Special packaging glass with medium-high softening point and wide expansion coefficient and preparation method thereof

Abstract

The invention belongs to the technical field of glass materials, and particularly discloses special packaging glass with a medium-high softening point and a wide expansion coefficient and a preparation method of the special packaging glass with the medium-high softening point and the wide expansion coefficient. 15.0%-25.0% of Al2O3 (aluminum oxide); 0 to 7.0% of B2O3; 5.0% to 15.0% of Na2O; 0 to 1 percent of Li2O; 1 to 10% of MgO; 0 to 1.0 percent of CaO; 0 to 3.0% of BaO; 0 to 4.0% of ZrO2; 0 to 2.0 percent of TiO2; 0 to 6.0% of Y2O3; 0-0.5% of a clarifying agent; and unavoidable impurities. According to the special packaging glass provided by the invention, silicate is used as a network main body of the glass, and different metal oxide components are added and adjusted, so that the expansion coefficient of the sealing glass is adjusted to (39-80) * 10 <-7 > K <-1 >, the softening point is 850-920 DEG C, and the Kirschner hardness is gt; the density is 410 kgf / mm < 2 > and the density is lt The expansion coefficient regulation space is huge, the expansion coefficient can be matched with the expansion coefficients of materials such as gold, metal, ceramic and glass, the sealing of base materials such as alloy, metal, ceramic or glass can be realized, and the application scene is rich.

Description

Technical Field

[0001] The present invention belongs to the technical field of glass materials, and particularly relates to a special packaging glass with a medium-high softening point and a wide expansion coefficient and a preparation method thereof. Background Art

[0002] Special glass is a kind of glass material with special properties and uses. Its main characteristics include high temperature resistance, corrosion resistance, high strength, low thermal conductivity, etc. There are many types of special glass. Classified by use, the common ones are as follows: 1) High-temperature resistant glass: This kind of glass can maintain stable performance in high-temperature environments and is commonly used in chemical experiments, instruments, and industrial furnaces; 2) Optical glass: It is used in optical instruments such as microscopes and telescopes, and has excellent light transmission performance and low optical distortion; 3) Acid-resistant glass: It can resist strong acid corrosion and is suitable for industries such as chemical engineering and pharmaceuticals; 4) Fiber glass: This kind of glass is drawn into fine filaments, has good tensile strength and heat resistance, and is widely used in composite materials, heat insulation, and insulation fields; 5) Synthetic quartz glass: Because of its high transparency and chemical stability, this kind of glass is widely used in semiconductor and optoelectronic devices.

[0003] Packaging glass is a kind of special glass, which is specifically used to protect and seal electronic components (such as integrated circuits, sensors, etc.), optical devices (such as lasers, camera lenses, etc.), and other industrial applications. Sealing glass is a kind of packaging glass. Through the molten glass material, it can achieve good wetting and close bonding with the surface of the pre-prepared sealing substrate, and can ensure that the substrates are firmly sealed together at the use temperature to form a whole.

[0004] With the rapid development of the electronics industry, electronic components are developing towards smaller and more precise directions. Correspondingly, it is required that the sealing glass based on metals and ceramics has higher airtightness, flexible matching, and excellent heat resistance; in addition, the linear expansion coefficient of the sealing glass should be adapted to that of the sealing material and match within the range below the sealing temperature. In the prior art, for example, the patent document CN102050577B provides a sealing glass for special purposes. Its component range contains, by weight percentage in terms of compounds: SiO 2 : 62-75%; B 2 O 3 : 3-10%; Al 2 O 3 : 1-9%; La 2 O 3 : 0-5%; Li 2 O: 0-3%; Na 2 O: 3-15%; K 2O: 4 - 14%; BaO: 0 - 3%; SrO: 0 - 3%; CaO: 2 - 12%; ZnO: 0 - 2%; Sb 2 O 3 : 0 - 1%; The sum of each component is 100%; The above sealing glass is mainly used for sealing the ports of metal tubes or internally coated metal tubes, and has a narrow coefficient of thermal expansion.

[0005] For another example, patent document CN103342451B provides a method for manufacturing a lead-free sealing glass with a transition coefficient of thermal expansion. The weight part ratio of the effective components of the raw materials is as follows: SiO 2 50.39 - 51.96%, Al 2 O 3 2.40 - 2.48%, Bi 2 O 3 13.43 - 13.85%, Fe 2 O 3 2.10 - 2.16%, Na 2 O 9.74 - 10.05%, K 2 O 14.81 - 15.27%, MgO 0 - 2.72%, CaO 0 - 1.52%, BaO 0 - 4.16%, ZnO 0 - 6.41%; The softening point of the above sealing glass is only 500 - 600 °C.

[0006] In fact, the current sealing glass materials have the following problems when sealing with substrate materials: 1) The coefficient of thermal expansion range is relatively narrow, which leads to a low adaptability of the coefficient of linear thermal expansion between the sealing glass material and substrates such as alloys, metals, glasses or ceramics, and further makes the sealing fields where the sealing glass material is used narrow; 2) The softening point is relatively low. Although a low softening point can improve the sintering bonding rate, for sealing parts with shape requirements, they are deformed during sintering, and the glass strength after sintering is insufficient and not wear-resistant; 3) The softening point is relatively high, which will lead to a relatively high temperature required for sealing sintering, making the sintering difficult. And when the sintering temperature is relatively high, it is easy to cause the softening and damage of the sealing substrate. Summary of the Invention

[0007] Aiming at the deficiencies of the existing technology, one of the purposes of the present invention is to provide a special packaging glass with a medium-high softening point and a wide coefficient of thermal expansion. The obtained special packaging glass has a moderate softening point and a high coefficient of thermal expansion, and can achieve good sealing with various materials such as alloys, metals, glasses or ceramics, and has a wide application scenario.

