JPS59174543A - Crystallizable glass solder with low thermal expansion rate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to partially crystallized glass solder,
This glass solder is available in powder form for quartz glass, transparent h-quartz mixed crystal-containing glass ceramics and opaque h+
-5 to +33.10-7 in the temperature range of 20 to 500 °C, such as IJ pyroxene-containing glass ceramics, and materials with p8II tension of K heat, such as 20 to 30
Suitable for mechanically strong bonding of DURAN 50 type borosilicate glass having an alpha value of 33.10-7.-' in the 0° C. range with low fusion stress.

The composition of glass solder is 50 to 90 layers of ti2o-AQ205-5i.
o2-based h-quartz mixed crystal phase and boric anhydride (B203
), -lead oxide (pbo), sodium oxide (Na20)
, 10-50% consisting of components not incorporated into the h-quartz mixed crystal lattice, such as potassium oxide (F20), fluorine (F2), etc.
The glass phase further comprises titanium oxide (Tj02) in an amount of up to 4% by weight as a nucleating agent.

Furthermore, this welding glass contains magnesium oxide (Mgo) and copal oxide 1-(Co□) which form mixed crystals.
It can contain up to tIj. Fusion (welding) (f
It has already been proposed that a B2O3 content of at least 3% by weight, preferably 5.0% by weight or more, is a prerequisite for the bond strength of the bonding process (soldering) to be technically useful.

Due to the presence of the glass phase part, the molar ratio t, i2o:AF
, 205: 8102 = 1: 1: 2
i.e. 11,86 LM % Li2O and 40.
AQ2o3 of 46-layered and sio of 47.68-layered
, , and the pure h-quartz mixed crystal-containing composition, which tends to crystallize significantly during the fusion process at 1420-1300 °C, is well stabilized, so that the glass solder has a homogeneous glass state. It can be melted and processed into glass powder.

For welding, finer than 100 μm, preferably 20
It has been demonstrated that atomization finer than μm is appropriate. The glass solder powder can be used in the form of a paste or with a thickness of 10
It is applied in the welding process as a screen printed layer of ~250 μm, preferably 25-100 ttm.

The welding process includes the following steps. Evaporation of the solvent of the paste, -nucleation of the h-quartz mixed crystal phase, -sintering or welding and crystallization of the h-quartz mixed crystal phase of the Li2O-AQ205-5io2 system.

Evaporation of the solvent is achieved during the heating process at temperatures below 500°C. Nucleation and crystallization from 550℃ to 850℃
occurs between. It is useful for welding or sintering to maintain temperatures above 650° C. for borosilicate glass and above 780° C. for quartz glass and glass ceramics for a relatively long period of time.

There are two programs specific to the welding of transparent h-quartz-containing glass-ceramics, such as ZE)"tODUR.

Program ■: 2 K/Tia 10 K/1nia-1-→
600℃ −→ZT.

(ZT-room temperature) Program ■: 4.8 K/h 10 K/h--11 600
0G---→zT Program I has been demonstrated to be suitable for welding borosilicate glasses. : Furnace 24 Otowa ZT -4500°C 680°C 1 hour duration 2V-Furnace m-→450°C--→ZT For fusion processes for transparent glass-ceramics realized at temperatures lower than 850°C, welding is It is advantageous to carry out under pressure. 500, g
/c++! It has been found that the above pressure significantly increases the mechanical strength of the weld. Pressurization can be achieved both by external loads and, in the case of hollow bodies, by the application of a vacuum.

The welding process must be carried out at temperatures below 900°C, since at temperatures above 900°C the h-quartz mixed crystals convert to spodumene.

Welding under pressure has also been demonstrated to be suitable for mechanically strong bonding of borosilicate glasses.

Evaluation of the bonding strength of the glass solder in each case is carried out with L-shaped fused specimens loaded to failure by bending stress. As a result, the strength values obtained for suitable glass solders are 10-24 N/mrs,
It is 2.

The stresses that can occur in the glass solder layer and the fusion partner are diffusion stress and 7
``Fusion stress''
Consists of.

