1. The method for improving the uniformity of the high-temperature melting calcium-boron-silicon glass is characterized by comprising the following steps:

(1) selecting glass raw materials:

selecting nano-scale silicon dioxide powder, boric acid and calcium carbonate as raw materials;

(2) and (3) measuring the burning loss value and the purity value of the glass raw material:

carrying out burning loss test on the nano silicon dioxide and the calcium carbonate at the temperature of 500-700 ℃, carrying out burning loss test on boric acid at the temperature of 100-200 ℃, and keeping the peak temperature for 1-3 h to obtain a burning loss value A of the raw materials;

testing the purity of the raw material by an X-ray spectrum analyzer XRF or an inductively coupled plasma spectrum generator ICP to obtain a purity value B of the raw material;

(3) calculating the amount of the raw materials needing to be actually added:

setting the design value of the raw material as D, and calculating the amount of the raw material to be actually added according to the formula C ═ D ÷ B ÷ (1-A);

(4) mixing glass raw materials:

grinding and mixing the nano-scale silicon dioxide, the boric acid and the calcium carbonate by using a dry mixing process;

(5) glass smelting:

glass is smelted by a high-temperature stirring smelting method, a crucible is fixed in a smelting furnace, and the glass is heated to be completely melted and then stirred to be fully homogenized in the smelting process;

(6) glass cooling and glass sheet synchronous forming:

the molten glass is cooled to a transparent and uniform glass sheet using a roller cooling process.

2. The method for improving the homogeneity of the high-temperature smelted calcium-boron-silicon glass according to claim 1, wherein the dry mixing process is to mix the raw materials by using a mixing device, and the mixing device is a high-speed disperser for three-dimensional mixing or a coulter type high-efficiency mixer.

3. The method of improving the homogeneity of a hot-melt calborosilicate glass according to claim 2, wherein the mixing device is lined with an alumina ceramic or a zirconia ceramic.

4. The method for improving the homogeneity of high temperature molten calborosilicate glass according to claim 1, wherein said high temperature stirring is stirring with a stir bar; the strength of the stirring rod can be effectively improved and deformation and glass adhesion are reduced by using the platinum-molybdenum alloy.

5. The method of improving the homogeneity of high temperature smelted calborosilicate glass as claimed in claim 4, wherein said stir bar is a platinum molybdenum alloy stir bar.

6. The method of claim 1, wherein the roll cooling and roll stretching process uses a twin roll cooling mill as the apparatus.

7. The method of claim 1, wherein the glass raw materials comprise, in mass percent: 33% of nano silicon dioxide, 34% of calcium carbonate and 33% of boric acid.

8. The method of claim 1, wherein the glass raw materials comprise, in mass percent: 33% of silicon dioxide, 34% of calcium oxide and 33% of boron trioxide.

9. The method for improving the uniformity of the high-temperature melting calcium-boron-silicon glass as claimed in claim 1, wherein the melting temperature of the high-temperature melting is 1500 ℃, and the holding time is 3h +/-0.1 h.

Background

Calcium borosilicate glass is widely used as microcrystalline glass in building materials and electronic materials. However, the phenomenon of non-uniformity of glass caused by phase separation easily occurs in the melting process of the calcium borosilicate glass, so that the phase separation of the glass is uncontrollable and the uniformity of the glass performance is seriously damaged. The main factors that induce phase separation of glass are: the formula of the glass, the precision of the glass raw material ingredients, the smelting process of the glass and the like. Regarding the formulation of the glass, the softening point of the borosilicate glass is fixed in a certain range in the electronic material, and therefore the glass formulation is also in a certain range. The fundamental reason of glass phase separation is that silicon dioxide and boron trioxide are substances forming a glass network structure, free oxygen is easily mutually snatched in the glass melting process, the network structure is preferentially constructed, and glass phase separation is easily formed when local boron network structure advantages or silicon network structure advantages appear in the process. Therefore, the uniformity of the calcium-borosilicate glass can be affected by the selection of raw materials, the uniform mixing of the raw materials, the glass melting process and the like. In the traditional glass melting method, mixed glass raw materials are filled into a crucible for static heating melting, so that local non-uniformity of glass components is easily caused, and phase separation of glass is caused. In addition, the traditional glass melting and cooling method adopts a water quenching cooling method, so that the phase separation phenomenon of glass is not easy to find, in order to avoid the phase separation condition, only calcium borosilicate glass with high calcium oxide content, low diboron trioxide (boric acid) content and low silicon dioxide content can be melted, and the prepared glass can not meet the use requirement of the LTCC ceramic material.

