CN107216042B

CN107216042B - High-modulus glass fiber composition and glass fiber

Info

Publication number: CN107216042B
Application number: CN201710413847.6A
Authority: CN
Inventors: 李红宾; 姚远; 杨国云; 韩利雄; 张聪; 宫白江
Original assignee: Chongqing Polycomp International Corp
Current assignee: Chongqing Polycomp International Corp
Priority date: 2017-06-05
Filing date: 2017-06-05
Publication date: 2020-09-08
Anticipated expiration: 2037-06-05
Also published as: CN107216042A

Abstract

The invention provides a high modulus glass fiber composition, which comprises the following components: SiO 2₂50wt％～58wt％；Al₂O₃18wt％～24wt％；SiO₂With Al₂O₃72.5 wt% -79.5 wt% of the total content; al (Al)₂O₃/SiO₂The mass fraction ratio is 0.34-0.45; TiO 2₂0.2wt％～1.5wt％；ZnO 0～2.0wt％；ZrO₂0～2.0wt％；Fe₂O₃0.1 wt% -0.6 wt%; 9.2 to 11 weight percent of CaO; 9 to 12 weight percent of MgO; the total content of CaO and MgO is 18.2 wt% -22 wt%; the ratio of the mass fraction of MgO to the mass fraction of CaO is 1.0-1.3; na (Na)₂O、K₂O and Li₂The total content of O is 0.2 to 1.0 weight percent; the above components amounted to 100%.

Description

High-modulus glass fiber composition and glass fiber

Technical Field

The invention relates to the technical field of inorganic nonmetallic materials, in particular to a high-modulus glass fiber composition and glass fibers.

Background

The glass fiber belongs to an inorganic non-metallic material, has the advantages of high mechanical strength, good electrical insulation, strong heat resistance, stable physical and chemical properties and the like, is widely applied to the fields of aerospace, automobiles, ships, petrifaction, energy sources, electric power, buildings and the like, and is an inorganic fiber reinforced material with the largest application amount at present. In the application process of the glass fiber, along with the continuous increase of the size of the composite material product, people put higher and higher requirements on the mechanical property, especially the elastic modulus of the glass fiber.

There are many related studies on the method for improving the strength and modulus of glass fibers. Most typical are S glass and R glass. The basic composition of the S glass is as follows: 65 wt% SiO₂25 wt% of Al₂O₃10 wt% MgO. The theoretical monofilament strength of the S glass fiber is up to 4500MPa, the elastic modulus exceeds 85GPa, and the mechanical property is very excellent. But the molding temperature of the material exceeds 1470 ℃, and the material is easy to crystallize and has high production difficulty, so that the material cannot be popularized and applied on a large scale. R glass is also a high strength high modulus glass fiber, typically made of SiO₂、Al₂O₃CaO, MgO is generally considered a compromise between manufacturing difficulty and mechanical properties, and is therefore more productive than S glass.

Japanese patent JP8231240 discloses a glass fiber composition comprising 62 to 67 wt% of SiO₂22 to 27 wt% of Al₂O₃7 to 15 wt% of MgO, 0.1 to 1.1 wt% of CaO, 0.1 to 1.1 wt% of B₂O₃. The glass fiber is prepared by adding small amount of CaO and B₂O₃The number of bubbles is obviously improved relative to S glass fiber, but the forming is still very difficult, and the forming temperature exceeds 1460 ℃.

Japanese patent JP2003171143 also describes a high strength and high modulus glass fiber containing 55 to 65 wt% of SiO₂17 to 23 wt% of Al₂O₃7-15 wt% of MgO, 2-6 wt% of CaO, 1-7 wt% of TiO₂. Compared with S glass, the glass fiber has sacrifice in mechanical property, but obviously improved forming performance, and the forming temperature is about 1340-1380 ℃. But TiO in the glass fiber₂The high content makes the glass darker in color, which limits its application in certain fields.

