CN107540211B

CN107540211B - Alkali silicate glass containing alumina and zirconia

Info

Publication number: CN107540211B
Application number: CN201711007123.8A
Authority: CN
Inventors: 田英良; 杨宝瑛; 孙诗兵; 吕锋; 李辉
Original assignee: Beijing University of Technology
Current assignee: Beijing University of Technology
Priority date: 2017-10-25
Filing date: 2017-10-25
Publication date: 2020-11-06
Anticipated expiration: 2037-10-25
Also published as: CN107540211A

Abstract

The invention discloses alkali silicate glass containing aluminum oxide and zirconium oxide, which comprises the following components in percentage by mol: SiO 2₂45-80% of R₂O is 10-30%, ZrO₂+Al₂O₃10 to 25 percent; wherein: ZrO (ZrO)₂:Al₂O₃In a molar ratio of 1:4, R₂O:(Al₂O₃+ZrO₂) Is 1.0 to 1.2. The invention introduces Al into alkali silicate glass₂O₃And ZrO₂Effectively realizing the recombination and reconstruction of the glass structure; the components and the proportion are adopted, so that the melting characteristic, the forming characteristic and the process characteristic of the glass can be considered, and the glass provided by the invention has relatively excellent mechanical property, good toughness, impact resistance and scratch resistance.

Description

Alkali silicate glass containing alumina and zirconia

Technical Field

The invention relates to the technical field of glass, in particular to alkali silicate glass containing aluminum oxide and zirconium oxide.

Background

Alkali silicate glass (R)₂O-SiO₂) Is a basic binary glass system, R₂O is an alkali metal oxide and has a good melting property, but has poor chemical stability and mechanical strength, thus becoming a fatal weakness even when a complex alkali metal oxide (Li) is used₂O，Na₂O，K₂O) is used for adjusting and improving the performance, and the performance improvement is relatively limited. R is generally satisfied and controlled if it is desired to form a relatively stable glass₂O/SiO₂In a molar ratio of<0.5, then the total alkali metal oxide requirement is that the total alkali silicate glass (R) be present₂O＝Li₂O，Na₂O，K₂O) less than 33 mol% can meet the requirements of glass.

Alkali silicate glass (R)₂O-SiO₂) The structure in three-dimensional space is basically a layered structure, and only when the chemical composition of the glass is relatively reasonable, the devitrification can be prevented under the influence of the viscosity resistance of the glass. However, in practical production processes, even if the chemical composition is chosen properly, two immiscible liquid phases (SiO) will appear due to the relatively unreasonable cooling rate₂Component phase, Na₂Component phase O).

For improving alkali silicate glass (R)₂O-SiO₂) The performance is traditionally realized by adding alkaline earth metal oxide RO, wherein RO is CaO, MgO and the like, the most used chemical component is CaO, and R is formed₂O-CaO-SiO₂Glass systems, of which the most commonly used glass is typically Na₂O-CaO-SiO₂The glass system almost occupies more than 90 percent of the glass products in the current glass industry, including plate glass, bottle glass, vessel glass, process glass and the like. In alkali silicate glass (R)₂O-SiO₂) The addition of CaO also further improves the glass properties, such as chemical stability, glass stability, and forming process characteristics. Because CaO is still an alkaline oxide, the glass has relatively large brittleness, low hardness and relatively weak mechanical property, and cannot obtain relatively excellent wear resistance, scratch resistance, impact resistance and bending toughness.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides alkali silicate glass containing alumina and zirconia.

In order to achieve the above object, the present invention provides an alkali silicate glass containing alumina and zirconia, which comprises, in mole percent:

SiO₂45-80％；

R₂O 10-30％；

ZrO₂+Al₂O₃10-25％；

wherein:

ZrO₂:Al₂O₃in a molar ratio of 1:4, R₂O:(Al₂O₃+ZrO₂) Is 1.0 to 1.2.

As a further improvement of the invention, R₂O comprises Li₂O、Na₂O and K₂O，Na₂O stands for R₂60-100% of the total molar amount of O, K₂O stands for R₂0-30% of total molar amount of O, Li₂O stands for R₂0-15% of the total molar amount of O.

As a further development of the invention, the SiO₂Is 52-75 mol%.