In the prior art, in terms of raw materials, diboron trioxide and calcium oxide are easy to absorb moisture to influence the purity of the raw materials, so that the batching is inaccurate; in the aspect of raw material mixing, the raw material mixing of oxides is not easy to be uniform; in the aspect of glass smelting, the particle sizes of quartz sand and boron trioxide are large, the particle size of calcium carbonate (calcium oxide) is small, the particle size difference of raw materials is too large, so that the material mixing is not uniform, gaps formed by overlapping large particle substances in the smelting process are large, the softened material flows to the bottom of a crucible, so that the glass components of an upper layer and a lower layer are inconsistent, and a boron network structure or a silicon network structure is easily enriched in the smelting process, so that the glass is easily layered and split in phase when being smelted.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The purpose of the invention is: the problem of how to improve the homogeneity of calcium borosilicate glass when the current calcium borosilicate glass is smelted at high temperature is solved.

The technical conception adopted by the invention is as follows: the uniformity of the calcium-boron-silicon glass smelting is improved from the aspects of raw material selection, uniform mixing of raw materials, glass smelting process and the like. The nanometer-level silicon dioxide, the boric acid and the calcium carbonate are used as raw materials to be fully mixed, the uniformity of the raw materials is improved after the nanometer-level raw materials are fully mixed, the glass solution is fully homogenized again by using a stirring mode after the glass raw materials are melted in the glass melting process, the local advantages of a boron network structure and a silicon network structure in the glass solution are reduced, and the phase splitting probability of calcium borosilicate glass with high content of boron trioxide and high content of silicon dioxide is reduced.

In the aspect of raw material selection, nano-scale silicon dioxide, boric acid and calcium carbonate are used as raw materials, and the actual demand of the raw materials is calculated through the tests on the burning loss and the purity of the raw materials; in the aspect of uniform mixing of raw materials, the raw materials with large particle size difference are better than the raw materials with large particle size difference after the raw materials with the nanometer level are fully mixed; in the aspect of a glass smelting process, in the glass smelting process, the nanoscale boric acid is liquefied at about 800 ℃, nanoscale liquid drops are adsorbed by the same nanoscale calcium oxide and silicon dioxide, and aggregation and delamination of glass raw materials are not easy to generate; after the glass raw materials are completely melted, the glass liquid is further fully homogenized by using a stirring mode, the local advantages of a boron network structure and a silicon network structure in the glass liquid are reduced, and the phase splitting probability of the calcium borosilicate glass with high content of boron trioxide and high content of silicon dioxide is reduced.

Therefore, the invention provides a method for improving the uniformity of high-temperature melting calcium-boron-silicon glass, which comprises the following steps:

1. selection of raw materials

Nanometer silicon dioxide powder, boric acid and calcium carbonate are selected as raw materials.

2. Measurement of raw Material burnout value and purity value

Carrying out burning loss test on the nano silicon dioxide and the calcium carbonate at the temperature of 500-700 ℃, carrying out burning loss test on boric acid at the temperature of 100-200 ℃, and keeping the peak temperature for 1-3 h to obtain a burning loss value A of the raw material (removing moisture and organic impurities contained in the material at high temperature, wherein the removed part is burning loss); and testing the purity of the raw material by using an X-ray spectrum analyzer XRF or an inductively coupled plasma spectrum generator ICP to obtain a purity value B of the raw material.

