阅读说明：本技术 一种防火耐高温的透明玻璃及其制备方法 (Fireproof high-temperature-resistant transparent glass and preparation method thereof ) 是由 郑勇民 郑勇海 程洁 于 2020-12-08 设计创作，主要内容包括：本发明涉及防火玻璃领域,尤其涉及一种防火耐高温的透明玻璃及其制备方法。按照重量份计,其原料包括：SiO_2 62-75份,B_2O_5 5-15份,Al_2O_3 2-10份,Fe_2O_3 0.2-1.4份,R_2O 3-17份,MO 5-14份。本发明通过提供一种防火耐高温的透明玻璃及其制备方法,解决了现有玻璃耐火性差,保护功能有限的缺点；制得的玻璃具有优异的耐火性,玻璃的热膨胀软化温度高达600℃以上。且玻璃表观均匀,无气泡、条纹、析晶等缺陷,耐磨性强,应用前景广阔。(The invention relates to the field of fireproof glass, in particular to fireproof high-temperature-resistant transparent glass and a preparation method thereof. The raw materials comprise the following components in parts by weight: SiO 2 2 62-75 parts of B 2 O 5 5-15 parts of Al 2 O 3 2-10 parts of Fe 2 O 3 0.2-1.4 parts of R 2 O3-17 parts and MO 5-14 parts. The invention provides the fireproof high-temperature-resistant transparent glass and the preparation method thereof, so that the defects of poor fire resistance and limited protection function of the conventional glass are overcome; the prepared glass has excellent fire resistance, and the thermal expansion softening temperature of the glass is as high as more than 600 ℃. The glass has uniform appearance, no defects of bubbles, stripes, crystallization and the like, strong wear resistance and wide application prospect.)

1. The fireproof high-temperature-resistant transparent glass is characterized by comprising the following raw materials in parts by weight: SiO 2₂62-75 parts of B₂O₅5-15 parts of Al₂O₃2-10 parts of Fe₂O₃0.2-1.4 parts of R₂O3-17 parts and MO 5-14 parts.

2. The fireproof high-temperature-resistant transparent glass according to claim 1, wherein the raw materials of the glass further comprise 1-5 parts of a clarifying agent.

3. The fire-resistant, high temperature-resistant transparent glass according to claim 1, wherein R is₂O comprises Na₂O，K₂O，Li₂At least one of O.

4. The fire-resistant, high temperature-resistant transparent glass according to claim 1, wherein the MO comprises at least one of MgO, CaO, BaO.

5. The transparent glass of claim 2, wherein the fining agent comprises La₂O₃，Y₂O₃，CeO₂And NaCl.

6. The transparent glass of claim 5, wherein the fining agent comprises La₂O₃，Y₂O₃And NaCl.

7. The transparent glass of claim 1, wherein the SiO is a fire-resistant and high temperature-resistant glass₂，B₂O₅And Al₂O₃The weight ratio of (10-24): (3-9): 1.

8. the transparent glass of claim 1, wherein the SiO is a fire-resistant and high temperature-resistant glass₂The particle size of (1) is 100-400 meshes.

9. A method of making a fire-resistant, high temperature-resistant transparent glass according to any one of claims 1-8, wherein the glass is made by the steps comprising:

adding the raw materials into a platinum crucible according to the formula amount, melting into glass liquid, and introducing oxygen to the bottom of the glass liquid for 15-54min at the flow rate of 0.5-3L/min by using a platinum pipe; and then standing for 0.5-2h, stirring the glass liquid for 1.5-4h at the rotating speed of 20-100rpm by using a frame type platinum stirrer, cooling, forming, annealing and physically polishing to obtain a glass finished product.

10. The method as claimed in claim 9, wherein the melting temperature is 1440-1580 ℃.

Technical Field

The invention relates to the field of fireproof glass, in particular to fireproof high-temperature-resistant transparent glass and a preparation method thereof.