Compared with the prior art, the invention has the beneficial effects that:

the invention introduces Al into alkali silicate glass₂O₃And ZrO₂Effectively realizing the recombination and reconstruction of the glass structure; by the components and the preparationIn comparison, the melting characteristic, the forming characteristic and the process characteristic of the glass can be taken into consideration, and the glass provided by the invention has relatively excellent mechanical property, good toughness, impact resistance and scratch resistance.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

The invention is described in further detail below:

the hardness and brittleness of the glass severely restrict the application and development of the glass, and at present, the widely used soda-lime glass (Na)₂O-CaO-SiO₂) The glass has relatively good melting preparation aspect, can meet the requirements of low melting temperature and long glass frit property, but has insufficient physical and chemical properties of the glass, such as poor chemical stability, scratch resistance of the glass surface, poor bending toughness and low impact strength, which are mainly caused by alkaline earth metal oxides RO in soda-lime glass, such as CaO, MgO, BaO, SrO and the like, wherein the alkaline earth metal oxides endow the glass with good fluxing property, but have relatively weak action on oxygen atoms, so that the glass network structure is loosened, the glass brittleness is increased, the micro crack extension rate of the glass surface is easily increased under the impact action, and the glass is more easily damaged.

In order to suppress the influence of alkaline earth metal oxides (RO ═ CaO, MgO, BaO, SrO) on the mechanical properties of soda-lime glass, the present invention uses a binary alkali-silica glass system (R) in which the alkaline earth metal oxides are excluded from the glass composition design₂O-SiO₂) As the basis for modifying and adjusting the glass performance, silicon oxide (SiO)₂) Network formation using alkali metal oxide (R)₂O) is used as a network outer body, the glass breaking efficiency is promoted, and the glass melting preparation characteristic requirement is effectively realized.

In order to improve the relative insufficiency of the mechanical property of the alkali-silicon binary glass, the invention introduces and uses alumina (Al)₂O₃) And zirconium oxide (ZrO)₂) And finishing the recombination and reconstruction of the glass structure.

Alumina (Al)₂O₃) Is an intermediate oxide which is used as a contact body of silicon oxide and alkali metal oxide, so that the binary alkali silicate glass has a compact network structure, the dissociation of the alkali metal oxide is reduced, and the improvement of the chemical stability of the glass is promoted. Under the synergistic effect of sodium oxide, when Na is used₂O/Al₂O₃When the molar ratio of the aluminum oxide to the glass is less than or equal to 1, the aluminum oxide can be promoted to be converted into a network forming body, the compactness of a glass structure is optimal, the mechanical property of the glass is improved, the brittleness of the glass is greatly improved particularly, the bending and impact strength is increased by 50-80%, the expansion of microcracks is inhibited and hindered, and the toughness of the glass is obviously enhanced.

Zirconium oxide (ZrO)₂) Is an oxide showing anion characteristic, zirconium ion is a subgroup element with relatively large radius, basically takes part in the connection of glass network in the glass structure, and is accumulated mainly in the form of anion group due to (ZrO)₂) Has a very high melting point of 2450 ℃ and ZrO₂The self hardness reaches and approaches to alumina (Al)₂O₃) The Mohs hardness of 8.5 to 9.0 is inferior to that of diamond (Mohs hardness of 10), thereby promoting and improving scratch resistance of the glass surface due to ZrO₂Low solubility in glass, ZrO₂In the general Na₂O-CaO-SiO₂Only 3 wt% of the glass exists, mainly in the form of anionic groups; relative to Al₂O₃The high-temperature viscosity of the glass can be properly reduced, the phase separation and the crystallization of the glass can be induced, the devitrification of the glass is caused, the stability of the glass state is poor, even if the concentration condition of a crystallization substance is not reached, the viscosity of the glass is improved, the melting temperature is improved, the liquidus temperature is improved, the production and the manufacture of the glass become extremely difficult, and the relative practicability is poor.

The invention finds application in binary alkali silicate glass systems (R)₂O-SiO₂) In (1),the zirconia solubility has interdependence relation with the alumina content, and gradually increases with the increase of alumina, so that the mode of singly depending on alumina is adopted to get rid of the enhancement of glass mechanics, the alumina (Al) and the zirconia respectively meet different characteristic requirements by virtue of double functions of the alumina and the zirconia₂O₃) Improved toughness of zirconium oxide (ZrO)₂) The scratch resistance is improved, so that the comprehensive mechanical property of the glass is better improved. The synergistic solubility relationship of zirconia and alumina is: ZrO (ZrO)₂/Al₂O₃1:4, and an alkali metal oxide R₂O/(Al₂O₃+ZrO₂) 1.0 to 1.2, and ZrO₂+Al₂O₃The total molar amount of the glass accounts for 10 to 25 percent of the total molar amount of the glass; when the conditions are met, the melting property, the forming property and the process property of the glass can be taken into consideration, and the glass with relatively excellent mechanical property, good toughness, impact resistance and scratch resistance can be obtained. Glasses of the above-mentioned composition in which the alkali metal oxide R₂O comprises Li₂O、Na₂O and K₂O, limited in the action characteristics and economy of the glass components, sodium oxide (Na) being preferably used₂O), followed by potassium oxide (K)₂O), furthermore lithium oxide (Li)₂O), can be used alone or in combination, has better combined use effect, is favorable for mixed alkali effect, and preferably selects alkali metal oxide R₂The total mole amount of O is 10-30% of the total mole amount of glass, wherein Na₂O stands for R₂60-100% of the total molar amount of O, K₂O stands for R₂0-30% of total molar amount of O, Li₂O stands for R₂0-15% of the total molar amount of O.

