 3659187A JP S62188752 A JPS62188752 A JP S62188752A
Authority
JP
Japan
Prior art keywords
alloy
oxide film
soft glass
corrosion resistance
sealing
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
Application number
JP3659187A
Other languages
Japanese (ja)
Other versions
JPS6319587B2 (en
Inventor
Masakazu Umeda
梅田 正和
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Proterial Ltd
Original Assignee
Sumitomo Special Metals Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Special Metals Co Ltd filed Critical Sumitomo Special Metals Co Ltd
Priority to JP3659187A priority Critical patent/JPS62188752A/en
Publication of JPS62188752A publication Critical patent/JPS62188752A/en
Publication of JPS6319587B2 publication Critical patent/JPS6319587B2/ja
Granted legal-status Critical Current

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Abstract

PURPOSE:To obtain a soft glass sealing alloy having improved corrosion resistance and improving the electrical conductivity of a formed oxide film by adding specified amounts of Zr and Be to a 15-30 Cr-Fe alloy. CONSTITUTION:The composition of a soft glass sealing alloy is composed of, by weight, 15-30% Cr, 0.1-1% Ti, 0.05-1% Al, <0.75% Si, <0.1% Mn, <0.03% C, <0.03% N2, 0.005-0.5% Zr, 0.005-0.5% Be and the balance Fe with inevitable impurities. The oxidation resistance of the alloy and the electrical conductivity of a formed oxide film are improved by reducing the amounts of C and N and adding Zr and Be.

Description

【発明の詳細な説明】 利用産業分野 この発明は、軟質ガラスとの封着に供する封着用合金に
係り、特に、耐蝕性及び酸化被膜の導電性を改善した軟
質ガラス到着合金に関する。
DETAILED DESCRIPTION OF THE INVENTION Field of Application This invention relates to a sealing alloy used for sealing with soft glass, and more particularly to a soft glass arrival alloy with improved corrosion resistance and electrical conductivity of an oxide film.

イj6ψJ古2Il:F 軟質ガラス封着用合金は、例えば、カラーブラウン管の
シャドーマスクを支持するスタットピン等に用いられ、
従来より軟質ガラス到着合金については種々の提案がな
されている。
Ij6ψJ古2Il:F Soft glass sealing alloys are used, for example, in stud pins that support the shadow mask of color cathode ray tubes.
Various proposals have been made for soft glass arrival alloys.

一般に封着用合金は、 ■封着用合金の熱膨張係数が軟質ガラスの熱膨張係数に
近似すること、 ■合金表面の酸化被膜が合金素地に強固に密着すること
、 ■合金表面の酸化被膜の導電性が良好なこと、■合金表
面を酸化被膜処理した後の状態で各稀酸に対する耐蝕性
にすぐれていること、等の性質を具備することが必要で
ある。現在、熱膨張係数が軟質ガラスのそれに近似して
いることから、18Cr−Fe合金が多用されている。
In general, sealing alloys: ■ The thermal expansion coefficient of the sealing alloy is close to that of soft glass; ■ The oxide film on the alloy surface firmly adheres to the alloy base; ■ The conductivity of the oxide film on the alloy surface. It is necessary to have properties such as (1) excellent corrosion resistance against various dilute acids after the alloy surface has been treated with an oxide film. Currently, 18Cr-Fe alloy is widely used because its coefficient of thermal expansion is close to that of soft glass.

  ゛また、ガラス到着は、18Cr−Fe合金を所望
形状に成形加工した後、湿潤水素中で、 1000℃〜1250℃に加熱して酸化被膜を形成し、
さらに大気中で1000℃〜1250℃に加熱すること
によって実施されているが、通常、ガラス到着後の部品
は、ガラスの表面処理を施す際に、硝酸、弗酸、混合酸
等の各種酢に浸漬されることがあり、上記した如く、耐
蝕性にすぐれていることが必要である。
゛Also, to arrive at the glass, after forming the 18Cr-Fe alloy into the desired shape, it is heated to 1000°C to 1250°C in wet hydrogen to form an oxide film.
This process is further carried out by heating the glass to 1000°C to 1250°C in the atmosphere, but normally, when glass parts are surface treated after they arrive, they are heated to various vinegars such as nitric acid, hydrofluoric acid, and mixed acids. It may be immersed in water, and as mentioned above, it must have excellent corrosion resistance.