[0008] The second purpose of the present invention is to provide a preparation method of the above special packaging glass, which has a simple process and is easy to implement on a large scale.

[0009] The third object of the present invention is to provide an application of the above special encapsulation glass. For example, sintering and sealing the above special encapsulation glass with one of an alloy, a metal, a glass or a ceramic.

[0010] To achieve the above object, the present invention adopts the following technical solutions:

[0011] In a first aspect, the present invention provides a special encapsulation glass with a medium-high softening point and a wide expansion coefficient, which comprises the following components in mass percentage: SiO 2 50.0 - 65.0%; Al 2 O 3 15.0 - 25.0%; B 2 O 3 0 - 7.0%; Na 2 O 5.0 - 15.0%; Li 2 O 0 - 1%; MgO 1 - 10%; CaO 0 - 1.0%; BaO 0 - 3.0%; ZrO 2 0 - 4.0%; TiO 2 0 - 2.0%; Y 2 O 3 0 - 6.0%; a clarifying agent 0 - 0.5%; and inevitable impurities.

[0012] As a further preference of the technical solution of the present invention, the total mass percentage of SiO 2 + Al 2 O 3 + B 2 O 3 in the special encapsulation glass is 65 - 85 wt%.

[0013] As a further preference of the technical solution of the present invention, the softening point of the special encapsulation glass is 850 - 930 °C, and / or the expansion coefficient of the special encapsulation glass within 40 - 400 °C is (39 - 80) × 10 -7 K -1 .

[0014] As a further preference of the technical solution of the present invention, the clarifying agent includes at least one of Na 2 SO 4 , NaCl, CaSO 4 , SnO 2 , Sb 2 O 3 .

[0015] As a further preference of the technical solution of the present invention, the transition temperature of the special encapsulation glass is 640 - 680 °C, the density is less than 2.5 g / cm 3 , and the Knoop hardness > 410 kgf / mm2 。

[0016] In a second aspect, the present invention provides a method for preparing the above special packaging glass, comprising the following steps:

[0017] S1. Weigh the component raw materials and mix them evenly to obtain the glass batch;

[0018] S2. Add the glass batch into a hot crucible heated at a high temperature;

[0019] S3. After raising the temperature, keep it warm, then carry out stirring treatment, and continue to keep it warm after stopping stirring to obtain the glass melt;

[0020] S4. After the heat preservation is completed, pour the obtained glass melt into a preheated mold to obtain the formed glass material;

[0021] S5. Anneal the obtained formed glass material to obtain the special packaging glass.

[0022] As a further preference of the above preparation method, in step S2, the high-temperature heating temperature is 1550 - 1630 °C.

[0023] As a further preference of the above preparation method, in step S3, raise the temperature to 1640 - 1700 °C, and the heat preservation time after raising the temperature is 1 - 4 h;

[0024] The stirring treatment time is 4 - 12 h;

[0025] The heat preservation time after stopping stirring is 10 - 60 min.

[0026] As a further preference of the above preparation method, in step S5, the specific steps of the annealing treatment are: keep it warm at 610 - 650 °C for 6 - 24 h, then cool it at a rate of 4 °C / h to 510 - 550 °C and at a rate of 20 °C / h to 270 - 290 °C, stop heating, and cool down.

[0027] In a third aspect, based on the above-prepared special packaging glass, it can be applied to any one of sintering and sealing with alloys, metals, glasses or ceramics, and the application scenarios are extensive.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) For the special packaging glass provided by the present invention, through the glass material components and contents, and by optimizing the process parameters, the prepared special packaging glass material has excellent comprehensive performance.

[0030] (2) For the special packaging glass provided by the present invention, using silicate as the network main body of the glass, by adding and adjusting different metal oxide components, the expansion coefficient of the sealing glass is adjusted to be in the range of (40 - 80) * 10-7 K -1 , with a softening point of 850 - 920 °C and a Knoop hardness > 410 kgf / mm 2 , with a density < 2.5 g / cm -3 , with a large adjustment space for the coefficient of thermal expansion, which can be adapted to the coefficients of thermal expansion of materials such as alloys, metals, ceramics, and glasses, and is used for the sealing of substrates such as alloys, metals, ceramics, or glasses, with rich application scenarios. Specific embodiments

[0031] In order to make the objectives, technical solutions, and advantages of the present invention clearer, the following further elaborates on the present invention in conjunction with embodiments. Of course, the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0032] Although the steps in the present invention are arranged with reference numerals, they are not used to limit the order of the steps. Unless the order of the steps is clearly stated or the execution of a certain step requires other steps as a basis, the relative order of the steps can be adjusted. It can be understood that the term "and / or" used herein covers any and all possible combinations of one or more of the associated listed items.

[0033] Unless otherwise specified, the raw materials in the present invention are purchased through market channels.

[0034] In the present invention, a special packaging glass with a medium to high softening point and a wide coefficient of thermal expansion is provided. In terms of mass percentage (total 100%), it includes the following components: SiO 2 50.0 - 65.0%; Al 2 O 3 15.0 - 25.0%; B 2 O 3 0 - 7.0%; Na 2 O 5.0 - 15.0%; Li 2 O 0 - 1%; MgO 1 - 10%; CaO 0 - 1.0%; BaO 0 - 3.0%; ZrO 2 0 - 4.0%; TiO 2 0 - 2.0%; Y 2 O 3 0 - 6.0%; fining agent 0 - 0.5%; and inevitable impurities.