Diffusion stress is developed by ion exchange between the glass solder and the fusion partner. The magnitude of the diffusion stress as well as the thickness of the stress layer depends, as is known, on the various chemical potentials of the two binding partners, the temperature and the diffusion time. If the diffusion time is not too long (unit: time), iooμ
For glass solder layers larger than m, the diffusion stress profile is independent of the glass solder layer thickness.

The magnitude of the fusion stress is measured by the coefficient of thermal expansion of the fusion region of the fusion partner and the 6 transition temperature, which can be approximately equated to the Tg wet temperature of the glass solder upon slow cooling.

The diffusion stress can be easily measured since the diffusion layer usually has a thickness of only a few μm (5-10 μm) after a short tempering of a few hours (for example according to Program I). The stress that develops in this thin diffusion layer is often greater than the fusion stress. Therefore, the stress in the diffusion layer can be regarded as diffusion stress.

Glass solder 1 in Table 1 was applied to the surface layer of ZERODUR during tempering according to program I with a layer thickness of 30 μm.
A compressive residual stress of 0 nm/am to 83 N/ynm2 is generated. It is desirable that the diffused compressive stress, which opposes the fusion stress, be generated on the surface layer of the fusion partner because it increases the mechanical strength of the fusion.

Fusion stress can only be measured indirectly in the presence of diffusion stress. For this quantification, a fusion partner (e.g. ZERO
DUR), two specimens with a thickness of one inch may be provided with glass solder layers on both sides thereof. One of the two samples had a glass solder layer with a thickness of 10071 m, and the other had a thickness of 200 m.
Each is provided with a .mu.m glass solder layer on both sides and tempered according to program I. By considering the diffusion stress, the fused stress is 40 nm/am for a 100 μm sample and 80 nm/am for a 1200 μm sample.
A compressive stress of nm/am is relieved over the entire width of 1 mm. Glass solder thickness and fusion partner (ZERODUR
) are equal, the fusion stress is 20 from the above fact.
0 nm/am to 6.7 N/, 2.

The temperature dependence of the stresses generated during welding is of great importance in optical applications, such as for example telescope mirrors.

The temperature dependence of the stress inside the fusion partner (ZF, RODUR) is shown in Figure 1 for glass solders 1-4.6 and 8. FIG. 2a shows a measurement sample for investigating this.

ZERODUR small piece 1 of lxlOxlOmm size is connected with two ZERODUR pieces of 0.5x10x10 fighting dog on both sides through a glass solder layer 3 with a thickness of 60-80μm.
It is welded to a small piece, and reference numeral 4 indicates the measurement direction.

The following points are important in evaluating and selecting glass solder. : 1. Fully reliable crystallization during fusion. Glass solder can be manufactured in a glass state.

2. Differential thermal analysis (DTA) of powders finer than 20 μm carried out at a heating rate of 2.7 m/min for glass solders for glass ceramics and quartz glass, and 6 m/min for glass solders for borosilicate glass. The devitrification properties of glass solder as measured by. The peak maximum value, peak height and peak area provide qualitative information about the crystallization properties.

3. Thermal expansion coefficient of crystallized glass solder after the fusion process. To test this, we moistened 20
Glass powder finer than .mu.m is compression molded into 125.times.12.times.10 mm bars and sintered according to Program I above. Thereby, the coefficient of thermal expansion is measured in the range from 50.degree. to 500.degree. C., and the crystal phase content of the sample is also measured using X-rays.

4. To measure the strength of welding, manufacture L-shaped samples. Fix the vertical arm and apply a load to the horizontal arm. The glass solder joining the vertical and horizontal arms is larger than ION/**2, preferably 15
It should have a weld strength greater than N/mm2.

Breakage most often occurs in the fusion partner rather than in the glass solder layer.

In the composition range of glass solders for transparent glass ceramics, h is always used as the main crystalline layer during the fusion process.
- The crystallization of a quartz mixed crystal phase has a decisive meaning, and it is known that the mixed crystal phase has a significant thermal expansion in the negative direction. For glass solders for borosilicate glasses that are relatively rich in pbo, an additional unknown pb-silicate phase appears. Due to the simultaneous positive thermal expansion of the various glass phases, the thermal expansion of this partially crystallized glass solder can be varied both in the negative and in the positive direction.

