CN112125529A - Glass fiber ingredient and glass fiber prepared from same - Google Patents

Abstract

The glass fiber ingredient comprises the following components in percentage by mass: SiO 2₂50‑65wt.%、TiO₂10‑18wt.%、CaO+MgO 10‑16wt.%、Li₂O+Na₂O+K₂O 6‑11wt.%、Al₂O₃+ZrO₂0‑4wt.%、Y₂O₃+La₂O₃+CeO₂0.5‑2wt.%、B₂O₃0‑2wt.%、Fe₂O₃0.1 to 1 wt%. In the glass fiber mixture, high content of TiO is used₂While using an extremely low Al content₂O₃And ZrO₂The glass fiber with high performance can be prepared with low cost and high efficiency. Specifically, the raw materials are put into a melting device to melt glass fiber ingredients in advance, and then the molten glass is drawn and formed through a pore plate, so that the high-performance glass fiber can be obtained.

Description

Glass fiber ingredient and glass fiber prepared from same

Technical Field

The invention relates to the field of glass fibers, in particular to a glass fiber ingredient and a glass fiber prepared from the same.

Background

The main component of the glass fiber is silicon dioxide. Depending on the properties of the particular application for which the glass fiber is used, the most commonly used glass fibers at present comprise mainly SiO₂-Al₂O₃-ZrO₂、SiO₂-Al₂O₃-B₂O₃、SiO₂-Al₂O₃RO (R is Mg, Ca), SiO₂-Al₂O₃-R¹ ₂O（R¹Na, K, Li), etc., and then various modifying components, such as Fe, are added thereto₂O₃、ZnO、P₂O₅、F、SO₃、Y₂O₃、La₂O₃、CeO₂、Gd₂O₃、Sm₂O₃、TiO₂、CuO、Nb₂O₅、WO₃And the like.

For the production of glass fibers, manufacturers often need to make a compromise between performance and ease of handling, cost of the production process. It is known that in the production of glass fibers, it is necessary to melt a glass fiber batch in advance in a melting apparatus and then draw and shape the molten glass through an orifice plate.

However, in order to improve the mechanical strength, modulus, acid resistance, alkali resistance, etc. of the glass fiber, it is generally necessary to add a modifying component to the glass fiber formulation. For example, in order to improve alkali resistance, it is common practice to add ZrO₂But ZrO₂The liquid phase temperature of the glass fiber is greatly increased, so that a specific melting device is needed to melt the glass fiber ingredients, the corresponding wire drawing forming temperature is increased due to the increase of the liquid phase temperature, the requirement on the pore plate is increased, and the cost is increased. For example, it is common practice to add Y in order to improve the modulus of the glass fibers₂O₃、La₂O₃、CeO₂Etc., but the rare earth oxide is expensive, and the use of a large amount of rare earth oxide increases the cost of the glass fiber. In addition, some of the usual components in glass fibres, e.g. TiO₂、SiO₂、Al₂O₃CaO, etc., are easily crystallized in the glass fiber or are crystallized during the molding process, which seriously affect the strength, modulus, etc. of the glass fiber.

The invention aims to provide a high-performance glass fiber compound which is easy to produce glass fibers, thereby obtaining the high-performance glass fibers with good production operability and low forming temperature.

Disclosure of Invention

The inventors of the present invention have discovered in their research that prior glass fiber formulations, typically SiO, are used in the present invention₂+Al₂O₃And/or ZrO₂Is the main component. Wherein, Al₂O₃The mechanical strength, the elastic modulus, the chemical stability and the like of the glass fiber can be improved; ZrO (ZrO)₂The alkali resistance of the glass fiber can be improved. They are an essential component for high performance glass fibers and are generally present in amounts of between 5 and 15wt.% or even higher to achieve good results. However, it is the high content of these two components that causes difficulty in the easy handling of the glass fiber, and although the easy handling of the glass fiber can be achieved by adding some modifying components, the cost increases and the performance of the glass fiber cannot be guaranteed.

To this end, in the glass fiber formulation of the present invention, Al₂O₃And ZrO₂The dosage of the compound is small, and relatively speaking, the TiO is increased₂The dosage of the additive is increased by MgO, CaO and K₂O、Na₂The dosage of the components such as O and the like not only reduces the liquid phase temperature of the glass fiber ingredient, is easy to prepare the glass fiber, but also ensures the performance of the prepared glass fiber.

Specifically, the glass fiber ingredient comprises the following components in percentage by mass:

SiO₂ 50-65wt.%

TiO₂ 10-18wt.%

CaO+MgO 10-16wt.%

Li₂O+ Na₂O+ K₂O 6-11wt.%

Al₂O₃+ZrO₂ 0-4wt.%

Y₂O₃+La₂O₃+CeO₂ 0.5-2wt.%

B₂O₃ 0-2wt.%

Fe₂O₃ 0.1-1wt%。

furthermore, in the glass fiber formula, the molar ratio of Al atoms to Ti atoms is less than or equal to 0.2; the molar ratio of Zr atoms to Ti atoms is 0.08 or less.