Background

With the continuous improvement of national economic level, the requirements of various buildings on the safety of the glass curtain wall on the market are also improved. Ordinary curtain wall glass all is all non-refractory, ordinary float glass meets fire and breaks damage time only for 1 minute, toughened glass is only for 5 minutes, and in the curtain wall structure system that comprises frame, joint strip, glass jointly, glass can explode about 250 ℃, after curtain wall glass explodes and falls, flame will leap to upper strata wall from the curtain outside and flee into the upper strata indoor behind the upper glass curtain wall that burns apart, fire prevention glass is as building safety and protection new material, is concerned with people's life and property safety. The 'design fire prevention standard of high-rise civil buildings' and 'technical specification of glass curtain wall engineering' of China clearly stipulate that the outer enclosure of a part of the high-rise buildings must be provided with the fireproof glass. As high-end building glass, the fireproof glass has the performance of common glass, and also needs to have the functions of smoke insulation, heat insulation, fire spread control and the like, so that a fire can be prevented from spreading to other areas of a building through a partition and an outer wall, the life safety of people is guaranteed, and property loss is reduced.

The fire-resistant glass can be classified into a composite fire-resistant glass and a single fire-resistant glass according to the structure. The composite fireproof glass adopts a sandwich structure, transparent fireproof glue is added between two layers or multiple layers of glass, and the flame and heat are separated by the foaming collision of the glue layer after the glass meets fire, so that the personal and property safety of the back fire surface is protected. The composite fireproof glass has stable fire resistance, but has poor water resistance and weather resistance, is easy to generate bubbles, whiten, degum and the like under ultraviolet irradiation, has heavy products, and has shorter service life than single fireproof glass. The single-piece fireproof glass has the advantages of rich raw material sources, simple production process and the like, and occupies an important share in the market, but because of possible defects (stones, scratches and the like) of the original piece of glass and possible process factors such as stress unevenness or stress concentration and the like in the strengthening process, the stability and consistency of the product quality are difficult to ensure, and the application of the single-piece fireproof glass is limited by the properties.

Based on the above, the preparation of transparent glass with strong fire resistance, stability and durability becomes a problem to be solved in the field.

Disclosure of Invention

The invention provides the fireproof high-temperature-resistant transparent glass and the preparation method thereof, so that the defects of poor fire resistance and limited protection function of the conventional glass are overcome; the prepared glass has excellent fire resistance, uniform glass appearance, no defects of bubbles, stripes, crystallization and the like, and wide application prospect.

The invention provides fireproof high-temperature-resistant transparent glass in a first aspect. The raw materials comprise the following components in parts by weight: SiO 2₂62-75 parts of B₂O₅5-15 parts of Al₂O₃2-10 parts of Fe₂O₃0.2-1.4 parts of R₂O3-17 parts and MO 5-14 parts.

In a preferred embodiment, the raw materials of the glass further comprise 1-5 parts of a fining agent.

In a preferred embodiment, R is₂O comprises Na₂O，K₂O，Li₂At least one of O.

In a preferred embodiment, the MO comprises at least one of MgO, CaO, BaO.

In a preferred embodiment, the fining agent comprises La₂O₃，Y₂O₃，CeO₂And NaCl.

In a preferred embodiment, the fining agent comprises La₂O₃，Y₂O₃And NaCl.

In a preferred embodiment, the SiO is₂，B₂O₅And Al₂O₃The weight ratio of (10-24): (3-9): 1.

in a preferred embodiment, the SiO is₂The particle size of (1) is 100-400 meshes.

The invention provides a preparation method of fireproof and high-temperature-resistant transparent glass, which comprises the following specific preparation steps:

adding the raw materials into a platinum crucible according to the formula amount, melting into glass liquid, and introducing oxygen to the bottom of the glass liquid for 15-54min at the flow rate of 0.5-3L/min by using a platinum pipe; and then standing for 0.5-2h, stirring the glass liquid for 1.5-4h at the rotating speed of 20-100rpm by using a frame type platinum stirrer, cooling, forming, annealing and physically polishing to obtain a glass finished product.