さらに、封着合金は、シャドウマスク支持用部品として
使用する場合、表面に形成された酸化被膜を介して電子
回路を構成するため、かかる酸化被膜の導電性がすぐれ
ていることが必要である。
Furthermore, when the sealing alloy is used as a shadow mask supporting component, an electronic circuit is constructed through the oxide film formed on the surface, so the oxide film must have excellent electrical conductivity.

発明の目的 この発明は、上述した軟質ガラス封着用合金として必要
な性質を満足し、特に、耐蝕性及び酸化被膜の導電性を
改善した到着合金を目的としている。
OBJECTS OF THE INVENTION The object of the present invention is to provide an alloy that satisfies the above-mentioned properties necessary for an alloy for sealing soft glass, and in particular has improved corrosion resistance and electrical conductivity of the oxide film.

発明の構成 この発明は、 Cr 15wt%〜30wt%、Ti 0.1wt%〜
1.0wt%、AI 0.05 wt%〜1.0wt%
、Si 0.75wt%以下、Mn 1.0wt%以下
、C0.03wt%以下、N20.03wt%以下に、 Zr 0.005wt%〜0.5wt%及びBe 0.
005wt%〜0.5wt%を含有し、残部はFe及び
不可避的不純物からなることを特1散とする軟質ガラス
到着用合金である。
Structure of the invention This invention includes 15 wt% to 30 wt% of Cr and 0.1 wt% to Ti.
1.0wt%, AI 0.05wt%~1.0wt%
, Si 0.75wt% or less, Mn 1.0wt% or less, C 0.03wt% or less, N2 0.03wt% or less, Zr 0.005wt% to 0.5wt%, and Be 0.
0.005 wt% to 0.5 wt%, with the remainder consisting of Fe and unavoidable impurities.

この発明による封着用合金は、18Cr−Fe合金中の
C,N等の不純物は前記酸化被膜形成の熱処理及びガラ
ス封着時に、結晶粒界付近にCr炭化物またはCr窒化
物を形成し、粒界付近に低Cr層が形成されて耐蝕性が
低下することに鑑み、C,N量を低減し、CrよりC,
Nとの親和力の大きい元素を含有せしめてC,Nを固定
すること、及び結晶粒を微細化して粒界面積を増大して
粒界付近での低Cr層を低減することにより、耐蝕性を
大きく改善したもので、さらには緻密かつ高密着の酸化
被膜を形成することにより、一段と改善できる。
In the sealing alloy according to the present invention, impurities such as C and N in the 18Cr-Fe alloy form Cr carbide or Cr nitride near the grain boundaries during the heat treatment for forming the oxide film and glass sealing. In view of the fact that a low Cr layer is formed nearby and the corrosion resistance decreases, the amount of C and N is reduced, and C,
Corrosion resistance is improved by fixing C and N by containing elements with a high affinity for N, and by making the crystal grains finer, increasing the grain boundary area, and reducing the low Cr layer near the grain boundaries. This is a great improvement, and can be further improved by forming a dense and highly adhesive oxide film.

また、この発明による封着用合金は、Cr−Fe合金の
前記した酸化処理による表面酸化被膜は、主として、P
型半導体のCr2O3で構成され、この酸化被膜中に、
Cr3より原子価の大きい、例えば、Ti4+、Si4
+のイオンが存在すると、電気抵抗が増加することに鑑
み、酸化被膜中の前記金属イオンを極力少なくしたこと
により、導電性を改善したものである。
Further, in the sealing alloy according to the present invention, the surface oxide film formed by the above-mentioned oxidation treatment of the Cr-Fe alloy is mainly composed of P.
It is composed of Cr2O3 type semiconductor, and in this oxide film,
Higher valence than Cr3, for example, Ti4+, Si4
Considering that the presence of + ions increases electrical resistance, conductivity is improved by minimizing the amount of metal ions in the oxide film.

