JPS61147851A - Alloy for sealing glass - Google Patents

Abstract

PURPOSE:To obtain an inexpensive alloy for sealing glass having superior sealing performance and capable of being substituted for a 42Ni-6Cr-Fe alloy by incorporating specific amounts of Cr, C, O, N, H, P, and S to Fe. CONSTITUTION:The alloy for sealing glass consists of, by weight, 10-15% Cr, <0.02% C, <0.015% O, <0.025% N, <0.0005% H, <0.05% P, <0.05% S, and the balance Fe with inevitable impurities, or further contains, as the auxiliary component, 1 or >=2 kinds among 0.1-3% Si, 0.1-1% Mn, and 0.05-1% Al, or 1 or >=2 kinds among 0.05-1% Ti, 0.05-1% Zr, 0.05-1% Nb, 0.01-2% Cu, 0.01-3% Mo, 0.01-0.5% Mg, 0.01-0.5% Ca, 0.01-0.5% V, and 0.005-0.2% B, or both of the above two components.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] The present invention relates to a sealing alloy used for sealing with soft glass.

[Conventional technology]

Conventionally, 42Ni-60r- is used for sealing with soft glass.
Although Fe alloy and 180r-Pe alloy are used.

42Ni-6Or-Fe alloy has excellent compatibility with soft glass in terms of thermal expansion properties and sealing strength.
Since it contains as much as 2%, it has the disadvantage of being extremely expensive. On the other hand, 1BOr-Fe alloy is inexpensive, but has problems in terms of compatibility of thermal expansion characteristics with soft glass and sealing strength.
At present, it has not reached the point where it can replace alloys. However, there is a strong demand for an inexpensive material with sealing properties equivalent to that of the 421)1-6Cr-Pa alloy.

In response to these demands, the present invention was developed as a result of various studies on the 0r-Pa alloy, which has high sealing properties and 42
The present invention provides an inexpensive alloy that can sufficiently replace the Ni-60r-Fe alloy. That is, 1 weight -0r10~1
Less than 551, Cα020 or less, less than paoss, less than 5aoss, balance Fe and unavoidable impurities, glass sealing alloy and weight less than 0r10 to 15ts, Cα02- or less, 010151 or less, N(0.02
5- or less.

H CLOO05% or less, P0.05 or less, 5(1
05- Below, S1α1~3chi, Mn(L1
~1-, AX (1ai or 2 or more types out of 105 ~1%.

Glass sealing alloy consisting of balance Fe and unavoidable impurities and weight - less than 0r10-15, 0L102S or less, 010151 or less, N0. O25 arrogance or lower, aaooo
s* or less, pcLos* or less.

Sα05Ls or less, T1α05 or more ~ 1* as a subcomponent,
Zr105~1%, Nbα05~1%, Cuα01~
2%, MO(Lol ~5'lk, MgCLO1 ~G
．． 5%.

Cal101-1) 5s, vQ. 01~cL59b,B
Glass sealing alloy consisting of one or more of CL005 to cL2-, balance Fe and unavoidable impurities, and Cr10 to less than 15% by weight, an02n or less, O
O. 015% or less, Nl1025% or less, Hα0005
2105% or less, Sα05% or less, S1α1-3 as a subcomponent, Mn1)-1).

1'M or 2 or more of A1α05-1- and Ti
lO5~1%, Zr(LO5~1s
, N'b0. O5~1%, Ouα01~2-, Mo
101~3%, Mgα01~(15%, 0a(LO
1~cL5%, Vα01~α5chi, B[1005~02
%, the balance F's and unavoidable impurities, and an alloy for glass sealing in which the crystal grain size is 8.0 or more.

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

Or greatly affects the compatibility of thermal expansion characteristics with glass, and if it is less than 10, the α phase becomes unstable and is not compatible with glass. In terms of compatibility of thermal expansion characteristics, 3
It is possible to contain up to about 0%, but if it is included in a large amount, workability and soldering properties will deteriorate, so from these points of view it is set to less than 10-15.

The content of C must be reduced in order to stabilize the α phase, and if it is contained in excess of α02-, it may cause bubbles to be generated in the glass during sealing, so the upper limit of C must be reduced.
It was set at 0.02%.

If P is contained in excess of 1los*, oxidation unevenness tends to occur, so the upper limit was set at αaSS.

If S is contained in an amount exceeding α0591, oxidation unevenness tends to occur, and the adhesion between the oxide film and the base metal also decreases, so the upper limit was set at (LO5-).

If the content of 0 exceeds α015%, the oxide film becomes uneven and the density of the oxide film deteriorates, resulting in a significant loss of sealing strength. In addition, since bubbles are easily created in the glass during sealing, the upper limit was set at α015.

Similar to 0, if N is contained in excess of cL025%, the sealing strength will be significantly impaired, so the upper limit was set at 0.025%.

If H is contained in excess of cL0005%, the sealing strength will be impaired, so the upper limit was set at 10005*.

As a subcomponent, 81 forms a concentrated layer of Sl between the Or oxide layer and the base metal during oxidation treatment.

Although it improves the adhesion between the oxide film and the base metal, it is not effective when α is less than 1%, and when it is contained in more than 3%, the thermal expansion characteristics change and workability deteriorates, which is not preferable.

Mn forms an oxide with good wettability with glass on the outer layer of the oxide film, improving the wettability between the oxide film and glass, but α1
If it is less than -, there is no effect, and if it exceeds -, the oxidation rate will be high and the oxide film will be too thick, making it unsuitable for sealing.

A1 improves the adhesion strength between the oxide film and the base metal.

If it is less than α05-, there is no effect, and if it is more than 1-, the thermal expansion characteristics change, which is not preferable.