Further, in the glass fiber compound, the molar ratio of Al atoms + Zr atoms to Ti atoms is less than or equal to 0.2.

In the glass fiber formulation of the present invention, SiO₂Is the main component for forming the glass skeleton structure, and provides basic guarantee for the mechanical strength and acid resistance of the glass fiber.

TiO₂Has the function of improving the water resistance and alkali resistance of the glass fiber. For improving alkali resistance, its action and ZrO₂Similarly. However, if a high content of ZrO is simultaneously used in the glass fibre batch₂And TiO₂Easy formation of zirconium titanate or ZrO during wire drawing₂·TiO₂Crystallization can cause the blockage of the orifice plate, which is not beneficial to the smooth operation of the wire drawing forming process. Thus, the present invention uses high levels of TiO₂At the same time, an extremely low ZrO content is used₂To avoid the above situation. Furthermore, TiO₂But also has positive effect on reducing the liquidus temperature and the drawing forming temperature of the glass fiber, and conversely, ZrO₂The use of (a) will substantially raise the liquidus temperature and the draw forming temperature of the glass fibers. Therefore, in the present invention, for ZrO₂And TiO₂The amount of the glass fiber is also used in consideration of the liquidus temperature and the drawing temperature of the glass fiber, and the ease of handling in the preparation of the glass fiber.

TiO₂Also oxides forming the skeleton of the glass fibres, possibly with SiO₂The backbone body of (a) is well matched and further improves the mechanical strength and modulus of the glass fiber. Improvement of mechanical strength and modulus, effect thereof and Al₂O₃Similarly. However, if a high Al content is used simultaneously in the glass fiber batch₂O₃And TiO₂Easy formation of Al during wire drawing₂O₃·TiO₂Crystallization can also cause the blockage of the orifice plate, which is not favorable for smooth feeding of the wire drawing forming processAnd (6) rows. Therefore, in the present invention, high TiO content is used in consideration of a combination of factors such as liquid phase temperature, mechanical strength, and alkali resistance₂At the same time, the extremely low content of Al is used₂O₃To avoid the above situation.

For TiO₂If the amount of (2) is more than 18%, TiO-containing particles are liable to be precipitated in the glass fibers₂The possibility of crystallization of (a) reduces the ease of production. If the content is less than 10%, the glass fiber is insufficient in properties such as alkali resistance, mechanical strength and modulus.

For Al₂O₃And ZrO₂In consideration of Al during molding₂O₃·TiO₂Zirconium titanate or ZrO₂·TiO₂In the crystal composition relationship of (3), it is preferable that the molar ratio of Al atoms to Ti atoms is 0.2 or less and the molar ratio of Zr atoms to Ti atoms is 0.08 or less, whereby clogging of a perforated plate and wire breakage due to crystallization can be further effectively prevented. More preferably, when the above atomic ratio is satisfied, it is more advantageous to set the molar ratio of Al atoms + Zr atoms to Ti atoms to 0.2 or less.

CaO and MgO have the effects of reducing the viscosity of glass, controlling the crystallization of the glass and promoting the melting of glass fiber ingredients, and simultaneously, in the melting process, the CaO and the MgO can also remove bubbles from a glass melt and improve the mechanical strength and the elastic modulus of the glass fiber.

Li₂O、Na₂O、K₂O has the functions of reducing the viscosity of the glass and improving the melting performance of the glass. And the alkali metal oxide can provide a large amount of free oxygen which can promote the refining effect of the rare earth oxide on the glass melt.

Fe₂O₃Has the effect of improving the homogeneity of the molten glass by improving the meltability of the glass fiber ingredients by absorbing heat rays. In addition, the temperature uniformity of the glass fiber ingredients in the processes of temperature rise and temperature drop is facilitated, the local crystallization rate of glass is improved, and the productivity of the glass fiber is improved.

B₂O₃The function of the glass fiber is to reduce the liquidus temperature and the drawing forming temperature of the glass fiber. However, B₂O₃Should not be too high, too much B₂O₃The alkali resistance of the glass fiber is easily reduced.

The glass fiber compound of the invention can contain the following components with the total content of 0-2wt.% in addition to the above components: F. SO (SO)₃、ZnO、P₂O₅、CuO、Nb₂O₅、WO₃、Cr₂O₃、Gd₂O₃、Sm₂O₃。

The liquid phase temperature of the glass fiber material is about 1030 ℃ to 1100 ℃, and the wire drawing forming temperature is about 1200 ℃ to 1250 ℃. The glass fiber ingredient is put into a melting device to melt the glass fiber ingredient in advance, and then the molten glass is drawn and formed through a pore plate, so that the glass fiber with high performance and easy preparation can be obtained.

