JPS60103159A - Seal bonding alloy - Google Patents

Abstract

PURPOSE:To obtain a relatively inexpensive seal bonding alloy having a proper coefft. of thermal expansion, ensuring high airtightness with soft glass, and undergoing almost uniform oxidation by providing a specified composition consisting of Cr, Al, Si, C, N, Ti, Zr and Fe and satisfying specified relation. CONSTITUTION:This seal bonding alloy consists of, by weight, 20-35% Cr, 0.05-0.5% Al, 0.05-0.5% Si, 0.02-0.07% C, 0.005-0.04% N, 0.2-0.7% Ti and/ or 0.3-1.0% Zr (Ti+Zr/2=0.3-1.2%) and the balance Fe with inevitable impurities and satisfies relation represented by an equation (Ti+Zr/2)-4X(C+N)= 0.15-0.8%. The alloy has 100-115X10<-7>/ deg.C average coefft. of thermal expansion at 30-500 deg.C and high adhesive strength to glass, ensures high airtightness, and contains no expensive Ni. When the alloy is subjected to oxidation treatment, it undergoes almost uniform oxidation and hardly causes crack in glass.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to Fe-0r used for airtight terminals with soft glass.
The purpose is to create a sealing alloy that is good for other alloys, has excellent airtightness, and does not cause oxidation unevenness during oxidation treatment.

Conventionally, 42 is used as an alloy for sealing with glass.
Ni-60r-Fe alloy (hereinafter referred to as 426 alloy),
29111-170o -Fe alloy, 42-52111
-Fe alloy, 180r --Fe alloy (hereinafter 430T
i-alloy) are known. Each type of material is used according to its unique thermal expansion coefficient, oxidation properties, etc.

426 alloy, which is an alloy for sealing with soft glass, has excellent sealing properties with glass and workability, and is mainly used for gamma node buttons of TV cathode ray tubes and spacer frames of fluorescent display tubes. It has the disadvantage that it is expensive because it contains it.

Fe-Or as a resource-saving material for near-m spacer frames
Although alloys are being considered, the coefficient of thermal expansion α (
30~500℃) -108Xlo-f/℃ compared to 1
80r series 430Ti alloy has α, 119XIO″′ f/
℃, and the distortion during glass sealing becomes large.

The coefficient of thermal expansion of the Fe-0r alloy becomes smaller as the Or content increases, and becomes close to the value of the 426 alloy, making it a sufficient substitute for the 426 alloy.

Prior to sealing with glass, glass sealing alloys are generally subjected to oxidation treatment in a weakly oxidizing atmosphere after molding in order to improve the tight layer strength. 426 alloy and 'fPe-Or alloy are usually treated at 1050-1200°C in 30m1n-2H in wet hydrogen or wet ammonia decomposition gas.
O2 is then mixed with the glass through this oxide film. However, when conventional 'Fe-0r alloys are oxidized, the crystal grains of the alloy become coarse and irritable, causing the thickness of the plate to become thicker, like spacer frames for fluorescent display tubes. When the thickness is as thin as 025111 or less, there is a problem that both sides of the plate are connected by one crystal grain boundary, and there is a problem of slow leakage due to the diffusion of gas at the grain boundary. In addition, in the oxidation treatment, color unevenness was caused by differences in whisker size, and there was a risk of glass cracking.

The present invention is based on the fact that, through research on the relationship between Fe-Or gold alloy composition, thermal expansion grain size, oxidation properties, and glass adhesion strength, it was discovered that there is an alloy composition range that compensates for the above-mentioned drawbacks.

i.e. 0r2Q-35%, AID, 05-0.5%,
5in-05-0.5%oo, 02-0.07%, lJ
O, o05-0.04%, T10.2-0.7%, Zr
In the case of any one or two types of O2-10% (Ti% +
9%) and α3 to L2%, and the above ON, Ti, Zr
Between (T? 10 Zr%” 2) 4 X (0%+N
%) or 0.15-0.8, with the remainder being substantially I
The alloy, which is composed of re, has an average thermal expansion coefficient of 100115Xlo-'/°C between 30°C and 500'C, and has high airtightness, oxidation unevenness, and close layer strength with glass, and has properties equivalent to or better than 426 alloy. 0 Next, we will discuss the reason for limiting the range of components.