Furthermore, in order to further improve the sealing property, it is effective to add a small amount of the following elements that improve the sealing property.

That is, more than 1% of Tiα05, Zrα05~1−,
Nb(LO5~1%, Ou(L(M~2%, Mo0.
01-3%, Mgα01-α5%, Ca001-15-
When one or more of 17105 to CL5% and Bα005 to 12% are contained, the sealing property is further improved.

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

T1 improves the adhesion between the oxide film and the base metal.

If it is less than α05ts, there is no effect, and if it exceeds 1%, workability becomes poor 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 it has no effect below cLoss.
Exceeding 1) will impair workability.

Nl) improves the adhesion between the oxide film and the base metal.

[If it is less than 105 inches, there is no effect, and if it exceeds 1-, it will impair workability.

Although Ou makes the oxide film dense and improves sealing properties.

If it is less than CLO1S, there is no effect, and if it exceeds CLO1S, the oxide film becomes too thick and unsuitable for sealing.

MO improves the adhesion between the oxide film and the base metal.

If it is less than (101), there is no effect (and if it exceeds 3 degrees, workability will be impaired and oxidation unevenness will easily occur.

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 Q, 01), it has no effect;
(If it exceeds lss, the oxide film will be too thick, which is not preferable.

Although Oa improves the adhesion between the oxide film and the base metal.

If it is less than (101), there is no effect, and if it exceeds α51, oxidation unevenness tends to occur, which is not preferable.

V improves the adhesion between the oxide film and the base metal.

If α is less than 01%, there is no effect, and if it exceeds α5, workability will be impaired and oxidation unevenness will easily 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 when it is less than lloss, and when it exceeds α2- it tends to cause oxidation unevenness.

It has also been confirmed that excellent sealing properties can be stably obtained by appropriately controlling the grain size of these alloys, and favorable effects can be obtained when the grain size is a grain size number a0 or more. .

Next, the present invention will be explained in detail using examples.

〔Example〕

Tables 1 and 2 show the alloys of the present invention and comparative examples. Each alloy was melted and cast in a vacuum high-frequency induction melting furnace, and then heat treated and rolled repeatedly to produce a plate with a thickness of 15 m. After degreasing the surface of this sample, it was heated at 950°C in wet hydrogen for 2 hours. After forming an oxide film on the surface of 2, it was subjected to a sealing test with glass.The adhesion strength was determined after sealing the glass.
It was measured by a tensile test.

Samples 1 to 26 are alloys of the present invention, and comparative alloys 427 to 31 are alloys of the present invention. The alloy of the present invention has an adhesion strength of 3.
It shows OK4/- or higher and is suitable as a sealing alloy. Among them, 81. M0. Mums 4 to 10 containing Al and A1 to 15 containing elements such as T1 have an adhesion strength of 53/- or more, 81. M0. Mums 16 to 26 to which elements such as A1 and T1 are added exhibit adhesion strength a of ok4/- or more and are optimal as sealing alloys. On the other hand, the comparative alloy has low adhesion strength (, sl
, M0. Even if elements such as Al and T1 are added, at most 2
．． Since it is only ob/-, it is not suitable as a sealing alloy.

Next, regarding the influence of crystal grain size, Table 3 shows the results of a test using 41.7.25 as a test material.

It can be seen from Table 3 that as the crystal grains become smaller, the adhesion strength improves. Therefore, in order to stably obtain excellent sealing properties, it is effective to make the crystal grain size equal to or larger than the grain size number &O.

As described above, the alloy of the present invention has excellent sealing properties and can be used in parts requiring high quality, for which conventional 42Ni-6Or-Fe alloys have been used.

Moreover, it is an industrially extremely valuable alloy that can be produced at a much lower cost than the 42N1-6Or-Fe alloy.

Table 3

Claims (5)

[Claims] (1) Cr 10-15% by weight, C 0.02% or less, O 0.015% or less, N 0.025% or less, H0.
An alloy for glass sealing consisting of 0.0005% or less, P 0.05% or less, S 0.05% or less, and the remainder Fe and unavoidable impurities. (2) Cr 10-15% by weight, C 0.02% or less, O 0.015% or less, N 0.025% or less, H0.
0005% or less, P 0.05% or less, S 0.05% or less, Si 0.1-3%, Mn 0.1-1% as subcomponents,
One or more types of Al0.05-1%, balance F
An alloy for glass sealing consisting of e and unavoidable impurities. (3) Cr less than 10-15% by weight, C 0.02% or less, O 0.015% or less, N 0.025% or less, H0.
0005% or less, P 0.05% or less, S 0.05% or less, Ti more than 0.05 to 1% as subcomponents, Zr 0.05 to
1%, Nb0.05-1%, Cu0.01-2%, Mo
0.01-3%, Mg0.01-0.5%, Ca0.0
1-0.5%, V0.01-0.5%, B0.005-
An alloy for glass sealing consisting of one or more of 0.2% and the remainder Fe and unavoidable impurities. (4) Cr 10-15% by weight, C 0.02% or less, O 0.015% or less, N 0.025% or less, H0.
0005% or less, P 0.05% or less, S 0.05% or less, Si 0.1-3%, Mo 0.1-1% as subcomponents.
One or more of Al0.05-1% and Ti
More than 0.05 to 1%, Zr0.05 to 1%, Nb0.05
~1%, Cu0.01-2%, Mo0.01-3%, M
g0.01-0.5%, Ca0.01-0.5%, V0
．． An alloy for glass sealing comprising one or more of 0.01 to 0.5%, B0.005 to 0.2%, and the remainder Fe and unavoidable impurities. (5) In the alloy according to claim (1) or (2) or (3) or (4),
An alloy for glass sealing whose crystal grain size is 8.0 or more.