JPH02236256A - Alloy for sealing glass - Google Patents

Abstract

PURPOSE:To produce the alloy for sealing soft glass having low thermal expendability and excellent glass sealability by incorporating specific ratios of Ni, Cr, C, O, N, P, S, Ti, Nb, Cu, Mo, Mg, Ca, V, and B into Fe. CONSTITUTION:The alloy contg., by weight %, 30 to <37% Ni, 1 to 10% Cr, <=0.1% C, <=0.015% O, <=0.025% N, <=0.05% P, and <=0.05% S, contg., as auxilia ry components, one or >=2 kinds among over 0.05 to 1% Ti, 0.05 to 1% Nb, 0.01 to 2% Cu, 0.01 to 3% <=0.01 to 0.5% Mg, 0.01 to 0. 5% Ca, 0. 01 to 0.5% V, and 0.005 to 0.2% B, and consisting of the balance Fe and unavoidable impuri ties is prepd. and the crystal grain size thereof is specified to >=8.0 grain size number. The alloy which is liable to form Fe3O4 is formed in this way and the soft glass sealing is easily executed.

Description

[Detailed description of the invention] Kashiri Gowasen The present invention relates to an alloy for sealing soft glass.

′ and are alloys traditionally used for sealing with soft glass.
A 42%Ni-6%Cr-Fe alloy is often used because its thermal expansion coefficient matches that of soft glass and its sealing strength is good. This conventional 42%Ni-6%Cr
When sealing the -Fe alloy, first, as a preliminary treatment, Cr is preferentially oxidized in wet hydrogen, and then the alloy is sealed with glass in the atmosphere. At that time, Fe,0, which has a strong bonding force with glass,
．． is formed, and good sealing strength with glass is obtained.

However, the 42%Ni-6%Cr-Fe alloy contains 48% of non-ferrous elements including Ni and Cr, so in normal processing, Fe, 0. is not formed sufficiently, and this Fe
,0. The problem was that it took too much time to form a sufficient amount.

115. The present invention was made in view of this point, and provides an alloy that has a low coefficient of thermal expansion, excellent sealing properties to glass, and can be efficiently sealed to glass. That is, Ni30 to less than 37%, Or1 to 10%, C0.1 in weight%
% or less, 00,015% or less, N0.025% or less, P
0.05% or less, 80.05% or less, Ti as a subcomponent
e, more than 05 to l%, Zr0.05 to 1%, Nb0.05
~1%, Cu0.01~2%, Mo0.01%~3%,
Mg0.01-0.5%, Ca0. OI ~0.5%,
An alloy for glass sealing consisting of one or more of V0.01 to 0.5% and 80.005 to 0.2%, the balance Fe and unavoidable impurities, and in this alloy, the crystal grain size is grain size number 8 The present invention relates to an alloy for glass sealing which is .0 or more.

As a result, 42%Ni, which has the excellent low thermal expansion properties of the conventional
-6%Fe, which has the same thermal expansion characteristics as Cr-Fe alloy, and has a strong bond with glass due to the reduced amount of non-ferrous elements. is formed more easily, increasing the work efficiency of glass sealing and improving the overall sealing performance of 42%Ni-6%Cr-Fe.
An alloy superior to that of the alloy was obtained.

Furthermore, since the alloy of the present invention has a lower content of expensive N1 than the conventional alloy, it is inexpensive in terms of cost and is an extremely excellent alloy.

Next, the reasons for limiting the composition of the alloy of the present invention will be explained.

Ni has the greatest influence as an element on compatibility with glass, that is, on adapting to the thermal expansion characteristics of glass. If the Ni content is less than 30%, the thermal expansion coefficient becomes high and the thermal expansion characteristics become incompatible with glass. Moreover, if it exceeds 37%, the content of non-ferrous elements becomes too high and Fe, ○. It becomes difficult to form, and it is also economically disadvantageous. For this reason, the Ni content was reduced to 3
0% to less than 37%.

Cr is an element that greatly affects compatibility with glass and sealing strength. As the content of Or increases, the coefficient of thermal expansion increases. Therefore, by controlling the contents of Ni and Cr in accordance with the glass used for sealing, it is possible to finely adjust the thermal expansion characteristics of the alloy of the present invention to the optimum one.

However, if the Cr content exceeds 10%, the coefficient of thermal expansion becomes too large, making it unsuitable for glass sealing. In addition, prior to sealing the alloy of the present invention with glass, an oxide film is formed on the surface as a preliminary treatment, and the glass is sealed via this oxide film, but the sealing strength is determined by the bonding strength between this oxide film and the alloy base metal. It also depends on the adhesion.

In order to improve the adhesion between the oxide film and the alloy base metal, it is necessary to preferentially oxidize chromium and form a chromium oxide film in the preliminary treatment. For this purpose, the Cr content must be 1
% or more is required. Based on the above, the Cr content was set to 1 to 10%.

If C is contained in an amount exceeding 0.1%, bubbles are likely to form in the glass during sealing, which significantly reduces the sealing strength. For this reason, the upper limit of the C content was set at 0.1%.

O is an element that greatly affects the formation and sealing of the oxide film, and if it is contained in an amount exceeding 0.015%, the oxide film becomes uneven and the density of the oxide film deteriorates, resulting in a significant loss of sealing strength. It will be done. Furthermore, in the worst case, bubbles may be formed in the glass during sealing, which is undesirable. Therefore, the upper limit of the ○ content was set at 0.015%.