[0035] In the above technical solution, for the special glass provided, with SiO 2As the glass network backbone, by adjusting the types and contents of alkali metal elements Na, Li or alkaline earth metal elements Mg, Ca, Ba, sufficient free oxygen is provided in the glass to enable the intermediate oxide Al2O3 to participate in the network composition in the form of aluminum-oxygen tetrahedron [AlO4], improve the network strength, and at the same time play a role of "breaking the network" to reduce the melting temperature; secondly, B 2 O 3 The coordination form of depends on the content of metal oxides in the glass. Due to its different coordination numbers, it plays a role in adjusting the glass viscosity and thermal expansion coefficient; introducing divalent cations Ti or Zr with high coordination numbers and strong field strengths can make the glass structure have both a high ion packing density and a tight structure, achieving the effect of reducing the thermal expansion coefficient. Rare earth metal oxides Y with high field strengths 2 O 3 In the glass, it can not only play a role in destroying silicon-oxygen tetrahedrons, increasing the number of non-bridging oxygens, and increasing the expansion coefficient, but also has an aggregating effect on the glass structure, promoting the formation of Si-O-Y or Y-O-Y units, and modifying the high-temperature performance and chemical stability of the encapsulated glass.

[0036] In the above technical solution, the content range of TiO 2 is 0 to 2.0%, and the content range of ZrO 2 is 0 to 4.0%. When the content of TiO 2 or ZrO 2 is 0, that is, no corresponding substance is added.

[0037] Exemplarily, the contents of the above substances can be selected as: SiO 2 : 52.66 wt%, Al 2 O 3 : 22.52 wt%, B 2 O 3 : 4.31 wt%, Na 2 O: 9.16 wt%, MgO: 9.11 wt%, Sb 2 O 3 : 0 wt%, SnO 2 : 0.24 wt%.

[0038] Exemplarily, the contents of the above substances can be selected as: SiO 2 : 60.82 wt%, Al 2 O 3 : 20.11 wt%, B 2 O 3 : 4.22 wt%, Na 2 O: 11.18 wt%, MgO: 3.34 wt%, Sb 2 O 3 : 0.22 wt%, SnO2 : 0.12 wt%.

[0039] Exemplarily, the content of the above substances can be selected as: SiO 2 : 60.70 wt%, Al 2 O 3 : 20.30 wt%, B 2 O 3 : 4.21 wt%, Na 2 O: 10.92 wt%, MgO: 3.33 wt%, ZrO 2 : 0.19 wt%, Sb 2 O 3 : 0.22 wt%, SnO 2 : 0.12 wt%.

[0040] Exemplarily, the content of the above substances can be selected as: SiO 2 : 60.65 wt%, Al 2 O 3 : 20.05 wt%, B 2 O 3 : 4.21 wt%, Na 2 O: 10.20 wt%, MgO: 3.33 wt%, TiO 2 : 1.22 wt%, Sb 2 O 3 : 0.22 wt%, SnO 2 : 0.12 wt%.

[0041] Exemplarily, the content of the above substances can be selected as: SiO 2 : 62.71 wt%, Al 2 O 3 : 21.45 wt%, B 2 O 3 : 4.10 wt%, Na 2 O: 3.09 wt%, MgO: 2.65 wt%, Y 2 O 3 : 0 wt%, Sb 2 O 3 : 0.22 wt%, SnO 2 : 0.11 wt%.

[0042] Exemplarily, the content of the above substances can be selected as: SiO 2 : 59.41 wt%, Al 2 O 3 : 19.26 wt%, B 2 O 3 : 4.12 wt%, Na2 O: 10.22 wt%, MgO: 3.26 wt%, Y 2 O 3 : 3.39 wt%, Sb 2 O 3 : 0.22 wt%, SnO 2 : 0.11 wt%.

[0043] Exemplarily, the content of the above substances can be selected as: SiO 2 : 61.01 wt%, Al 2 O 3 : 19.78 wt%, B 2 O 3 : 4.23 wt%, Na 2 O: 10.97 wt%, MgO: 3.66 wt%, Sb 2 O 3 : 0.22 wt%, SnO 2 : 0.12 wt%.

[0044] Exemplarily, the content of the above substances can be selected as: SiO 2 : 61.11 wt%, Al 2 O 3 : 19.81 wt%, B 2 O 3 : 4.24 wt%, Na 2 O: 10.51 wt%, MgO: 3.98 wt%, Sb 2 O 3 : 0.22 wt%, SnO 2 : 0.12 wt%.

[0045] During the actual use of the above substances, B 2 O 3 is introduced in the form of H 2 BO 3 , and Na 2 O is introduced in the form of Na 2 CO 3 and NaNO 3 and can form gases during the glass melting process to accelerate the clarification of the glass.

[0046] In some embodiments, the fining agent can be selected from at least one of Na 2 SO 4 , NaCl, CaSO 4 , SnO 2 , Sb 2 O 3 ; more preferably, Sb 2 O3 and SnO 2 As a fining agent, it accelerates the fining of the glass system. Specifically, compared with the mass percentage of the overall glass components, its composition is: Sb 2 O 3 : 0 to 0.3%, SnO 2 : 0 to 0.2%.

[0047] In some embodiments, the total mass percentage of SiO 2 + Al 2 O 3 + B 2 O 3 in the special encapsulation glass is 65 to 85 wt%.