SiO₂Is a glass network former and is a necessary component for forming silicate glass. In order to meet the requirements of glass on physical, chemical and technological properties, SiO₂The total molar amount of (B) is preferably 45 to 80%, more preferably 52 to 75%, based on the total molar amount of glass.

Based on the research, the invention provides alkali silicate glass containing alumina and zirconia, which comprises the following components in percentage by mol:

SiO₂45-80％；

alkali metal oxide R₂O 10-30％；

ZrO₂+Al₂O₃10-25％；

Wherein:

ZrO₂:Al₂O₃in a molar ratio of 1:4, R₂O:(Al₂O₃+ZrO₂) The molar ratio of (A) to (B) is 1.0-1.2; r₂O comprises Li₂O、Na₂O and K₂O，Na₂O stands for R₂60-100% of the total molar amount of O, K₂O stands for R₂0-30% of total molar amount of O, Li₂O stands for R₂0-15% of the total molar amount of O.

Preferably, SiO₂Is 52-75 mol%.

The invention relates to a preparation method of alkali silicate glass containing alumina and zirconia, which comprises the following steps:

weighing the components according to the formula, mixing, melting at high temperature, clarifying, homogenizing, molding and annealing to obtain the glass product.

The glass provided by the invention is used as a material basis for physical toughening treatment and chemical strengthening treatment, creates technical conditions for improving and improving the mechanical property of a glass body, and can expand the application fields of the glass, such as high-speed traffic (high-speed rail and airplane), new energy automobiles, building curtain wall glass, safety glass and even screen display protection glass. The physical tempering is a commonly used airflow quenching process near the glass softening point, the chemical strengthening process adopts a low-temperature method ion exchange process, the potassium nitrate molten salt or the composite nitrate molten salt (the mass ratio of potassium nitrate to sodium nitrate is (70-95): (5-30)) is controlled to be heated to be about 100 ℃ lower than the glass strain point temperature and about 360-450 ℃, the strengthening treatment time is 90-450min, the surface pressure stress of the glass can reach 800-1200MPa, the ion exchange depth reaches 35-120 mu m, the impact strength of the glass can be only improved by 3-8 times, the physical toughening is improved by about 3-5 times, the chemical toughening can be improved by 5-8 times, the surface scratch resistance is improved by 30-50%, and the contribution rate of the strengthening process to the scratch resistance is improved by 60-70%.

Specific examples of the present invention are shown in tables 1 and 2, and the units in tables 1 and 2 are mol%:

TABLE 1

TABLE 2

The invention provides an alkali silicate glass containing alumina and zirconia, and a basic binary alkali silicate glass (R)₂O-SiO₂) For the purpose of improving mechanical property, a mechanical reinforcing component Al is adopted₂O₃And ZrO₂And recombining and reconstructing the glass structure space, and treating by a proper strengthening process to obtain a glass variety with relatively excellent mechanical properties.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An alkali silicate glass containing alumina and zirconia, which is characterized by comprising the following components in percentage by mol:

SiO₂45-80％；

R₂O 10-30％；

ZrO₂+Al₂O₃10-25％；

wherein:

ZrO₂:Al₂O₃in a molar ratio of 1:4, R₂O:(Al₂O₃+ZrO₂) The molar ratio of (A) to (B) is 1.0-1.2;

R₂o comprises Li₂O、Na₂O and K₂O，Na₂O stands for R₂Total amount of O moles60-100% of (A), K₂O stands for R₂0-30% of total molar amount of O, Li₂O stands for R₂0-15% of the total molar amount of O.

2. The alkali silicate glass comprising alumina and zirconia according to claim 1, wherein the SiO is₂Is 52-75 mol%.