In a preferred embodiment, the temperature of the melt is 1440-1580 ℃.

Has the advantages that:

the invention provides the fireproof high-temperature-resistant transparent glass and the preparation method thereof, so that the defects of poor fire resistance and limited protection function of the conventional glass are overcome; the prepared glass has excellent fire resistance, and the thermal expansion softening temperature of the glass is as high as more than 600 ℃. The glass has uniform appearance, no defects of bubbles, stripes, crystallization and the like, strong wear resistance and wide application prospect.

Detailed Description

The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.

As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present application, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention. In addition, the starting materials for the present invention are commercially available unless otherwise specified.

In order to solve the above problems, a first aspect of the present invention provides a fire-resistant and high-temperature-resistant transparent glass. The raw materials comprise the following components in parts by weight: SiO 2₂62-75 parts of B₂O₅5-15 parts of，Al₂O₃2-10 parts of Fe₂O₃0.2-1.4 parts of R₂O3-17 parts and MO 5-14 parts.

In some preferred embodiments, the raw materials for the glass further comprise 1-5 parts of a fining agent.

The invention adds the clarifying agent in the process of preparing the glass, and simultaneously, SiO₂、B₂O₅、Al₂O₃Under the combined action of the two components, the generated gas is promoted to be separated from the surface of the glass or absorbed by the molten glass in the process of melting the glass raw materials at high temperature, and the remaining bubbles in the finished glass product are obviously inhibited.

In some preferred embodiments, R is₂O comprises Na₂O，K₂O，Li₂At least one of O.

In some preferred embodiments, the MO comprises at least one of MgO, CaO, BaO.

In some preferred embodiments, the fining agent comprises La₂O₃，Y₂O₃，CeO₂And NaCl.

In some preferred embodiments, the fining agent comprises La₂O₃，Y₂O₃And NaCl.

The applicant further finds that the thermal expansion softening temperature of the glass can be improved by selecting the rare earth metal oxide and NaCl as the clarifying agents for compatibility; further selecting the clarifying agent as La₂O₃，Y₂O₃And NaCl capable of raising the thermal expansion softening temperature of the glass to 600 deg.c or higher. This is likely to be the rare earth ions dispersed with NaCl in the network voids, effectively reducing the free volume fraction of the glass, with the network units of the glass tending to be more tightly polymerized structures.

In some preferred embodiments, the SiO₂，B₂O₅And Al₂O₃The weight ratio of (10-24): (3-9): 1.

in some preferred embodiments, the SiO₂The particle size of (1) is 100-400 meshes.

Applicants have also found that SiO₂，B₂O₅And Al₂O₃The weight ratio of (10-24): (3-9): 1, the appearance of the glass finished product is further improved, and the product has no bubble, stripe or crystallization defect. Further preferably, the particle size of the silicon dioxide is 100-400 meshes, so that the optical uniformity of the glass surface is further improved. Guessing that the weight ratio is (10-24): (3-9): 1 SiO₂，B₂O₅And Al₂O₃Forming a homogeneous melt skeleton with R₂The coupling effect of modifiers such as O, clarifying agent and the like is strong, the tendency of glass micro-regional phase separation is inhibited, the integrity of a three-dimensional structure of a system is further optimized by silicon dioxide with a specific particle size, the volatilization and dissipation of boron are inhibited, and the effects of no defects such as bubbles, stripes, crystallization and the like are achieved.

The invention provides a preparation method of fireproof and high-temperature-resistant transparent glass, which comprises the following specific preparation steps:

adding the raw materials into a platinum crucible according to the formula amount, melting into glass liquid, and introducing oxygen to the bottom of the glass liquid for 15-54min at the flow rate of 0.5-3L/min by using a platinum pipe; and then standing for 0.5-2h, stirring the glass liquid for 1.5-4h at the rotating speed of 20-100rpm by using a frame type platinum stirrer, cooling, forming, annealing and physically polishing to obtain a glass finished product.