[0048] In some embodiments, the softening point of the special encapsulation glass is 850 to 930 °C, and / or the coefficient of thermal expansion of the special encapsulation glass within 40 to 400 °C is (39 to 80) × 10 -7 K -1 .

[0049] In some embodiments, the transition temperature of the special encapsulation glass is 640 to 680 °C, the density is less than 2.5 g / cm 3 , and the Knoop hardness > 410 kgf / mm 2 .

[0050] Obviously, the special encapsulation glass prepared by the present invention has a wide range of coefficients of thermal expansion, can be suitable for sealing different substrates, and at the same time has a moderate softening point and excellent comprehensive performance.

[0051] Of course, for the above special encapsulation glass, the present invention also provides a corresponding preparation method. During the preparation of the glass, the glass raw materials are placed in a high-temperature melting apparatus (such as a crucible, a kiln, etc.), and glass forming is carried out during the processes of melting, fining, and homogenization. Finally, after annealing treatment, the final glass product can be obtained. Specifically, the preparation of the special encapsulation glass provided by the present invention includes the following steps:

[0052] S1. Weigh the component raw materials and mix them evenly to obtain the glass batch;

[0053] S2. Add the glass batch to a hot crucible heated at high temperature;

[0054] S3. After heating up, keep the temperature, then carry out stirring treatment, and continue to keep the temperature after stopping stirring to obtain the glass melt;

[0055] S4. After the heat preservation is completed, pour the obtained glass melt into a preheated mold to obtain the formed glass material;

[0056] S5. Anneal the obtained formed glass material to obtain the special encapsulation glass.

[0057] In some embodiments, in step S2, the high-temperature heating temperature is 1550-1630 °C. Exemplarily, the high-temperature heating temperature can be a certain value among 1550 °C, 1560 °C, 1570 °C, 1580 °C, 1590 °C, 1600 °C, 1610 °C, 1620 °C, 1630 °C, 1640 °C, 1650 °C or any value within the above range; preferably, the high-temperature heating temperature is 1580-1640 °C; more preferably, it is 1600 °C.

[0058] In some embodiments, in step S3, the temperature is raised to 1640-1700 °C, and the holding time after heating is 1-4 h;

[0059] The stirring treatment time is 4-12 h;

[0060] The holding time after stopping stirring is 10-60 min.

[0061] Exemplarily, the heating temperature can be a certain value among 1640 °C, 1650 °C, 1660 °C, 1670 °C, 1680 °C, 1690 °C, 1700 °C or any value within the above range; preferably, it can be 1645-1670 °C; more preferably, it is 1650 °C. The holding time after heating can be adjusted according to actual needs, and preferably it is 2 h. The stirring treatment can be a certain value among 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, and more preferably it is 7 h; the stirring time after stopping stirring is preferably 30 min.

[0062] In some embodiments, in step S5, the specific steps of the annealing treatment are: holding at 610-650 °C for 6-24 h, then cooling at 4 °C / h to 510-550 °C and at 20 °C / h to 270-290 °C, and then stopping heating and cooling. Preferably, the treatment steps can be: holding at 632 °C for 10 h, then cooling at 4 °C / h to 532 °C and at 20 °C / h to 282 °C, stopping heating (power off) at 290 °C, and cooling to 50 °C.

[0063] Of course, it should be particularly noted that in step S1, after weighing the glass raw materials according to the formula of the encapsulating glass material to obtain the glass batch, the glass batch can be added in batches, and it can be added according to the situation of adding once every half hour. The specific addition frequency can be flexibly adjusted according to the melting time of the glass, which is a general technical means that those skilled in the art can master.

[0064] Based on the excellent properties of the above-mentioned special sealing glass, it can be applied to the sintering seal with any one of alloys, metals, glasses or ceramics to meet the application requirements in different scenarios.

[0065] Next, the technical solutions of the present invention will be further described through the following specific embodiments.

[0066] Example 1

[0067] A special sealing glass is composed of the following components: SiO 2 : 52.66 g, Al 2 O 3 : 22.52 g, B 2 O 3 : 4.31 g, Na 2 O: 9.16 g, MgO: 9.11 g, Sb 2 O 3 : 0 g, SnO 2 : 0.24 g. Among them, the above-mentioned B 2 O 3 is introduced in the form of H 2 BO 3 , and Na 2 O is introduced in the form of Na 2 CO 3 and NaNO 3 .

[0068] This embodiment also provides a preparation method of the above-mentioned special sealing glass, including the following steps:

[0069] S1. Weigh the component raw materials and mix them evenly to obtain the glass raw material;

[0070] S2. Add the glass raw material to a platinum crucible heated to 1600 °C at high temperature, add it once every 30 minutes until the raw materials are added up;

[0071] S3. Raise the temperature to 1650 °C at a heating rate of 5 °C / min and keep it warm for 2 h. After the heat preservation ends, stir at this temperature for 7 h, the stirring rate is 30 rpm, and then stop stirring and keep it warm for 30 min to obtain the glass liquid;

[0072] S4. Pour the obtained glass liquid into a mold preheated to 500 °C to obtain the formed glass material;

[0073] S5. After cooling the obtained formed glass material to 700 °C, pour it out of the mold, wrap it with silicon fiber cotton, and put it into a muffle furnace for annealing: keep it at 632 °C for 10 h, cool it from 632 °C to 532 °C at a rate of 4 °C / h, cool it from 532 °C to 282 °C at a rate of 20 °C / h / h, and cut off the power to cool it at 290 °C; take out the glass at 50 °C, and the special encapsulation glass is obtained.