Like ○, N is also an element that greatly affects the sealing property, and is 0.0
If the N content exceeds 25%, the sealing strength will be significantly impaired, so the upper limit of the N content was set at 0.025%.

If P exceeds 0.05%, oxidation unevenness tends to occur, so the upper limit was set at 0.05%.

If S exceeds 0.05%, oxidation unevenness tends to occur, and the adhesion between the oxide film and the base metal decreases, so the upper limit was set at 0.05%.

In addition, Ti0.
More than 0.05 to l%, Zr0.05 to 1%, Nb0.05 to 1
%, Cu0.01-2%, Mo0. O1-3%, Mg
0.01-0.5%, Ca0. O1~0.5%, V0
．． The sealing properties are further improved by containing one or more of 01 to 0.5% and 80,005 to 0.2%.

The reason for adding these subcomponents and the reason for limiting the range of the components will be described below.

Ti improves the adhesion between the oxide film and the base metal, but at 0.05
% or less, there is no effect, and if it exceeds 1%, workability deteriorates and the oxide film tends to become uneven.

Zr improves the adhesion between the oxide film and the base metal and the wettability of the oxide film with the glass, but if it is less than 0.05% it has no effect, and if it exceeds 1% it impairs workability.

Nb improves the adhesion between the oxide film and the base metal, but 0.05
If it is less than 1%, it will have no effect, and if it exceeds 1%, it will impair workability.

Cu makes the oxide film dense and improves the sealing property, but 0.0
If it is less than 1%, there is no effect, and if it exceeds 2%, the oxide film becomes too thick and becomes unsuitable for sealing.

Mo improves the adhesion between the oxide film and the base metal, but at 0.01
If it is less than 3%, it is ineffective, and if it exceeds 3%, it impairs workability and tends to cause uneven oxidation.

Mg improves the adhesion between the oxide film and the base metal and the wettability of the oxide film with the glass, but if it is less than 0.01%, it has no effect, and if it exceeds 0.5%, the oxide film becomes too thick, which is not preferable.

Ca improves the adhesion between the oxide film and the base metal, but at 0.01
If it is less than 0.5%, there is no effect, and if it exceeds 0.5%, oxidation unevenness tends to occur, which is not preferable.

(2) improves the adhesion between the oxide film and the base metal, but 0. Ol%
If it is less than 0.5%, there is no effect, and if it exceeds 0.5%, workability is impaired and oxidation unevenness tends to occur.

B improves the adhesion between the oxide film and the base metal and the wettability between the oxide film and the glass, but it has no effect if it is less than 0.005%.
The alloy components of the present invention have been explained above because if the content exceeds 0.2%, oxidation unevenness tends to occur. However, by appropriately controlling the crystal grain size of these alloys, it is possible to stably achieve even better sealing properties. It was confirmed that it was obtained. That is, when the crystal grain size is 8.0 or more, excellent sealing properties are obtained.

Next, the present invention will be explained in detail with reference to examples.

Examples and comparative examples of the alloy of the present invention are shown in Table 1. After vacuum melting and casting, each alloy is heat treated and rolled repeatedly to produce a plate with a thickness of 0.
Finished with 3M board. The thermal expansion coefficient of this sample was measured, and the sealing strength was determined by degreasing the surface of this sample, heating it in wet hydrogen at 1050°C for 20 minutes to form an oxide film on the surface, and then sealing it with glass. The adhesion strength was determined and evaluated by a tensile test.

Samples Nα1 to Nα5 are alloys of the present invention, and comparison alloys thereof are grades 6 to 11. The alloy of the present invention has a coefficient of thermal expansion α3
0-350 is 7-12X10=/'C, it is well compatible with glass, and the adhesion strength is 4.0 kg/m
m" or higher, making it suitable as a sealing alloy. On the other hand, comparative alloys 6 to 10 are out of the composition range of the present invention, so their thermal expansion coefficients are either too high or too low, or their adhesion strength is insufficient. Therefore, it is not suitable as a sealing alloy.kl
1 is a 42% Ni-6% Cr-Fe alloy, but its overall adhesion strength is inferior to that of the alloy of the present invention.

Next, regarding the influence of crystal grain size, in order to stably obtain excellent sealing properties, it is effective to set the crystal grain size to a grain size number of 8.0 or more.

As described above, the alloy of the present invention has excellent sealing properties and is an inexpensive, industrially extremely useful alloy that can sufficiently replace the conventional 42% Ni-6% Cr-Fe alloy.

Margin below

Claims (2)

[Claims] (1) Ni 30 to less than 37%, Cr 1 to 10% by weight
, C0.1% or less, O0.015% or less, N0.025
% or less, P 0.05% or less, S 0.05% or less, Ti over 0.05 to 1% as subcomponents, Zr 0.05 to 1%, N
b0.05-1%, Cu0.01-2%, Mo0.01
%~3%, Mg0.01~0.5%, Ca0.01~0
．． 5%, V0.01-0.5%, B0.005-0.2
A glass sealing alloy consisting of one or more of the following, the balance being Fe and unavoidable impurities. (2) The glass sealing alloy according to claim (1), wherein the crystal grain size is 8.0 or more.