すなわち、この発明による封着用合金は、15〜30C
r−Fe合金系に、特定量のZrとBeを含有すること
により、上述した軟質ガラス封着用合金として必要な性
質を満足し、特に、耐蝕性及び酸化被膜の導電性にすぐ
れた封着合金を得たものである。
That is, the sealing alloy according to the present invention has a 15 to 30C
By containing specific amounts of Zr and Be in the r-Fe alloy system, a sealing alloy that satisfies the above-mentioned properties necessary for a soft glass sealing alloy, and has particularly excellent corrosion resistance and oxide film conductivity. This is what I got.

組成限定理由 以下に、この発明による封着合金の成分組成の限定理由
を詳述する。
Reasons for limiting composition The reasons for limiting the composition of the sealing alloy according to the present invention will be explained in detail below.

Crは、この到着合金の基本成分であるが、15wt%
未満では熱膨張係数が大きくなり、軟質ガラスの熱膨張
係数との差が大きくなり好ましくなく、また、30wt
%を越えると、加工性が劣化し、所定形状に成形困難と
なるため、 15wt%〜30wL%とする。
Cr is the basic component of this arriving alloy, with 15 wt%
If it is less than 30 wt, the thermal expansion coefficient becomes large and the difference with the thermal expansion coefficient of soft glass increases, which is not preferable.
If it exceeds 15 wt% to 30 wL%, processability deteriorates and it becomes difficult to form into a predetermined shape.

Tiは、合金中のγ相析出の防止及び酸化被膜の密着性
、耐蝕性改善に有効であるが、0.1wt%未満酸化被
膜の電気抵抗が高くなりすぎて導電性が劣化するため、
0.1wt%〜1.0wt%とする。
Ti is effective in preventing γ phase precipitation in the alloy and improving the adhesion and corrosion resistance of the oxide film, but if it is less than 0.1 wt%, the electrical resistance of the oxide film becomes too high and the conductivity deteriorates.
The content is set at 0.1 wt% to 1.0 wt%.

Atは、合金の脱酸及び酸化被膜の密着性の改善に有効
であるが、0.05wt%未満ではその効果がなく、ま
た、1.0wt%を越えると上記効果が飽和すると共に
硬化し、加工が困難となるため、0.05wt%〜1.
0wt%とする。
At is effective in deoxidizing the alloy and improving the adhesion of the oxide film, but if it is less than 0.05 wt%, it has no effect, and if it exceeds 1.0 wt%, the above effects are saturated and it hardens. Since processing becomes difficult, the amount of 0.05 wt% to 1.
It is set to 0wt%.

Siは、脱酸のため含有するが、0.75wt%を越え
ると脱酸効果が飽和するため好ましくない。
Si is included for deoxidation, but if it exceeds 0.75 wt%, the deoxidation effect will be saturated, which is not preferable.

Mnは、脱酸効果及び酸化被膜の最外側層に、Mn、C
r2O4スピネル酸化物を形成し、ガラスとの濡れ性を
改善する効果があるが、1.0wt%を越えると、合金
の熱膨張係数が大きくなりすぎるため好ましくない。
Mn has a deoxidizing effect and the outermost layer of the oxide film.
Although it has the effect of forming r2O4 spinel oxide and improving wettability with glass, if it exceeds 1.0 wt%, the coefficient of thermal expansion of the alloy becomes too large, which is not preferable.

Cは、到着時の発泡防止及びγ相析出の防止かつ耐蝕性
改善のためには、極力少ないほうが好ましいが、0.0
3wt%以下の含有であれば、実用上問題がない。
In order to prevent foaming upon arrival, prevent γ phase precipitation, and improve corrosion resistance, it is preferable that C be as small as possible, but 0.0
If the content is 3 wt% or less, there will be no practical problem.

N2は、γ相析出の防止かつ耐蝕性改善のためには、極
力少ないほうが好ましいが、0.03wt%以下の含有
であれば、実用上問題がない。
In order to prevent γ phase precipitation and improve corrosion resistance, it is preferable that N2 be as small as possible, but if the content is 0.03 wt% or less, there will be no practical problem.