[0074] After testing: the above special sealing glass has a coefficient of thermal expansion of α in the temperature range of 40 - 400 °C 1 = 73.11×10 - 7 K -1 , a density of 2.439 g / cm 3 , a softening point of 874 °C, and a Knoop hardness of 430.16 kgf / mm 2 .

[0075] Example 2

[0076] A special sealing glass is composed of the following components: SiO 2 : 60.82 g, Al 2 O 3 : 20.11 g, B 2 O 3 : 4.22 g, Na 2 O: 11.18 g, MgO: 3.34 g, Sb 2 O 3 : 0.22 g, SnO 2 : 0.12 g. Among them, the above B 2 O 3 is introduced in the form of H 2 BO 3 , and Na 2 O is introduced in the form of Na 2 CO 3 and NaNO 3 .

[0077] In this example, a preparation method of the above special sealing glass is also provided, including the following steps:

[0078] S1. Weigh the component raw materials and mix them evenly to obtain the glass batch.

[0079] S2. Add the glass batch into a platinum crucible heated to 1600 °C at high temperature, add it once every 30 min until all the raw materials are added.

[0080] S3. Heat it to 1650 °C at a heating rate of 5 °C / min and keep it for 2 h. After the holding is completed, stir it at this temperature for 7 h at a stirring rate of 30 rpm, then stop stirring and keep it for 30 min to obtain the glass melt.

[0081] S4. Pour the obtained glass liquid into a mold preheated to 500 °C to obtain a formed glass material;

[0082] S5. After cooling the obtained formed glass material to 700 °C, pour it out of the mold, wrap it with silicon fiber cotton, and put it into a muffle furnace for annealing: keep it at 632 °C for 10 h, cool it from 632 °C to 532 °C at a rate of 4 °C / h, cool it from 532 °C to 282 °C at a rate of 20 °C / h / h, and cut off the power for cooling at 290 °C; take out the glass at 50 °C / h to obtain the special encapsulation glass.

[0083] After testing: the above special sealing glass has a coefficient of thermal expansion of α in the temperature range of 40 - 400 °C 1 = 69.7×10 -7 K -1 , a density of 2.4039 g / cm 3 , a softening point of 902 °C, and a Knoop hardness of 428.4 kgf / mm 2 .

[0084] Example 3

[0085] A special sealing glass is composed of the following components: SiO 2 : 60.70 g, Al 2 O 3 : 20.30 g, B 2 O 3 : 4.21 g, Na 2 O: 10.92 g, MgO: 3.33 g, ZrO 2 : 0.19 g, Sb 2 O 3 : 0.22 g, SnO 2 : 0.12 g. Among them, the above B 2 O 3 is introduced in the form of H 2 BO 3 , and Na 2 O is introduced in the form of Na 2 CO 3 and NaNO 3 .

[0086] This example also provides a preparation method of the above special sealing glass, including the following steps:

[0087] S1. Weigh the component raw materials and mix them evenly to obtain a glass raw material;

[0088] S2. Add the glass raw material to a platinum crucible heated to 1600 °C at high temperature, add it once every 30 min until all the raw materials are added;

[0089] S3. Heat it to 1650 °C at a heating rate of 5 °C / min, hold for 2 h, stir for 7 h at this temperature after holding, with a stirring rate of 30 rpm, then stop stirring and hold for 30 min to obtain molten glass;

[0090] S4. Pour the obtained molten glass into a mold preheated to 500 °C to obtain a formed glass material;

[0091] S5. After cooling the obtained formed glass material to 700 °C, pour it out of the mold, wrap it with silicon fiber cotton, and put it into a muffle furnace for annealing: hold at 632 °C / h for 10 h, cool from 632 °C / h to 532 °C / h at a rate of 4 °C / h, cool from 532 °C / h to 282 °C / h at a rate of 20 °C / h / h, cut off the power for cooling at 290 °C / h; take out the glass at 50 °C / h to obtain the special encapsulation glass.

[0092] After testing: the above special sealing glass has a coefficient of thermal expansion of α 1 = 68.01×10 - 7 K -1 in the temperature range of 40 - 400 °C, a density of 2.4122 g / cm 3 , a softening point of 907 °C, and a Knoop hardness of 434.38 kgf / mm 2 .

[0093] Example 4

[0094] A special sealing glass is composed of the following components: SiO 2 : 60.65 g, Al 2 O 3 : 20.05 g, B 2 O 3 : 4.21 g, Na 2 O: 10.20 g, MgO: 3.33 g, TiO 2 : 1.22 g, Sb 2 O 3 : 0.22 g, SnO 2 : 0.12 g. Among them, the above B 2 O 3 is introduced in the form of H 2 BO 3 , and Na 2 O is introduced in the form of Na 2 CO 3 and NaNO 3 .

[0095] This example also provides a preparation method for the above special sealing glass, including the following steps:

[0096] S1. Weigh the component raw materials and mix them evenly to obtain the glass batch material;

[0097] S2. Add the glass batch material into a platinum crucible heated to 1600 °C at high temperature, adding it once every 30 minutes until all the raw materials are added;

[0098] S3. Raise the temperature to 1650 °C at a heating rate of 5 °C / min and hold for 2 hours. After the holding is completed, stir at this temperature for 7 hours with a stirring rate of 30 rpm. Then stop stirring and hold for 30 minutes to obtain the glass melt;

[0099] S4. Pour the obtained glass melt into a mold preheated to 500 °C to obtain the formed glass material;

[0100] S5. After cooling the obtained formed glass material to 700 °C, pour it out of the mold, wrap it with silicon fiber cotton, and put it into a muffle furnace for annealing: hold at 632 °C for 10 hours, cool from 632 °C to 532 °C at a rate of 4 °C / h, cool from 532 °C to 282 °C at a rate of 20 °C / h / h, and cut off the power for cooling at 290 °C; take out the glass at 50 °C / h to obtain the special encapsulation glass.

