CN114180843A - Sealing glass and preparation method thereof - Google Patents
Sealing glass and preparation method thereof Download PDFInfo
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- CN114180843A CN114180843A CN202111631561.8A CN202111631561A CN114180843A CN 114180843 A CN114180843 A CN 114180843A CN 202111631561 A CN202111631561 A CN 202111631561A CN 114180843 A CN114180843 A CN 114180843A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
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Abstract
The invention relates to the technical field of glass sealing, in particular to sealing glass and a preparation method thereof. The preparation raw materials of the sealing glass comprise: v2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3(ii) a The V is2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3The mass ratio of (A) to (B) is 10-50: 1-10: 20-60: 0.001-0.55: 0.003 to 0.54: 0.002 to 0.23: 0.003 to 0.78: 0.002 to 0.81. The sealing glass provided by the invention is V2O5‑B2O3‑TeO2(VBT) sealing glass, V provided by the invention2O5‑B2O3‑TeO2The (VBT) sealing glass has the advantages of higher expansion coefficient, higher resistivity and better chemical stability.
Description
Technical Field
The invention relates to the technical field of glass sealing, in particular to sealing glass and a preparation method thereof.
Background
The sealing glass is one of glass materials with special performance, has many advantages in properties and performance, can carry out special sealing treatment on materials such as metal, ceramic and the like with different properties or the same properties in the production process, determines the research direction of a ternary system for ensuring that a glass substrate has lower melting temperature and larger expansion coefficient, tests various properties of the sealing glass, such as melting temperature, chemical stability, conductivity and the like, and further popularizes the sealing glass on the basis of experimental research to be applied to more electronic technologies, building industry, automobile space navigation and other scientific and technological lives to realize good sealing and sealing effects of the sealing glass on different materials.
At present, the research on sealing glass shows the shunting of different systems, the main content of the sealing glass comprises various glass compositions which take boric acid, phosphoric acid, vanadic acid and bismuthic acid as matrixes, and the component properties are different, wherein the vanadate system sealing glass receives more and more attention due to the lower sealing temperature, the moderate expansion coefficient, the higher sealing property and the wide application.
Sealing glasses come in a wide variety of types, and are classified according to their properties and chemical compositions.
The most common classifications can be classified as: boric acid-based sealing glass, vanadic acid-based sealing glass, and oxide-containing sealing glass.
The glass composition can be divided into: oxide-containing glasses, oxide-type glasses, and mixed glasses.
The following can be classified according to whether crystallization occurs or not: crystalline sealing glass capable of crystallizing, non-crystallized sealing glass and composite sealing glass.
The oxide can be divided into the following components according to the types of the contained oxides: sulfur-containing glasses, oxygen-sulfur containing glasses, fluoride-containing glasses.
Wherein, the characteristics and the advantages and the disadvantages of the three sealing glasses of crystallinity, non-crystallinity and composite type show relatively complex differences.
(1) Crystalline sealing glass
The crystalline sealing glass is characterized in that the properties of the glass material, such as physicochemical effect, can be influenced to generate larger change, which shows that crystals are precipitated, and in order to improve the defect, the improvement of the sealing strength, the stability and the thermal shock resistance function can be realized under the action of stress when the matched expansion coefficient is matched. However, the sealing process of the glass is complex, and the sealing function of the glass can be influenced if the crystallization is solved improperly.
(2) Amorphous sealing glass
The noncrystalline sealing glass has the characteristics of no crystallization phenomenon in glass sealing materials, so that the noncrystalline sealing glass has better glass flowability, wettability and air tightness. Good sealing airtightness can be realized by keeping the expansion coefficient and the stress relatively constant, but the sealing process has defects in stability maintenance, so that the glass is poor in mechanical property and easy to fall off under stress.
(3) Composite sealing glass
The composite sealing glass combines the characteristics of a crystalline phase and an amorphous phase of the material in the glass material, the components mainly comprise crystalline powder and glass powder, the performance of the sealing glass can be improved by adjusting the parameters of the glass sealing process such as temperature condition, shrinkage coefficient and the like, but the sealing quality can be influenced by uneven control of main powder.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a sealing glass and a preparation method thereof, and the sealing glass provided by the present invention has the advantages of high expansion coefficient, high resistivity and excellent chemical stability.