3. Calculating the amount of the raw materials to be actually added

The design value of the raw material was set to D. The amount of the raw material to be actually added can be calculated from the formula C ═ D ÷ B ÷ (1-a).

The formula C is a formula commonly used in the prior art, namely D/B/1-A, the burning loss of the value C is weighed as A, and the effective raw material in the raw material with the purity of B is weighed as D.

4. Mixing of raw materials

The boric acid/boron trioxide can not be ground and mixed by using water or alcohol as a medium, only dry grinding can be used, and dry ball milling mixing is preferred because the nano silicon dioxide powder is easy to form hardening in the dry grinding and mixing process. In the invention, the raw materials are mixed by using a three-dimensional mixing high-speed disperser or a coulter type efficient mixer, and alumina or zirconia ceramic lining is used as mixing equipment to reduce the pollution of metal abrasion to the raw materials.

5. Glass melting

The method comprises the steps of smelting glass by using a high-temperature stirring smelting method, fixing a crucible in a smelting furnace, heating the glass to be completely molten, and then starting stirring, so that the glass is fully homogenized in the smelting process, the uniformity of the glass is improved, and the risk of phase splitting of the glass is reduced. The stirring rod is made of platinum-molybdenum alloy, so that the strength of the stirring rod can be effectively improved, and deformation and glass adhesion are reduced.

6. Glass cooling and glass sheet synchronous forming

And (3) cooling the molten glass into transparent and uniform glass sheets by using a double-roller cooling rolling mill, so that the uniformity of the glass can be observed, whether phase splitting occurs or not can be observed, and meanwhile, the subsequent grinding processing technology of the glass sheets is facilitated.

The invention has the main advantages that the calcium-borosilicate glass with an internal microstructure is formed, and the product performance, quality consistency and reliability of the calcium-borosilicate glass are improved. The method is widely applied to the fields of modern microwave electronic communication such as high-frequency electronics, aerospace electronic equipment, mobile communication, electronic countermeasure, satellite communication, a Beidou system (GPS), a Bluetooth technology, a wireless local area network (MLAN), an Internet of things and the like.

Drawings

FIG. 1 is a schematic diagram of a phase separation effect caused by whitening of a glass part manufactured by a conventional technology.

FIG. 2 is a schematic view of the glass manufactured by the present invention with overall transparency, uniformity and no phase separation effect.

Detailed Description

Compared with the traditional process, the method for improving the uniformity of the high-temperature melting calcium-boron-silicon glass comprises the following steps:

1. selecting glass raw materials: two groups of glass formulas are designed, wherein the component A uses nano silicon dioxide, calcium carbonate and boric acid as raw materials, and the component B uses 100-mesh quartz sand, calcium oxide and boron trioxide as raw materials. The amounts of the raw materials were calculated in the proportions shown in Table 1.

Table 1 raw material composition table (mass percentage)

2. Mixing raw materials: the raw materials are fully mixed by using a high-speed dispersion machine or a coulter type high-efficiency mixer.

3. High-temperature smelting: melting A, B two kinds of glass respectively by using a traditional crucible melting mode and a novel stirring melting mode, wherein the melting temperature is 1500 ℃, and the heat preservation time is 3h +/-0.1 h.

4. Cooling glass: the glass was cooled using a two-roll cooling mill and observed for homogeneity and phase separation. The results of the comparative test of the glass cooling method are shown in Table 2.

TABLE 2 glass Cooling method COMPARATIVE TABLE

Finally, it should be noted that: the above examples are merely examples for clarity of illustration, and the present invention includes but is not limited to the above examples, which are not necessarily exhaustive of all embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Embodiments that meet the requirements of the present invention are within the scope of the present invention.