[0101] After testing: The above special sealing glass has a coefficient of thermal expansion of α 1 = 67.75×10 - 7 K -1 in the temperature range of 40 - 400 °C, a density of 2.4135 g / cm 3 , a softening point of 905 °C, and a Knoop hardness of 433.68 kgf / mm 2 .

[0102] Example 5

[0103] A special sealing glass is composed of the following components: SiO 2 : 62.71 g, Al 2 O 3 : 21.45 g, B 2 O 3 : 4.10 g, Na 2 O: 3.09 g, MgO: 2.65 g, Y 2 O 3 : 0 g, Sb 2 O 3 : 0.22 g, SnO 2 : 0.11 g. Among them, the above B 2 O 3 is introduced in the form of H 2 BO 3 and Na 2 O is from Na 2 CO 3and NaNO 3 in the form of

[0104] This embodiment also provides a preparation method for the above special sealing glass, including the following steps:

[0105] S1. Weigh the component raw materials and mix them evenly to obtain the glass batch.

[0106] S2. Add the glass batch into a platinum crucible heated to 1600 °C at high temperature, adding it every 30 minutes until all the raw materials are added.

[0107] S3. Heat it up to 1650 °C at a heating rate of 5 °C / min and then hold for 2 hours. After the holding ends, stir at this temperature for 7 hours with a stirring rate of 30 rpm. Then stop stirring and hold for 30 minutes to obtain the glass melt.

[0108] S4. Pour the obtained glass melt into a mold preheated to 500 °C to obtain the formed glass material.

[0109] S5. After cooling the obtained formed glass material to 700 °C, pour it out of the mold, wrap it with silicon fiber cotton, and put it into a muffle furnace for annealing: hold at 632 °C / h for 10 hours, cool from 632 °C / h to 532 °C / h at a rate of 4 °C / h, cool from 532 °C / h to 282 °C / h at a rate of 20 °C / h / h, and cut off the power for cooling at 290 °C / h; take out the glass at 50 °C / h to obtain the special sealing glass.

[0110] After testing: The above special sealing glass has a coefficient of thermal expansion of α 1 = 39.25×10 - 7 K -1 in the temperature range of 40 - 400 °C, a density of 2.4932 g / cm 3 , a softening point of 915 °C, and a Knoop hardness of 452.8 kgf / mm 2 .

[0111] Example 6

[0112] A special sealing glass consists of the following components: SiO 2 : 59.41 g, Al 2 O 3 : 19.26 g, B 2 O 3 : 4.12 g, Na 2 O: 10.22 g, MgO: 3.26 g, Y 2 O 3 : 3.39 g, Sb 2 O 3 : 0.22 g, SnO 2: 0.11 g. Among them, the above-mentioned B 2 O 3 is introduced in the form of H 2 BO 3 , and Na 2 O is introduced in the form of Na 2 CO 3 and NaNO 3 .

[0113] In this embodiment, a preparation method of the above-mentioned special sealing glass is also provided, including the following steps:

[0114] S1. Weigh the component raw materials and mix them evenly to obtain the glass raw material;

[0115] S2. Add the glass raw material to a platinum crucible heated to 1600 °C at high temperature, add it once every 30 min until the raw materials are added up;

[0116] S3. Raise the temperature to 1650 °C at a heating rate of 5 °C / min and keep it warm for 2 h. After the heat preservation ends, stir at this temperature for 7 h, the stirring rate is 30 rpm, then stop stirring and keep it warm for 30 min to obtain the glass liquid;

[0117] S4. Pour the obtained glass liquid into a mold preheated to 500 °C to obtain the formed glass material;

[0118] S5. After cooling the obtained formed glass material to 700 °C, pour it out of the mold, wrap it with silicon fiber cotton, and put it into a muffle furnace for annealing: keep it warm at 632 °C / h for 10 h, cool it from 632 °C / h to 532 °C / h at a rate of 4 °C / h, cool it from 532 °C / h to 282 °C / h at a rate of 20 °C / h / h, cut off the power and cool it at 290 °C / h; take out the glass at 50 °C / h to obtain the special packaging glass.

[0119] After testing: The above-mentioned special sealing glass has a coefficient of thermal expansion of α 1 = 67.4×10 -7 K -1 in the temperature range of 40 - 400 °C, the density is 2.4650 g / cm 3 , the softening point is 907 °C, and the Knoop hardness is 409.0 kgf / mm 2 .

[0120] Example 7

[0121] A special sealing glass is composed of the following components: SiO 2 : 61.01 g, Al 2 O 3 : 19.78 g, B 2 O 3 : 4.23 g, Na 2O: 10.97 g, MgO: 3.66 g, Sb 2 O 3 : 0.22 g, SnO 2 : 0.12 g. Among them, the above-mentioned B 2 O 3 is introduced in the form of H 2 BO 3 and Na 2 O is introduced in the form of Na 2 CO 3 and NaNO 3 .

