CN103332862A

CN103332862A - Lead-free sealing glass with transitional expansion coefficient

Info

Publication number: CN103332862A
Application number: CN2013102456584A
Authority: CN
Inventors: 刘树江
Original assignee: Qilu University of Technology
Current assignee: Qilu University of Technology
Priority date: 2013-06-20
Filing date: 2013-06-20
Publication date: 2013-10-02
Anticipated expiration: 2033-06-20
Also published as: CN103332862B

Abstract

The invention belongs to the field of new glass materials, and particularly discloses lead-free sealing glass with a transitional expansion coefficient. The lead-free sealing glass with the transitional expansion coefficient is prepared by mixing the effective materials of SiO2, Al2O3, Bi2O3, Fe2O3, Na2O, K2O, MgO, CaO, SrO, BaO and ZnO according to a certain weight fraction. The lead-free sealing glass with the transitional expansion coefficient overcomes the defects of the conventional transitional sealing manner, has the advantages that the sealing process is simple, the cost is low and the product quality is easy to control, and is particularly suitable for the situation that the cross section of the device to be sealed is annular.

Description

A kind of excessive expansion coefficient barium crown sealed glass

(1) technical field

The present invention relates to the glass field of new, particularly a kind of excessive expansion coefficient barium crown sealed glass.

(2) background technology

Seal glass is the special glass that a class connects differing materials and seal, comprised metal, pottery and glass by the body material of sealing-in, be widely used in various fields such as electrovacuum and microelectronics, laser and infrared technique, high energy physics, the energy, aerospace, automobile.Along with the miniaturization of instrument component, the precise treatment level of structural group element continue to promote, the kind of electronic devices and components is more and more many, and the mode of appearance of product is also more and more numerous and diverse, and this requirement to the seal glass quality is also more and more higher.Lead glass has that glass formation range is big, specific refractory power is high and characteristics such as material property is long, for a long time in the widespread use of sealing-in field.But lead glass is paid close attention to by people also more and more to the hazardness of human body and environment, and the exploitation of barium crown sealed glass and application have become the common recognition in research and production field.

In the seal glass performance most important be exactly its coefficient of expansion should be complementary by the coefficient of expansion of seal, sealing materials, in general the two should be close as far as possible at room temperature to the coefficient of expansion between the glass annealing upper temperature limit.The control of the difference of the two thermal expansivity is 5 * 10 in the life-time service temperature range ^-7K ^-1Below, otherwise can in closure, form bigger stress, cause closure to crack or break.In actual production; through regular meeting run into need coefficient of expansion difference is bigger two kinds of situations that material carries out sealing-in; be to adopt the coefficient of expansion to carry out repeatedly transition sealing between the glass between the two traditionally; thermal expansivity between the adjacent materials is slowly transition successively, can not crack too greatly because of coefficient of expansion difference.But the sealing process complexity of this method, quality product are difficult to control.Particularly when being ring structure by the cross section of sealing device, adopt the difficulty of transition sealing mode further to increase.

(3) summary of the invention

The present invention provides the excessive expansion coefficient barium crown sealed glass that a kind of preparation method is simple, starting material are easy to get in order to remedy the deficiencies in the prior art.

The present invention is achieved through the following technical solutions:

A kind of excessive expansion coefficient barium crown sealed glass, made by effective material of following weight fraction:

SiO _2?46.92~52.18%，Al ₂O _3?2.24~2.49%，Bi ₂O _3?12.51~19.91%，Fe ₂O _3?1.95~2.17%，Na ₂O?9.07~10.09%，K ₂O?13.79~15.34%，MgO?0~3.83%，CaO?0~5.25%，SrO?0~9.28%，BaO?0~13.52%，ZnO?0~7.44%。

The weight proportion of its preferred each effective material is:

SiO _2?48.10~52.18%，Al ₂O _3?2.26~2.40%，Bi ₂O _3?16.32~18.01%，Fe ₂O _3?2.03~2.10%，Na ₂O?9.50~10.00%，K ₂O?14.00~15.11%，MgO?3.60~3.80%。

Described effective material SiO ₂The source be quartz sand, Al ₂O ₃The source be aluminium hydroxide, Li ₂The source of O is Quilonum Retard, Na ₂The source of O is yellow soda ash, K ₂The source of O is salt of wormwood, and the source of CaO is calcium carbonate.