The invention provides sealing glass, which is prepared from the following raw materials: v2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3；
The V is2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3The mass ratio of (A) to (B) is 10-50: 1-10: 20-60: 0.001-0.55: 0.003 to 0.54: 0.002 to 0.23: 0.003 to 0.78: 0.002 to 0.81.
Preferably, said V2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3The mass ratio of (A) to (B) is 10: 4: 51: 0.12: 0.003: 0.011: 0.78: 0.21, 42: 1: 60: 0.001: 0.012: 0.056: 0.008: 0.012, 32: 5: 20: 0.009: 0.078: 0.002: 0.003: 0.076, 36: 10: 42: 0.02: 0.54: 0.18: 0.12: 0.81 or 50: 7: 29: 0.54: 0.43: 0.23: 0.058: 0.002.
the invention also provides a preparation method of the sealing glass, which comprises the following steps:
A) mixing and melting the preparation raw materials to obtain molten glass;
B) rolling the molten glass on a casting plate, then grinding and pressing to form expansion strips;
C) and firing the expansion strip at 360-385 ℃, and annealing to obtain the sealing glass.
Preferably, in the step A), the melting temperature is 680-750 ℃ and the time is 15-30 min.
Preferably, step a), before the melting, further comprises:
drying the preparation raw materials at 200-300 ℃.
Preferably, in the step C), the firing temperature is 370 ℃ and the time is 5-30 min.
Preferably, in the step C), the annealing temperature is 250-340 ℃, and the time is 25-35 min.
Preferably, step C) further comprises, after the annealing: and cooling to room temperature.
The invention provides sealing glass, which is prepared from the following raw materials: v2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3(ii) a The V is2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3The mass ratio of (A) to (B) is 10-50: 1-10: 20-60: 0.001-0.55: 0.003 to 0.54: 0.002 to 0.23: 0.003 to 0.78: 0.002 to 0.81. The sealing glass provided by the invention is V2O5-B2O3-TeO2(VBT) sealing glass, V provided by the invention2O5-B2O3-TeO2The (VBT) sealing glass has the advantages of higher expansion coefficient, higher resistivity and better chemical stability.
Drawings
FIG. 1 is a DTA diagram of a sealing glass of example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides sealing glass, which is prepared from the following raw materials: v2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3；
The V is2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3The mass ratio of (A) to (B) is 10-50: 1-10: 20-60: 0.001-0.55: 0.003 to 0.54: 0.002 to 0.23: 0.003 to 0.78: 0.002 to 0.81.
In certain embodiments of the invention, said V2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3The mass ratio of (A) to (B) is 10: 4: 51: 0.12: 0.003: 0.011: 0.78: 0.21, 42: 1: 60: 0.001: 0.012: 0.056: 0.008: 0.012, 32: 5: 20: 0.009: 0.078: 0.002: 0.003: 0.076, 36: 10: 42: 0.02: 0.54: 0.18: 0.12: 0.81 or 50: 7: 29: 0.54: 0.43: 0.23: 0.058: 0.002。
The invention also provides a preparation method of the sealing glass, which comprises the following steps:
A) mixing and melting the preparation raw materials to obtain molten glass;
B) rolling the molten glass on a casting plate, then grinding and pressing to form expansion strips;
C) and firing the expansion strip at 360-385 ℃, and annealing to obtain the sealing glass.
In the preparation method of the sealing glass provided by the invention, the components and the proportion of the adopted preparation raw materials are the same as those in the above, and are not described again.
In step A):
in certain embodiments of the invention, the mixing is a homogeneous mixing.
In some embodiments of the present invention, the melting temperature is 680-750 ℃ and the time is 15-30 min. In certain embodiments, the melting temperature is 700 ℃ and the time is 20 min.
In some embodiments of the present invention, before the melting, further comprising:
drying the preparation raw materials at 200-300 ℃.
In certain embodiments, the temperature of the oven drying is 250 ℃.