Finally, to be suitable as a glass solder for welding transparent glass ceramics with an h-quartz mixed crystal phase (ZERODUR), the pot high crystallization temperature, measured as the peak maximum value of DTA, must be as low as 700°C. is an essential prerequisite.

That is, at a fusion temperature that occurs at 900° C., the h-quartz mixed crystal phase will convert to h+IJ chiapyroxene, thereby rendering the fusion partner opaque and increasing its coefficient of thermal expansion.

From this, it can be seen that the above glass solder has 20 to 5
It is clear that it is also suitable for bonding materials such as quartz glass and opaque h-spodumene-containing glass-ceramics which have a coefficient of thermal expansion of about +6 to 140.10 K in the temperature range of 00 DEG C.

Table 1 shown below lists nine composition examples, and Table 2 shows important characteristic values of the glass solder shown in Table 1.
These values characterize the suitable composition range of glass solders for glass ceramics and quartz glass as follows: 5102 35.77-43.71
wt% Al2O, 30, 34-36, 50 wt% Ls2
o 8.89-10. QO weight% B2O5
8,00-10,00% by weight pbo o -i5. oo
weight t% Na2O0-1,00 weight t% to 20 0 -0.65 weight 4'I
C%FO-0,10wt%Mg
0 0 -2.00 wt% Tl
O20-4,00% by weight B2O3+ PbO+ Na20 + 8,5
0-25,00 wt% to 20+F+T1
02 -7 Table 3 shows that -33.100 within the range of 20-300℃
1 shows composition examples 10 to 17 of partially crystallized glass solders for borosilicate glasses having an alpha value of 1. Table 4 shows important characteristic values of the glass solder. Preferred composition ranges for these glass solders are as follows. :8102 23.85-28.7
0 Weight% Al2O520,25-24,30wt%Li2.0 5.90-7.00wt%B2O510-00-20,00wt%PbO12,
50-36,00 wt% to 200-1.50 wt%Ti
O24,0 wt% MgOO-3,50 wt% Coo O-2,00 wt% B2O3+ P
bO+ 40.00-50.00 it%
20+ T i 02 Figures 3 and 4 show the heat-fusion process from 0 to 600°C followed by cooling to room temperature for a five-layer welded sample consisting of glass solder 12.14 and borosilicate glass DURAN50. D50 type glass sample ζ in the center between
The fused stress obtained here is expressed in nm/em.

The structure of the fused sample is shown in Figure 2b. 1χ10
10mm0) 3 pieces (7) DURAN small piece 5 is I
They are fused together via two glass solder layers 6 of 10x10. In FIG. 2b, arrow 4 indicates the measurement direction.

According to these figures, the two glass solders are DURAN
Maximum welding temperature 68 for welding type 50 borosilicate glass
Most suitable at 0°C.

The invention further relates to a transfer film having a glass solder layer as described above as a medium to be transferred from itself onto another object.

Transfer films are used in many fields.

For example, transfer films for decoration of pots, plates, and other tableware are known. This transfer film consists of a mount made of coated paper, on which a colored decorative pattern is pasted with a water-based adhesive. To decorate tableware, soften the film, peel off the decal, apply it to the tableware, and bake.

The invention in the above aspects provides for the ease of applying a layer of glass solder, crystallized glass solder, partially crystallized glass solder, or a mixture of these materials onto objects to be welded together by the glass solder. It is useful for metastasizing. That is, the glass solder layer constitutes the "decal mania" of the conventional transfer film.

The glass solder is preferably applied by screen printing, offset printing or a combined screen/offset printing process onto a backing, usually consisting of coated paper. The thickness of the glass solder layer is arbitrary, and preferably 10 to 250 μm.