“If Or is less than 20%, it has a large coefficient of thermal expansion and tends to form austenite when heated at high temperatures, and if it exceeds 35%, the workability deteriorates. It has the effect of increasing the strength of the oxide film by forming internal oxidation particles, but if the amount of each is less than 0.005%, it has no effect, and if it exceeds 0.05%, oxidation unevenness tends to occur, so 0.05-α5 %.

0 and N combine with T1 and Zr, for example, Ti(0,N
), which is effective in preventing coarsening of crystal grains and slow leakage during oxidation treatment. If it is less than 0.02% or NO, less than 0.005%, less T1 (0, N) is generated and there is no effect of preventing crystal grain coarsening. 0 is 0.07%
Exceeding this will result in foaming during glass sealing and a decrease in workability. Also, if N exceeds 0.04%, oxidation unevenness tends to occur, so 00.02-007%, NO, 005-0.
O T1 and Zr limited to 0.04% form a compound with O and N and exhibit a similar effect in preventing crystal grain coarsening, but Ti and Zr each have no effect at less than 0.2%. In addition, T1 and Zr are elements that also affect the adhesion and oxidation unevenness of the oxide film, and if Ti and Zr exceed α7% and 10%, respectively, there is no improvement in @N strength, and processing The upper limits were limited to 0.7% and 10%, respectively, because the properties of the two components decreased.

Also, for the same reason when containing 2 yuzu (T1+”/2)
was set at 0.3 to L2%.

Q, 11. Ti, Zr opening ratio 1 coefficient formula (T1%+”'J
) -4X (0%+N%) indicates the total IT of T1 and zr freely present in the alloy, and this may be related to oxidation behavior, and if it is less than 0.15%, oxidation unevenness tends to occur. Also 0・
If it exceeds 8%, it tends to impair the adhesion of the oxide film, so (Tl+Zr%l/2)-4X(0%+N%) is 0.1
5-0.8.

The actual m M will be described below.

After the Fe-Or thread alloy is processed in a high frequency vacuum furnace, it is forged, hot rolled and cold rolled to a plate thickness of 0.
．． A 251m strip was obtained. The coefficient of thermal expansion at this time was determined by taking a 5φ x 2o111it test piece from the forged material.
900 table (Note 1) λ is (Ti% + Zr%/2) -4X (0
%+N%].

(Note 2) α is the average coefficient of thermal expansion from 30℃ to 500℃ (×
℃] is shown.

(Note 3) G and S represent the crystal grain size, and coarser grains than G and S2 are indicated by ×, and finer grains are indicated by ○.

(Note 4) When it flashes to @-shaped unevenness, the Q mark is "none" and the X mark is "
"Yes".

(Note 5) Glass adhesion strength is based on the remaining oxide film area of 15%)
shows.

'Measured after QXIH furnace cooling treatment.

Oxidation treatment was performed from 20111 strips with a plate thickness of 025u.
A test piece of 20× was taken, polished with emery paper 700, and then heated to 1100°C in a hydrogen atmosphere with a dew point of +38°C.
I went 30m1n. The oxidation unevenness and crystal grain size of the alloy were investigated for this test piece.

In addition, the close layer strength with glass was measured by the following method.

First, place a small piece of glass on the oxidized test piece,
Glass was welded onto the oxidized BQ by treatment in the atmosphere at 1150° C. x 2 m4n. Thereafter, the test piece was bent with pliers at room temperature and the glass was peeled off, and evaluation was made based on the percentage of area where the oxide film remained.

The table shows the chemical compositions of the invention alloy and comparative alloy and the results of each glaze test.

As is clear from the table, the alloy of the present invention has excellent crystal grain size characteristics, oxidation unevenness, and close layer strength with glass, and can be used as a substitute for the expensive 426 alloy, so it has great industrial benefits. be.

Applicant: Nichibun Kinpū Co., Ltd. (b)

Claims (1)

[Claims] L Weight% Nite 0r20-35%, AIQ05-0.
5%, SiO, 05~05%, 0002~007 wire M
O1005 ~ (LO4% and 'l1OJ ~CL7%, z
rQ, any of 2~LO% 1'1fIM or 2yu (Ttz+2r%'/2) woo, 3~ha yb
Including Mi, ;6”) Above X element') OlN sTl, Z
(71% + 2% 7z) - aX (0% 10N%) has a relationship of 0.15-0.8 between A sealing alloy with an average coefficient of thermal expansion of 100-115 x 10-'/°C and excellent airtightness and oxidation unevenness.