Detailed Description

In order to further highlight the advantages of the glass fiber furnish of the present invention and the glass fibers produced therefrom, a detailed explanation and description is provided below using specific examples.

The high-performance glass fiber ingredient comprises the following components in percentage by mass:

SiO₂ 50-65wt.%

TiO₂ 10-18wt.%

CaO+MgO 10-16wt.%

Li₂O+ Na₂O+ K₂O 6-11wt.%

Al₂O₃+ZrO₂ 0-4wt.%

Y₂O₃+La₂O₃+CeO₂ 0.5-2wt.%

B₂O₃ 0-2wt.%

Fe₂O₃ 0.1-1wt%。

wherein the molar ratio of Al atoms to Ti atoms is less than or equal to 0.2; the molar ratio of Zr atoms to Ti atoms is not more than 0.08, and the molar ratio of Al atoms + Zr atoms to Ti atoms is not more than 0.2

The glass fiber ingredient is put into a melting device to melt the glass fiber ingredient in advance, and then the molten glass is drawn and formed through a pore plate, so that the glass fiber with high performance and easy preparation can be obtained.

Examples 1 to 4 and comparative examples 1 to 3

Corresponding glass fibers were prepared with reference to the component ratios in table 1. Examples 1-4 are labeled A1-A4, respectively, and comparative examples 1-3 are labeled B1-B3.

In the performance test and comparison, the liquidus temperature, the forming temperature, the temperature difference between the forming temperature and the liquidus temperature, the elastic modulus, the alkali resistance, the acid resistance, the water resistance and the wire breakage of the glass fiber compound and the prepared glass fiber are listed, and the specific results are shown in table 1.

TABLE 1

From the specific results in the above table, it can be seen that a high amount of TiO is used₂While using an extremely low Al content₂O₃And ZrO₂The blockage of the pore plate can be avoided, and the occurrence of the wire breakage condition in the wire drawing forming process can be further avoided. High content of TiO₂The use of the method effectively reduces the liquid phase temperature and the forming temperature of the glass fiber ingredient, the operability of preparing the glass fiber is good, the production efficiency is high, and the produced glass fiber has excellent mechanical strength, modulus, acid resistance, alkali resistance and other properties. However, in comparative example 1, the molar ratio of Al atoms to Ti atoms was 0.065; the molar ratio of Zr atoms to Ti atoms was 0.162, and the molar ratio of Al atoms + Zr atoms to Ti atoms was 0.227. The high Zr/Ti atomic ratio and (Al + Zr)/Ti atomic ratio ensure that zirconium titanate or ZrO is easy to form in the glass fiber forming process₂·TiO₂Of (2) aThere is a tendency that slight wire drawing and breakage occur in a part of the molding process. The glass fiber molding temperature of the invention is in the range of 1200-1250 ℃, the requirements on a melting device and an orifice plate device are relatively low, and the production cost is low.

Claims (6)

1. The glass fiber ingredient comprises the following components in percentage by mass:

SiO₂ 50-65wt.%

TiO₂ 10-18wt.%

CaO+MgO 10-16wt.%

Li₂O+ Na₂O+ K₂O 6-11wt.%

Al₂O₃+ZrO₂ 0-4wt.%

Y₂O₃+La₂O₃+CeO₂ 0.5-2wt.%

B₂O₃ 0-2wt.%

Fe₂O₃ 0.1-1wt%。

2. the glass fiber formulation according to claim 1, wherein the molar ratio of Al atoms to Ti atoms in the glass fiber formulation is 0.2 or less; the molar ratio of Zr atoms to Ti atoms is 0.08 or less.

3. The glass fiber formulation according to claim 2, wherein the molar ratio of Al atoms + Zr atoms to Ti atoms in the glass fiber formulation is 0.2 or less.

4. The glass fiber furnish of claim 1 further comprising the following in a total amount of 0 to 2 wt.%: F. SO (SO)₃、ZnO、P₂O₅、CuO、Nb₂O₅、WO₃、Cr₂O₃、Gd₂O₃、Sm₂O₃。

5. The glass fiber furnish of claim 1 wherein the liquidus temperature of the glass fiber furnish is about 1030 ℃ and the draw forming temperature is about 1200 ℃ and 1250 ℃.

6. A high-performance glass fiber, which is prepared by using the glass fiber batch as claimed in any one of claims 1 to 5 as a raw material, putting the raw material into a melting device to melt the glass fiber batch in advance, and drawing and molding the molten glass through an orifice plate.