[0122] In this embodiment, a preparation method of the above-mentioned special sealing glass is also provided, including the following steps:

[0123] S1. Weigh the component raw materials and mix them evenly to obtain the glass raw material;

[0124] S2. Add the glass raw material to a platinum crucible heated to 1600 °C at high temperature, add it once every 30 min until the raw materials are added up;

[0125] S3. Raise the temperature to 1650 °C at a heating rate of 5 °C / min and then keep it warm for 2 h. After the heat preservation ends, stir at this temperature for 7 h, the stirring rate is 30 rpm, then stop stirring and keep it warm for 30 min to obtain the glass liquid;

[0126] S4. Pour the obtained glass liquid into a mold preheated to 500 °C to obtain the formed glass material;

[0127] S5. After cooling the obtained formed glass material to 700 °C, pour it out of the mold, wrap it with silicon fiber cotton, and put it into a muffle furnace for annealing: keep it warm at 632 °C / h for 10 h, cool it from 632 °C / h to 532 °C / h at a rate of 4 °C / h, cool it from 532 °C / h to 282 °C / h at a rate of 20 °C / h / h, cut off the power and cool it at 290 °C / h; take out the glass at 50 °C / h to obtain the special packaging glass.

[0128] After testing: The above-mentioned special sealing glass has a coefficient of thermal expansion of α 1 = 70.06×10 - 7 K -1 in the temperature range of 40 - 400 °C, the density is 2.4117 g / cm 3 , the softening point is 897 °C, and the Knoop hardness is 435.4 kgf / mm 2 .

[0129] Example 8

[0130] A special sealing glass is composed of the following components: SiO 2 : 61.11 g, Al2 O 3 : 19.81 g, B 2 O 3 : 4.24 g, Na 2 O: 10.51 g, MgO: 3.98 g, Sb 2 O 3 : 0.22 g, SnO 2 : 0.12 g. Among them, the above B 2 O 3 is introduced in the form of H 2 BO 3 , and Na 2 O is introduced in the form of Na 2 CO 3 and NaNO 3 .

[0131] This embodiment also provides a preparation method for the above special sealing glass, including the following steps:

[0132] S1. Weigh the component raw materials and mix them evenly to obtain the glass raw material;

[0133] S2. Add the glass raw material to a platinum crucible heated to 1600 °C at high temperature, add it once every 30 min until all the raw materials are added;

[0134] S3. Heat it up to 1650 °C at a heating rate of 5 °C / min and then hold for 2 h. After the holding is over, stir at this temperature for 7 h, with a stirring rate of 30 rpm. Then stop stirring and hold for 30 min to obtain the glass liquid;

[0135] S4. Pour the obtained glass liquid into a mold preheated to 500 °C to obtain the formed glass material;

[0136] S5. After cooling the obtained formed glass material to 700 °C, pour it out of the mold, wrap it with silicon fiber cotton, and put it into a muffle furnace for annealing: hold at 632 °C / h for 10 h, cool from 632 °C / h to 532 °C / h at a rate of 4 °C / h, cool from 532 °C / h to 282 °C / h at a rate of 20 °C / h / h, and cut off the power for cooling at 290 °C / h; take out the glass at 50 °C / h to obtain the special packaging glass.

[0137] After testing: the above special sealing glass has a coefficient of expansion of α 1 = 70.45×10 - 7 K -1 in the temperature range of 40 - 400 °C, a density of 2.4106 g / cm 3 , a softening point of 895 °C, and a Knoop hardness of 437.3 kgf / mm 2 .

[0138] Comparative Example 1

[0139] A special sealing glass is composed of the following components by mass: SiO 2 : 72.10 g, B 2 O 3 : 18.93 g, K 2 O: 5.77 g, Al 2 O 3 : 3.2 g.

[0140] In this comparative example, a preparation method of the above special sealing glass is also provided, including the following steps:

[0141] S1. Weigh the component raw materials and mix them evenly to obtain glass raw materials;

[0142] S2. Add the glass raw materials to a platinum crucible heated to 1600 °C at high temperature, adding once every 30 min until all the raw materials are added;

[0143] S3. Raise the temperature to 1650 °C at a heating rate of 5 °C / min and then hold for 2 h. After the holding is completed, stir at this temperature for 7 h, with a stirring rate of 30 rpm. Then stop stirring and hold for 30 min to obtain glass liquid;

[0144] S4. Pour the obtained glass liquid into a mold preheated to 500 °C to obtain a formed glass material;

[0145] S5. After cooling the obtained formed glass material to 700 °C, pour it out of the mold, wrap it with silicon fiber cotton, and put it into a muffle furnace for annealing: hold at 632 °C / h for 10 h, cool from 632 °C / h to 532 °C / h at a rate of 4 °C / h, cool from 532 °C / h to 282 °C / h at a rate of 20 °C / h / h, and cut off the power for cooling at 290 °C / h; take out the glass at 50 °C / h to obtain the special packaging glass.

[0146] After testing: The expansion coefficient of the above special sealing glass in the temperature range of 40 - 400 °C is α 1 = 51.49×10 - 7 K -1 , and the softening point is at 756 °C.

[0147] Comparative Example 2

[0148] A special sealing glass is composed of the following components by mass: SiO 2 : 63.28 g, Al 2 O 3 : 13.08 g, MgO: 8.27 g, CaO: 11.89 g.

[0149] In this comparative example, a preparation method of the above special sealing glass is also provided, including the following steps:

[0150] S1. Weigh the component raw materials and mix them evenly to obtain the glass batch.

[0151] S2. Add the glass batch into a platinum crucible heated to 1600 °C at high temperature, adding it once every 30 minutes until all the raw materials are added.