In step B):
the process steps of flaking, grinding, pressing the expanded beads are not particularly limited in the present invention, and the process steps of flaking, grinding, pressing the expanded beads known to those skilled in the art may be used.
In step C):
in certain embodiments of the present invention, the firing temperature is 370 ℃. In some embodiments of the present invention, the firing time is 5 to 30 min. In certain embodiments, the firing time is 30 min.
In some embodiments of the present invention, the annealing temperature is 250-340 ℃ and the annealing time is 25-35 min. In certain embodiments, the temperature of the anneal is 300 ℃ for 30 min.
In some embodiments of the present invention, after the annealing, further comprising: and cooling to room temperature.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
In order to further illustrate the present invention, a sealing glass and a method for manufacturing the same according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
In the following examples, the starting materials were all used in analytical purity.
EXAMPLES 1 TO 5 COMPARATIVE EXAMPLE 1
Preparation of sealing glass:
1) weighing 50g of preparation raw materials according to the proportion, uniformly mixing, drying at 250 ℃, placing in a 50mL quartz crucible, melting in a silicon-molybdenum rod lifting electric furnace, and melting for 20min at 700 ℃ to obtain glass liquid;
2) rolling the molten glass on a casting plate, grinding, and pressing into expansion strips;
3) and firing the expansion strip at 370 ℃ for 30min, annealing at 300 ℃ for 30min, and cooling to room temperature to obtain the sealing glass.
The components and mass ratio of the raw materials, the process parameters and the effect data are shown in table 1.
Table 1 examples 1-5 components and mass ratios of raw materials, process parameters, and effect data for the preparation of comparative example 1
In table 1:
the glass expansion coefficient is measured by a thermal expansion instrument, and the specific operation method comprises the following steps: grinding the obtained sealing glass block into a cuboid with two parallel ends of 5mm multiplied by 25mm, and measuring on a DIL402PC type expansion instrument, wherein the heating rate is 4 ℃/min;
the resistivity is measured by adopting a Keysight B2987A electrometer high-resistance table produced by Dacron technology company of Agilent USA, and the experimental conditions are as follows: the voltage was 500V at the start and 500V at the stop, and the number of dots was 1. The range of a point source is +1000V, the measurement count is 13, the measurement delay is 500ms, and the experimental measurement time limit is 1 (start-stop) under the condition of sampling every 5 seconds;
chemical stability was tested according to standard SJ/T11035-96.
As can be seen from Table 1, the sealing glass prepared by the present invention has an expansion coefficient higher than 145X 10-7A resistivity of more than 6 x 1018Omega cm, chemical stability over 97.5%, greatly raised V2O5-B2O3-TeO2(VBT) is the property of sealing glass.
FIG. 1 is a DTA diagram of a sealing glass of example 1 of the present invention. As can be seen from FIG. 1, the sealing glass of example 1 of the present invention has a Tg of 291.3 ℃ and a lower Tg, and the sintering temperature of the expansion bar is higher than Tg, so that the firing temperature of the expansion bar in step 3) is lower.
Sealing glass button test (i.e. measuring the flow temperature of the sealing glass):
the sealing glass powder which is sieved by a 140-mesh sieve is placed on a glass slide, pressed into a column shape (the height is 125mm multiplied by the width is 5mm), and then sintered for 20min at a corresponding flowing temperature, and the melting condition (whether the flowing is complete) of the column shape of the powder is observed. 10g of sealing glass powder ground and sieved by a 140-mesh sieve is pressed into a cylinder with the diameter of 10mm and the height of 12mm, the cylinder is melted in a muffle furnace, and when the flowing column is melted and flows into a button shape, the processing temperature can just meet the requirement of glass sealing temperature. The glass liquid can be fully expanded in the sealing interface, the fluidity is not too large or too small, the flat button shape is optimal, and otherwise, the filling sealing can not be carried out.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A sealing glass is prepared from the following raw materials: v2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3；
The V is2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3The mass ratio of (A) to (B) is 10-50: 1-10: 20-60: 0.001-0.55: 0.003 to 0.54: 0.002 to 0.23: 0.003 to 0.78: 0.002 to 0.81.