In some preferred embodiments, the temperature of the melt is 1440-1580 ℃.

The invention also unexpectedly discovers that when the platinum crucible melts the raw materials at 1440-1580 ℃, the wear resistance of the prepared glass is improved, probably the flowing capability of the glass liquid at the temperature is strong, the obtained glass finished product is uniform and compact, the grain boundary distribution grains are tortuous, the stress concentration in the dispersed material is favorably dispersed, and the wear resistance of the surface of the glass is improved.

Examples

Example 1.

The embodiment provides a fireproof high-temperature-resistant transparent glass, which comprises the following raw materials in parts by weight: SiO 2₂69 parts of (B)₂O₅17.5 parts of Al₂O₃4 parts of Fe₂O₃0.8 part of, R₂13 parts of O, 8 parts of MO and 3 parts of a clarifying agent.

The R is₂O is Na₂O and Li₂O，Na₂O and Li₂The weight ratio of O is 2: 3.

the MO is MgO and CaO, and the CaO,

the clarifying agent is La₂O₃，Y₂O₃And NaCl, La₂O₃，Y₂O₃And NaCl in a weight ratio of 3: 1: 6.

the SiO₂The particle size of (D) was 200 mesh and purchased from Qingdao Ponkiki separation materials Co., Ltd.

The preparation steps of the glass comprise:

adding the raw materials into a platinum crucible according to the formula amount, melting into molten glass, and introducing oxygen to the bottom of the molten glass for 40min at the flow rate of 2L/min by using a platinum pipe; and then standing for 1h, stirring the glass liquid for 3h at the rotating speed of 80rpm by using a frame type platinum stirrer, cooling, forming, annealing and physically polishing to obtain a glass finished product.

The temperature of the melt was 1500 ℃.

Example 2.

The specific implementation mode of the fireproof high-temperature-resistant transparent glass is the same as that of the embodiment 1. Except that no clarifying agent was added.

Example 3.

The specific implementation mode of the fireproof high-temperature-resistant transparent glass is the same as that of the embodiment 1. The difference is that the clarifying agent is La₂O₃And NaCl, La₂O₃And NaCl in a weight ratio of 1: 1.

example 4.

The specific implementation mode of the fireproof high-temperature-resistant transparent glass is the same as that of the embodiment 1. Different in that Al is present₂O₃Is 10 parts by weight.

Example 5.

The specific implementation mode of the fireproof high-temperature-resistant transparent glass is the same as that of the embodiment 1. The difference is that the SiO₂The particle size of (D) was 50 mesh and purchased from Fucai mineral products Co., Ltd, east China sea county.

Example 6.

The specific implementation mode of the fireproof high-temperature-resistant transparent glass is the same as that of the embodiment 1. Except that the melting temperature was 1400 ℃.

Performance test method

And (3) apparent evaluation:

the glass samples were observed for blisters, streaks, and devitrification using an optical microscope and a magnifying glass (x 3) and scored. The evaluation scale was from 0 (no bubble, streak, devitrification) to 5 (bubble, streak, devitrification).

Thermal expansion softening temperature:

the thermal expansion softening temperature of the obtained glass sample was measured by a thermal expansion instrument model DIL402C manufactured by Netzsch, Germany.

Wear resistance:

and (3) strongly rubbing the surface of the glass sample by using a steel wire soft cloth for 50 times, and grading the surface condition of the abraded glass sample. The rating was from A (intact as original) -D (with obvious scratch)

Performance test data

TABLE 1 results of the Performance test of examples 1 to 6

	Apparent evaluation	Thermal expansion softening temperature of	Wear resistance
				Example 1	0	612	A
Example 2	3	569	B
				Example 3	2	583	C
Example 4	4	576	B
				Example 5	3	582	D
Example 6	3	586	C

Finally, it is pointed out that the foregoing examples are illustrative only, serving to explain some of the characteristics of the process according to the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.