The preparation process of barium crown sealed glass of the present invention comprises:

(1) according to above-mentioned chemical constitution, accurately take by weighing the weight of respectively forming corresponding raw material and mix and make admixtion, admixtion is incubated 2 hours in 1743 ~ 1753K in silicon molybdenum rod furnace, make uniform glass metal, the glass metal of homogenizing is cast in the stainless steel mould of preheating, 700 ~ 730K annealing 1 hour, obtain transparent, even bubble-free parent glass;

(2) obtain the glass transformation temperature T of each sample according to the DSC test result of parent glass _g, parent glass is placed above the porous ceramics, put into the crucible that carbon dust is housed then together, in 1.09T _gTemperature insulation furnace cooling after 24 hours;

(3) parent glass is after reducing atmosphere thermal treatment, forms a layer thickness on the surface of glass and be 5 ~ 25 microns crystal, has the barium crown sealed glass that crosses the coefficient of expansion with namely getting to be after the crystal layer polishing.

In reducing atmosphere, parent glass is in surperficial crystallization process, and the modification body positively charged ion in the glass spreads from inside to outside and participates in crystal growth, causes and modifies the minimizing gradually from inside to outside of body cation concn, and then cause thermal expansivity to reduce gradually from inside to outside.The crystal layer thickness that the different glass samples of forming are separated out owing to the heat treatment time difference has difference slightly, but has tangible interface between crystal layer and the glass, and the surface crystal layer peels off easily, so polishing process is very simple.The glass surface thermal expansivity can be regulated by heat treatment time according to the thermal expansivity of sealing-in substrate material.

High and the outside coefficient of expansion of the coefficient of expansion of glass of the present invention inside is low, namely just can replace multilayer seal glass in the transition sealing mode with a glass, the various drawbacks that conventional transition sealing-in mode exists have been overcome, have advantages such as sealing process is simple, cost is low, the easy control of quality product, being fit to by the cross section of sealing device very much is the situation of ring structure.

(4) description of drawings

The present invention is further illustrated below in conjunction with accompanying drawing.

Fig. 1 is the linear expansivity comparison diagram before and after the parent glass thermal treatment among the embodiment 1.

(5) embodiment

Below by specific embodiment lead-free sealing glass material of the present invention is described further, wherein embodiment 1 is most preferred embodiment.Significant parameter and the performance of embodiment 1 ~ 5 are as shown in the table.

Figure 2013102456584100002DEST_PATH_IMAGE002

Embodiment 1:

Raw materials used weight part consists of: 52.18 parts of quartz sands, 3.85 parts in aluminium hydroxide, 14.05 parts of bismuthous oxide bismuth trioxides, 2.17 parts of ferric oxide, 3.85 parts in magnesium oxide, 14.53 parts in yellow soda ash, 4.66 parts of SODIUMNITRATE, 19.47 parts in salt of wormwood, 5.54 parts in saltpetre.

The manufacture method concrete steps are as follows:

Step 1: according to the accurate weighing of above-mentioned raw materials and evenly mixed, in silicon molybdenum rod furnace, in 1753K insulation 2 hours, make uniform glass metal.Uniform glass metal is cast in rapidly in the stainless steel mould of preheating, 720 K annealing 1 hour, obtain transparent, even bubble-free mass foundation glass.

Step 2: the glass transformation temperature T that obtains each sample according to the DSC test result of parent glass _g, parent glass is put into the sealing crucible that carbon dust is housed, be cooled to room temperature in the 803K insulation after 24 hours.Sample after the thermal treatment namely gets to be after polishing has the barium crown sealed glass that crosses the coefficient of expansion.

Embodiment 2:

Raw materials used weight part consists of: 51.41 parts of quartz sands, 3.79 parts in aluminium hydroxide, 13.84 parts of bismuthous oxide bismuth trioxides, 2.14 parts of ferric oxide, 9.46 parts in calcium carbonate, 14.31 parts in yellow soda ash, 4.59 parts of SODIUMNITRATE, 19.18 parts in salt of wormwood, 5.46 parts in saltpetre.

The manufacture method concrete steps are as follows:

Step 1: be raw material with quartz sand, aluminum oxide, aluminium hydroxide, bismuthous oxide bismuth trioxide, ferric oxide, calcium carbonate, soda ash, SODIUMNITRATE, salt of wormwood etc., according to the accurate weighing of above-mentioned chemical constitution and evenly mixed, in silicon molybdenum rod furnace, in 1753K insulation 2 hours, make uniform glass metal.Uniform glass metal is cast in rapidly in the stainless steel mould of preheating, 730K annealing 1 hour, obtain transparent, even bubble-free mass foundation glass.

Step 2: the glass transformation temperature T that obtains each sample according to the DSC test result of parent glass _g, parent glass is put into the sealing crucible that carbon dust is housed, be cooled to room temperature in the 821K insulation after 24 hours.Sample after the thermal treatment namely gets to be after polishing has the barium crown sealed glass that crosses the coefficient of expansion.

Embodiment 3:

Raw materials used weight part consists of: 49.22 parts of quartz sands, 3.63 parts in aluminium hydroxide, 13.25 parts of bismuthous oxide bismuth trioxides, 2.05 parts of ferric oxide, 13.36 parts of Strontium carbonate powders, 13.7 parts in yellow soda ash, 4.39 parts of SODIUMNITRATE, 18.37 parts in salt of wormwood, 5.23 parts in saltpetre.