2. A sealing glass according to claim 1, wherein V is2O5、B2O3、TeO2、La2O3、CeO2、Pr2O3、Eu2O3And Dy2O3The mass ratio of (A) to (B) is 10: 4: 51: 0.12: 0.003: 0.011: 0.78: 0.21, 42: 1: 60: 0.001: 0.012: 0.056: 0.008: 0.012, 32: 5: 20: 0.009: 0.078: 0.002: 0.003: 0.076, 36: 10: 42: 0.02: 0.54: 0.18: 0.12: 0.81 or 50: 7: 29: 0.54: 0.43: 0.23: 0.058: 0.002.
3. a method for producing a sealing glass according to claim 1, comprising the steps of:
A) mixing and melting the preparation raw materials to obtain molten glass;
B) rolling the molten glass on a casting plate, then grinding and pressing to form expansion strips;
C) and firing the expansion strip at 360-385 ℃, and annealing to obtain the sealing glass.
4. The method according to claim 3, wherein the melting temperature in step A) is 680-750 ℃ for 15-30 min.
5. The method according to claim 3, wherein the step A) further comprises, before the melting:
drying the preparation raw materials at 200-300 ℃.
6. The method according to claim 3, wherein in the step C), the firing is carried out at 370 ℃ for 5 to 30 min.
7. The method according to claim 3, wherein in the step C), the annealing temperature is 250-340 ℃ and the annealing time is 25-35 min.
8. The method according to claim 3, wherein the annealing in step C) further comprises: and cooling to room temperature.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289279A (en) * | 2008-05-29 | 2008-10-22 | 中国计量学院 | Vanadates leadless low-temperature sealing glass material and method for preparing same |
| CN101456674A (en) * | 2009-01-04 | 2009-06-17 | 武汉理工大学 | Rare-earth doped leadless and low-melting point sealing glass and its preparation method |
| CN101597136A (en) * | 2009-07-23 | 2009-12-09 | 苏州恒仓红外光学材料研发中心有限责任公司 | A kind of lead-free low-melting sealing glass and preparation method thereof |
| WO2012014619A1 (en) * | 2010-07-28 | 2012-02-02 | 日本電気硝子株式会社 | Sealing glass and sealing composite material |
| US20160060158A1 (en) * | 2014-08-29 | 2016-03-03 | Hitachi Chemical Company, Ltd. | Lead-free low-melting glass composition, low-temperature sealing glass frit, low-temperature sealing glass paste, conductive material, and conductive glass paste containing glass composition, and glass-sealed component and electric/electronic component prepared using the same |
| CN107986618A (en) * | 2017-12-28 | 2018-05-04 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of high strain-point alumina silicate glass with high-ohmic |
| CN110451805A (en) * | 2019-09-19 | 2019-11-15 | 成都光明光电有限责任公司 | Seal glass |
-
2021
- 2021-12-28 CN CN202111631561.8A patent/CN114180843B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289279A (en) * | 2008-05-29 | 2008-10-22 | 中国计量学院 | Vanadates leadless low-temperature sealing glass material and method for preparing same |
| CN101456674A (en) * | 2009-01-04 | 2009-06-17 | 武汉理工大学 | Rare-earth doped leadless and low-melting point sealing glass and its preparation method |
| CN101597136A (en) * | 2009-07-23 | 2009-12-09 | 苏州恒仓红外光学材料研发中心有限责任公司 | A kind of lead-free low-melting sealing glass and preparation method thereof |
| WO2012014619A1 (en) * | 2010-07-28 | 2012-02-02 | 日本電気硝子株式会社 | Sealing glass and sealing composite material |
| US20160060158A1 (en) * | 2014-08-29 | 2016-03-03 | Hitachi Chemical Company, Ltd. | Lead-free low-melting glass composition, low-temperature sealing glass frit, low-temperature sealing glass paste, conductive material, and conductive glass paste containing glass composition, and glass-sealed component and electric/electronic component prepared using the same |
| CN107986618A (en) * | 2017-12-28 | 2018-05-04 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of high strain-point alumina silicate glass with high-ohmic |
| CN110451805A (en) * | 2019-09-19 | 2019-11-15 | 成都光明光电有限责任公司 | Seal glass |
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