Zrは、合金中のC,N等の不純物と結合し、炭化物ま
たは窒化物を形成してC,Nを固定し、さらに、結晶粒
を微細化すると共に、酸化被膜の密着性を改善し、これ
らの相乗効果により、耐蝕性を著しく改善する効果があ
るが、0.005wt%未満ではその効果が少なく、ま
た、0.5wt%を越えると合金の熱間加工性が低下す
るため、0.005wt%〜0.5wt%とする。
Zr combines with impurities such as C and N in the alloy to form carbides or nitrides to fix C and N, further refines crystal grains and improves the adhesion of the oxide film. These synergistic effects have the effect of significantly improving corrosion resistance, but if it is less than 0.005 wt%, the effect is small, and if it exceeds 0.5 wt%, the hot workability of the alloy decreases. 0.05 wt% to 0.5 wt%.

Beは、合金中の結晶粒を微細化すると共に、酸化被膜
の緻密性、密着性を改善し、耐蝕性を著しく改善する効
果があるが、0.005wt%未満ではその効果が少な
く、また、0.5wt%を越えると硬化しすぎて合金の
冷間加工性が低下するため、0.005wt%〜0.5
wt%とする。
Be has the effect of refining the crystal grains in the alloy, improving the density and adhesion of the oxide film, and significantly improving the corrosion resistance, but if it is less than 0.005 wt%, the effect is small; If it exceeds 0.5 wt%, it will harden too much and the cold workability of the alloy will decrease, so 0.005 wt% to 0.5
Let it be wt%.

この発明の封着合金は、ZrとBeを複合含有すること
を特徴とするが、ZrとBeの複合含有量は、0.01
wt%未満では合金中の結晶粒の微it++化効果がな
いと共に、酸化被膜の緻密性、密着性の改善効果がなく
、また耐蝕性を改善する効果もなく、また、1.0wt
%を越えると、合金は硬化して熱間加工性が低下すると
ともに、冷間加工も困難となるため、0.01wt%〜
1.0wt%とする。
The sealing alloy of the present invention is characterized by containing a composite of Zr and Be, and the composite content of Zr and Be is 0.01
If it is less than 1.0wt%, there is no effect of making the crystal grains in the alloy micro-IT++, and there is no effect of improving the density and adhesion of the oxide film, and there is no effect of improving corrosion resistance.
If it exceeds 0.01wt%, the alloy will harden and its hot workability will decrease, and cold working will also become difficult.
It is set to 1.0 wt%.

Feは、この合金の主成分であり、上述した各成分を含
有した残余とする。
Fe is the main component of this alloy, and is the remainder containing the above-mentioned components.

また、不純物としてのNiは0.02wt%以下の含有
であれば、封着合金としての所要の性質を劣化させるこ
とがない。
Further, if Ni is contained as an impurity in an amount of 0.02 wt% or less, the required properties as a sealing alloy will not be deteriorated.

実施例 以下に、この発明による実施例を示しその効果を明らか
にする。
EXAMPLES Below, examples according to the present invention will be shown to clarify its effects.

第1表に示す組成成分に従って、この発明による封着合
金(試料No、1〜2)と、比較合金(試料No、3〜
5)を作製し、各合金の電気抵抗値測定、並びに耐蝕性
試験、酸化被膜の密着性試験を行ない、その結果を第2
表に示す。
According to the composition shown in Table 1, the sealing alloy according to the present invention (Sample No. 1-2) and the comparative alloy (Sample No. 3-2)
5), measured the electrical resistance value of each alloy, conducted a corrosion resistance test, and an oxide film adhesion test, and reported the results to the second
Shown in the table.

電気抵抗値の測定は、第1表の各合金より0.8mm厚
みX40mm幅X50mm長さに切り出した試験片を、
1200℃で60秒、露点40℃の湿潤水素ガス中で予
備酸化処理したのち、1200°Cで60秒、大気中の
酸化処理を施し、その酸化被膜表面に炭素系の導電性塗
料を一定面積塗布し、乾燥させたのち、酸化被膜の電気
抵抗を測定した。
To measure the electrical resistance value, a test piece of 0.8 mm thickness x 40 mm width x 50 mm length was cut from each alloy in Table 1.
After preliminary oxidation treatment at 1200°C for 60 seconds in humid hydrogen gas with a dew point of 40°C, oxidation treatment was performed at 1200°C for 60 seconds in the air, and a certain area of carbon-based conductive paint was applied to the surface of the oxide film. After coating and drying, the electrical resistance of the oxide film was measured.