A preferred glass solder is a partially crystallized glass solder, in which the crystalline phase of this glass solder consists primarily of h-quartz mixed crystals75), and this glass solder has an oxide-t
Next component expressed in C view%: S i 02
2.3.0-44.0 wt% Al2O3, 20,
0-37,0% by weight Li2O5, 5-11,0% by weight B2O3 3,0-20,0% by weight PbOO-36, Ot No. 1% Na2O0-1,0% by weight 20 0-1.5% by weight
F O-0,1 wt% TiO20-4
,0wt% MgOO-3,5wtgC% Coo O-2゜0wt%B2O3+P
bO+Na2O+ 8.5-:5 (2% for 1.0 type needle
Contains 0 + F + 'rto2.

[Brief explanation of the drawing]

Figure 1 is a graph showing the temperature dependence of the stress inside the fusion partner (ZERODUR) for glass solders 1-4.6 and 8. Figures 2a and 2b show the structures of two types of welded samples for measurement, respectively. The illustrations, FIGS. 3 and 4, are graphs showing the fusion stress measured in five-piece welded samples consisting of glass solders 12 and 14 and borosilicate glass. 1.2・-・-・ZERODUR small piece, 3.6・・・・・ZERODUR small piece
... Glass solder layer, 4 ... Measurement direction, 5 ... DURAN small piece. Figure 2Q Figure 2b Procedure? i13 J, Een Showa 59 Dogs 3n/3 Director General of the Special Advisory Agency Waken Wakasugi Tono 1, Indication of matter f1 1988 Patent Application No. 13229
July 2, Title of the invention: Crystallized glass solder with a low thermal expansion black rate 3, Relationship with the case of a person who exceeds the positive value Patent applicant name: Siddt Glass Reel 4, representative
Person Yamada Building, 1-1-14 Shinjuku, Shinjuku-ku, Tokyo (zip code 160) Telephone (+13) 351! −
(1G236, Number of inventions increased by amendment 7, Subject of amendment Drawing 8, Supplement II contents Official drawings are added as shown in the attached sheet. (No change in contents)

Claims (1)