[0152] S3. Heat it up to 1650 °C at a heating rate of 5 °C / min and then hold for 2 hours. After the holding is completed, stir at this temperature for 7 hours with a stirring rate of 30 rpm. Then stop stirring and hold for 30 minutes to obtain the glass melt.

[0153] S4. Pour the obtained glass melt into a mold preheated to 500 °C to obtain the formed glass material.

[0154] S5. After cooling the obtained formed glass material to 700 °C, pour it out of the mold, wrap it with silicon fiber cotton, and put it into a muffle furnace for annealing: hold at 632 °C / h for 10 hours, cool from 632 °C / h to 532 °C / h at a rate of 4 °C / h, cool from 532 °C / h to 282 °C / h at a rate of 20 °C / h / h, and cut off the power for cooling at 290 °C / h; take out the glass at 50 °C / h to obtain the special encapsulation glass.

[0155] After testing: the expansion coefficient of the above special sealing glass is α in the temperature range of 40 - 400 °C 1 = 47.49×10 - 7 K -1 , and the softening point is at 952 °C.

[0156] The compositions and test results of each example and comparative example are shown in Table 1.

[0157] Table 1 Compositions and Test Results of Examples and Comparative Examples

[0158]

[0159] Continued Table 1

[0160]

[0161] Among them, the determination of the expansion coefficient is carried out with reference to GB / T7962.16 - 2010; the determination of the density is carried out with reference to GB / T7962.20 - 2010; the determination of the Knoop hardness is carried out with reference to GB / T 7962.18 - 2010; the determination of the softening point is carried out with reference to GB / T28195 - 2011.

[0162] As can be seen from the above table, the expansion coefficients of Examples 1 - 8 of the present invention are all in the range of (39 - 80)×10 -7 K -1Within a certain range, the large expansion coefficient regulation range can better match the expansion coefficients of the sealing glass material with materials such as alloys, metals, ceramics, and glass, making it have a wider applicability. Secondly, the softening points are all in the range of 850-930 °C, and the Knoop hardness > 410 kgf / mm 2 . For the sealing glass of the prior art, if the softening point is higher than 930 °C, it is very difficult to sinter and may damage the sealing substrate. However, if the softening point is lower, the strength of the material will be affected. Therefore, after balancing the sealing temperature and material strength, the present invention can effectively solve the above problems.

[0163] In Comparative Example 1, the softening point of the prepared glass material is too low; in Comparative Example 2, the softening point of the prepared glass material is too high. The glass materials prepared by both are not suitable for actual industrial applications.

[0164] The present invention uses the above embodiments to illustrate the technical concept of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of individual raw materials of the products of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A special packaging glass with medium to high softening point and wide expansion coefficient, characterized in that: The invention comprises the following components in percentage by mass: SiO2 50.0-65.0%, Al2O3 15.0-25.0%, B2O3 0-7.0%, Na2O 5.0-15.0%, Li2O 0-1%, MgO 1-10%, CaO 0-1.0%, BaO 0-3.0%, ZrO2 0-4.0%, TiO2 0-2.0%, Y2O3 0-6.0%, clarifier 0-0.5%, and inevitable impurities.

2. The special packaging glass with medium-high softening point and wide expansion coefficient according to claim 1, characterized in that: The total mass percentage of SiO2+Al2O3+B2O3 in the special packaging glass is 65-85wt%.

3. The special packaging glass with medium-high softening point and wide expansion coefficient according to claim 1, characterized in that: The softening point of the special encapsulation glass is 850-930°C, and / or the expansion coefficient of the special encapsulation glass within 40-400°C is (39-80)×10 -7 K -1 .

4. The special packaging glass with medium-high softening point and wide expansion coefficient according to claim 1, characterized in that: The clarifier includes at least one of Na2SO4, NaCl, CaSO4, SnO2, and Sb2O3.

5. The special packaging glass with medium-high softening point and wide expansion coefficient according to claim 4, characterized in that: The transition temperature of special packaging glass is 640-680℃ and the density is less than 2.5g / cm 3 , Kirkmar hardness>410kgf / mm 2 .

6. A method for preparing the special packaging glass according to any one of claims 1 to 5, characterized in that: The steps include: S1. Weigh component raw materials and mix them evenly to obtain glass raw material; S2, adding raw glass material into a hot crucible heated at high temperature; S3, after heating, heat preservation is performed, and then stirring is performed, and stirring is stopped and then heat preservation is continued to obtain glass liquid; S4, after the heat preservation is completed, pouring the obtained glass liquid into the preheated mold to obtain a formed glass material; S5. Annealing the obtained shaped glass material to obtain special packaging glass.

7. The preparation method according to claim 6, characterized in that: In step S2, the high temperature heating temperature is 1550-1630°C.

8. The preparation method according to claim 6, characterized in that: In step S3, the temperature is raised to 1640-1700°C, and the holding time after the temperature is raised is 1-4 hours; The stirring treatment time is 4 to 12 hours; After stopping stirring, the heat preservation time is 10 to 60 minutes.

9. The preparation method according to claim 6, characterized in that: In step S5, the specific steps of annealing treatment are: keep at 610-650°C for 6-24h, then cool down to 510-550°C at 4°C / h, cool down to 270-290°C at 20°C / h, stop heating, and cool down.

10. Use of the special encapsulation glass according to any one of claims 1 to 5 or the special encapsulation glass prepared by the method according to any one of claims 6 to 9, characterized in that: The special packaging glass is sintered and sealed with one of alloy, metal, glass or ceramic.

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