The manufacture method concrete steps are as follows:

Step 1: be raw material with quartz sand, aluminum oxide, aluminium hydroxide, bismuthous oxide bismuth trioxide, ferric oxide, Strontium carbonate powder, soda ash, SODIUMNITRATE, salt of wormwood etc., according to the accurate weighing of above-mentioned chemical constitution and evenly mixed, in silicon molybdenum rod furnace, in 1743K insulation 2 hours, make uniform glass metal.Uniform glass metal is cast in rapidly in the stainless steel mould of preheating, 710K annealing 1 hour, obtain transparent, even bubble-free mass foundation glass.

Embodiment 4:

Raw materials used weight part consists of: 46.92 parts of quartz sands, 3.46 parts in aluminium hydroxide, 12.63 parts of bismuthous oxide bismuth trioxides, 1.95 parts of ferric oxide, 17.02 parts of barium carbonates, 13.06 parts in yellow soda ash, 4.19 parts of SODIUMNITRATE, 17.51 parts in salt of wormwood, 4.98 parts in saltpetre.

The manufacture method concrete steps are as follows:

Step 1: be raw material with quartz sand, aluminum oxide, aluminium hydroxide, bismuthous oxide bismuth trioxide, ferric oxide, barium carbonate, soda ash, SODIUMNITRATE, salt of wormwood etc., according to the accurate weighing of above-mentioned chemical constitution and evenly mixed, in silicon molybdenum rod furnace, in 1743K insulation 2 hours, make uniform glass metal.Uniform glass metal is cast in rapidly in the stainless steel mould of preheating, 700K annealing 1 hour, obtain transparent, even bubble-free mass foundation glass.

Embodiment 5:

Raw materials used weight part consists of: 50.22 parts of quartz sands, 3.7 parts in aluminium hydroxide, 13.52 parts of bismuthous oxide bismuth trioxides, 2.09 parts of ferric oxide, 7.51 parts in zinc oxide, 13.98 parts in yellow soda ash, 4.48 parts of SODIUMNITRATE, 18.74 parts in salt of wormwood, 5.33 parts in saltpetre.

The manufacture method concrete steps are as follows:

Step 1: be raw material with quartz sand, aluminum oxide, aluminium hydroxide, bismuthous oxide bismuth trioxide, ferric oxide, zinc oxide, soda ash, SODIUMNITRATE, salt of wormwood etc., according to the accurate weighing of above-mentioned chemical constitution and evenly mixed, in silicon molybdenum rod furnace, in 1743K insulation 2 hours, make uniform glass metal.Uniform glass metal is cast in rapidly in the stainless steel mould of preheating, 710K annealing 1 hour, obtain transparent, even bubble-free mass foundation glass.

Claims

1. an excessive expansion coefficient barium crown sealed glass is characterized by, and is made by effective material of following weight fraction: SiO ₂46.92 ~ 52.18%, Al ₂O ₃2.24 ~ 2.49%, Bi ₂O ₃12.51 ~ 19.91%, Fe ₂O ₃1.95 ~ 2.17%, Na ₂O 9.07 ~ 10.09%, K ₂O 13.79 ~ 15.34%, and MgO 0 ~ 3.83%, and CaO 0 ~ 5.25%, and SrO 0 ~ 9.28%, and BaO 0 ~ 13.52%, and ZnO 0 ~ 7.44%.

2. excessive expansion coefficient barium crown sealed glass according to claim 1 is characterized by, and is made by effective material of following weight fraction: SiO ₂48.10 ~ 52.18%, Al ₂O ₃2.26 ~ 2.40%, Bi ₂O ₃16.32 ~ 18.01%, Fe ₂O ₃2.03 ~ 2.10%, Na ₂O 9.50 ~ 10.00%, K ₂O 14.00 ~ 15.11%, and MgO 3.60 ~ 3.80%.

3. excessive expansion coefficient barium crown sealed glass according to claim 1 is characterized in that: described effective material SiO ₂The source be quartz sand, Al ₂O ₃The source be aluminium hydroxide, Li ₂The source of O is Quilonum Retard, Na ₂The source of O is yellow soda ash, K ₂The source of O is salt of wormwood, and the source of CaO is calcium carbonate.

4. excessive expansion coefficient barium crown sealed glass according to claim 1, it is characterized in that: after using above-mentioned materials to make parent glass, parent glass is put into the sealing crucible that carbon dust is housed, be cooled to room temperature in the insulation of 1.09Tg temperature after 24 hours, the sample after the thermal treatment namely gets to be after polishing has the barium crown sealed glass that crosses the coefficient of expansion.