[Claims] (1) A glass solder that partially crystallizes,
2 after being sintered from glass powder finer than 100 μm at a temperature below 0°C, preferably below 850°C.
-23,5~ within the range 1 of 0~500℃
This glass solder has a thermal expansion coefficient of -1 to +34.3 10-70 (IJtI thermal rate 2.7 K/tr
im to 6/-) DTA-peak maximum temperature is 71
The temperature is lower than 0°C, and its crystal phase mainly consists of an h-quartz mixed crystal phase, and furthermore, the glass solder has the following components expressed as oxide-weight tS: (hereinafter referred to as 1 Sohaku) 8f0223.0- 44.0 Heavy A1203
20.0-37.0 Weight% Lj20
5.5-11.0 wt%B203
3.0-20.0 wt%Pb0
0 -36.0 Weight - Na20
0 - 1.0 Weight - 20
0 - 1.5 wt% FO
-0.1% by weight TiQ20 - 4.0% by weight Mg0 0 - 3. Chongchang Ji coo
O-2,0% by weight B2O5+ PbO
+Na2O+ 8.5-50.0 2 to weight%
A glass solder characterized by containing 0+F+TiO2. (2) Particularly suitable for welding 5io2-AQ2o5-Li20 series quartz glass and transparent and opaque glass ceramics, in the sintered crystalline state at 20-500℃
DTA (at heating rate 2.7 to 7 m) with a coefficient of thermal expansion of -1 to -23.5 to +26.10-7.
- the peak maximum temperature is lower than 700 °C, the crystalline phase consists of h-quartz mixed crystal phase as a brush, and the following components expressed in t% by weight of oxides = sio235.0-44.0 wt% A12o3 30.0-37.0 Heavy-klLi20 8.5-11.0
wt% B2e53.0-10.0 wt% PbOO-15,0 wt% Np, 2o O-1,0 wt% 20
0 -0.65 wt%F
O-0,1 wt% TiO20-4, O amount MgOO-2,0i4i% B2Q3+ pbo + Na 2Q+ 8.5-2
5.0 The glass solder according to claim 1, characterized in that it contains 20 + F + TiO2 in weight (a). (3) In the sintered crystalline state, from -1 to -〇, 7.1 to -5,3 and 10-7 in the range of 20 to 500℃.
0-7 @ +13.3 after -1 @10-7 ・
The DTA-peak maximum temperature is 687°C, and the crystal phase is mainly composed of h-quartz mixed crystal phase, such as the transparent glass ceramic "ZEROD".
The fusion stress at UR” is 180 to 210 nrrVc
The compressive stress is rrL, and the bending tensile strength is 15N/i
+m', the elastic modulus is 10,000 to 20,0
0ON/mm," and the following components expressed in oxide-weight: (hereinafter 1° margin) sio243.71 Toryochi Al2O335°43 wt% Li2O10,17 wt-82058,95 Weight% Pb0 1.60 Weight - Na20 0.04 Weight% Fo, io
Weight-total Tio2 4.00 Weight - Total 10
The glass solder according to claim 1 or 2, characterized in that the glass solder contains 4.00% by weight. (1) Particularly suitable for welding borosilicate glasses of type DURAN 50, in the sintered crystalline state at up to 680°C, in the range of 20-400°C, 11.9-34.3.
It has a coefficient of thermal expansion of -1 to 10-7 ・(heating rate 6
K at 71m) DTA-peak maximum temperature is 710℃
lower, the crystalline phase consists mainly of an h-quartz mixed crystal phase and a somewhat less abundant secondary crystalline phase (two DTA-1-
5i02 23.00-29.00% Al2O, 20,00-25,00% Li2O5
,90-7,00% by weight 8203 10.00-20.00% by weight
PbO12,50-36,00 weight skin 20 0 - 1.50 weight skin T+
02 4.00 Weight% Mg
OO-3,50wt SkinCoo O-2,00wt%B2O5+Pb
20+ to O+ 40.00-50.00 wt%'
The glass solder according to claim 1, characterized in that it contains rto2. (5) Particularly suitable for welding glass DURAN50, in the sintered crystalline state, within the range of 20 to 400 °C
．． The fusion stress of the five-layer glass solder sample, which has a thermal expansion coefficient varying from -1 to 9 to 29.4° and 10-7°, corresponds to the curve in Figure 3, and the bending tensile strength of such a weld is 5i()2 28.70 Weight factor Al2O32
4,30 Weight Li2O7,00 B2O520,00% by weight pbo 14.00 Weight Chi Tio24.
The glass solder according to claim 1 or 4, characterized in that it contains 00% by weight NgO2, 00% by weight in total 100.00% by weight. (6) Weld the welded part 1c++! Use of the glass solder according to any one of claims 1 to 5, characterized in that the glass solder is carried out under a pressure of 500 g or more per piece. (Force) The use according to claim 6, characterized in that when welding a hollow body, pressure is generated using a vacuum. (8) The welding temperature is lower than 900°C, preferably 850°C.
Use of the glass solder according to any one of claims 1, 2, 3, 6 and 7, characterized in that the glass solder is carried out at a temperature lower than °C. /9) A transfer film constituted by a mount, preferably consisting of coated paper, and a layer of material to be transferred to another object, applied preferably with a water-soluble adhesive, comprising: Transfer film, characterized in that the material to be transferred is a glass solder, a crystallized glass solder, a partially crystallized glass solder or a mixture of these substances. (11 The above glass solder, crystallized glass solder,
Claims characterized in that a partially crystallized glass solder or a mixture of these substances is applied to a film in a predetermined thickness by a screen printing method, an offset printing method or a combined screen printing/offset printing method. The range of film solder described in item 9 (1υ) is a glass solder in which the material to be transferred is partially crystallized, and the crystalline phase of this! lath solder mainly consists of h-quartz mixed crystal, and The core glass solder has the following components expressed in oxide-wt%: 5io223.0-44.0 wt% Al2O320
,0,-37,0 double ambiguity 1j20 5.5-
11.0 Weight-n2o5 3.0-20.
0 wt% PbOO-36,0 wt% Na2O0-1,0 wt-20 0-1.5 wt% F
O-0, 1 layer tchi Tto2o -4
,0% by weight Mg0 0 - 3.5% by weightCoo
O-2,0 heavy B2O5+PbO+N
a2O+ 8.5-50.0 Weight-2 Q+
The film according to claim 9 or sio, characterized in that it contains F+T 102 .