耐蝕性試験は、上記の酸化処理後の試験片に、硝酸二部
酸=1=1の混合酸(20℃)に、2時間浸漬し、この
場合の溶解減量を測定して耐蝕性を評価した。
In the corrosion resistance test, the test piece after the above oxidation treatment was immersed in a mixed acid of nitric acid = 1 = 1 (20 ° C.) for 2 hours, and the loss in dissolution in this case was measured to evaluate the corrosion resistance. did.

酸化被膜の密着性試験は、上記の予備酸化処理後の試験
片に、軟質ガラスを載置し、1200°Cに保持した加
熱装置中で30秒間加熱し、その後常温まで冷却し、本
ハンマーでガラスを破壊した際のガラスとの接着面にお
いて、酸化被膜がガラスと共に剥離して金属素地が露出
した割合により評価した。また、各試料はそれぞれ10
個ずつ試験に供した。
In the adhesion test of the oxide film, a soft glass was placed on the test piece after the preliminary oxidation treatment, heated for 30 seconds in a heating device kept at 1200°C, then cooled to room temperature, and then heated with a real hammer. Evaluation was made based on the rate at which the oxide film peeled off together with the glass and the metal base was exposed on the adhesive surface with the glass when the glass was broken. In addition, each sample had 10
Each piece was subjected to the test.

すなわち、評価は、 G1:金属素地が全く認められない、 G2;金属素地の露出が5%未満、 G3;金属素地の露出が5%〜10%、である。In other words, the evaluation is G1: No metal base is recognized at all. G2; less than 5% of the metal base exposed; G3: The exposure of the metal base is 5% to 10%.

第2表の試験結果から明らかな如く、この発明による封
着合金は、所要の性質を満足すると共に、耐蝕性及び酸
化被膜の導電性にすぐれていることが分る。
As is clear from the test results in Table 2, the sealing alloy according to the present invention satisfies the required properties and has excellent corrosion resistance and electrical conductivity of the oxide film.

以下余白Margin below

Claims (1)

【特許請求の範囲】 1 Cr15wt%〜30wt%、Ti0.1wt%〜1.
0wt%、Al0.05wt%〜1.0wt%、Si0
.75wt%以下、Mn1.0wt%以下、C0.03
wt%以下、N_20.03wt%以下に、 Zr0.005wt%〜0.5wt%及び Be0.005wt%〜0.5wt%を含有し、残部は
Fe及び不可避的不純物からなることを特徴とする軟質
ガラス封着用合金。
[Claims] 1 Cr: 15wt% to 30wt%, Ti: 0.1wt% to 1.
0wt%, Al0.05wt%~1.0wt%, Si0
.. 75wt% or less, Mn 1.0wt% or less, C0.03
A soft glass characterized by containing 0.005 wt% to 0.5 wt% of Zr and 0.005 wt% to 0.5 wt% of Be in 20.03 wt% or less of N_20.03 wt% or less, with the remainder consisting of Fe and inevitable impurities. Alloy for sealing.
JP3659187A 1987-02-19 1987-02-19 Soft glass sealing alloy Granted JPS62188752A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3659187A JPS62188752A (en) 1987-02-19 1987-02-19 Soft glass sealing alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3659187A JPS62188752A (en) 1987-02-19 1987-02-19 Soft glass sealing alloy

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP12829883A Division JPS6021360A (en) 1983-07-13 1983-07-13 Alloy for sealing soft glass

Publications (2)

Publication Number Publication Date
JPS62188752A true JPS62188752A (en) 1987-08-18
JPS6319587B2 JPS6319587B2 (en) 1988-04-23

Family

ID=12474022

Family Applications (1)

Application Number Title Priority Date Filing Date
JP3659187A Granted JPS62188752A (en) 1987-02-19 1987-02-19 Soft glass sealing alloy

Country Status (1)

Country Link
JP (1) JPS62188752A (en)

Also Published As

Publication number Publication date
JPS6319587B2 (en) 1988-04-23

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