U.S. patent publication No. US2010/0160139 discloses a high performance glass fiber composition comprising: 64 to 75 wt% of SiO₂16 to 24 wt% of Al₂O₃8 to 12 wt% of MgO and 0.25 to 3 wt% of Li₂O+Na₂And O. Compared with S glass fiber, the glass fiber is added with a certain amount of Li₂O and Na₂O, thereby reducing the high-temperature viscosity and the molding difficulty of the glass. However, if Li is contained in the glass of the system₂O and Na₂The effect is not obvious if the adding amount of O is low; too high an amount of the additive seriously affects the insulating property and the corrosion resistance of the glass fiber, so that the fiber forming property of the glass fiber is difficult to control.

Patent application No. CN201080070857.0 discloses a high strength glass fiber, the composition of which comprises: 56 to 61 wt% of SiO₂16 to 23 wt% of Al₂O₃8-12 wt% of MgO, 6-10 wt% of CaO, 0-2 wt% of Na₂O, less than 1 wt% Li₂O, and less than 2 wt% of a transition metal oxide. The glass fibers do achieve good mechanical properties, but from their practical examplesIt can be seen that in order to balance the difficulty of production, it is added with more than 1% of Na₂O, and too high Na₂O can have an effect on the chemical stability of the glass fiber.

Patent application No. CN201180028428.1 also discloses a high strength glass fiber, the composition of which comprises: 57 to 63 wt% of SiO₂19 to 23 wt% of Al₂O₃10 to 15 wt% of MgO, 4 to 11 wt% of CaO, and SiO₂、Al₂O₃The total content of CaO and MgO is 99.5 wt% or more. The elastic modulus of the glass fiber in the patent can reach more than 96GPa, but the control of Fe is low because of the requirement₂O₃And the content of alkali metal oxide, so that the cost of raw materials is high, and the problems of crystallization and melting are all solved with certain difficulty.

Disclosure of Invention

In view of the above, the present invention provides a high modulus glass fiber composition and a glass fiber, which have excellent mechanical properties and low viscosity.

The invention provides a high modulus glass fiber composition, which comprises the following components:

the above components amounted to 100%.

Wherein the silicon dioxide (SiO)₂) Is one of the main oxides forming the glass network, which mainly plays a role in improving the mechanical strength, chemical stability and thermal stability of the glass, but too high content increases the viscosity and melting temperature of the glass, resulting in high difficulty in forming glass fibers and high production cost. SiO of the invention₂The content is 50 wt% to 58 wt%, preferably 50 wt% to 56 wt%, more preferably 52 wt% to 55.8 wt%.

Alumina (Al)₂O₃) Is also shapeOne of the main oxides forming the glass network, which has the effects of reducing the tendency of devitrification of the glass, increasing the chemical stability and mechanical strength of the glass, but if Al is present₂O₃Too high content will result in too high glass viscosity, difficult glass-forming and easy crystallization. Al of the invention₂O₃The content is 18 wt% to 24 wt%, preferably 19 wt% to 23.6 wt%.

The Al is₂O₃And SiO₂The ratio of the total content to the mass fraction has important significance on the elastic modulus of the aluminosilicate glass, and Al₂O₃The higher the relative proportion, the greater the elastic modulus of the glass, but the greater the difficulty of production and the tendency to devitrify at the same time, the invention being limited to SiO₂With Al₂O₃The total content of (A) is 72.5 wt% to 79.5 wt%, preferably 74.5 wt% to 78.6 wt%. Al (Al)₂O₃/SiO₂The mass fraction ratio is 0.34-0.45, and preferably, the Al is₂O₃/SiO₂The mass fraction ratio is 0.37-0.44. The proportion range can ensure that the glass fiber has the optimal elastic modulus, the optimal melt-drawing performance and the optimal crystallization temperature.

Titanium dioxide (TiO)₂) The addition of the glass fiber is beneficial to improving the high-temperature fluidity and the crystallization tendency of the glass, and improving the mechanical property and the corrosion resistance of the glass fiber. However, the content of titanium dioxide is not preferably more than 1.5% by weight, since the color of the glass is affected. TiO of the invention₂The content of (B) is 0.2 wt% to 1.5 wt%, preferably 0.2 wt% to 1.0 wt%.

The invention adds zinc oxide (ZnO) and zirconium oxide (ZrO) into glass fiber₂) The oxide with small ionic radius and large electric field intensity has the functions of improving the crystallization performance of the glass, and improving the elastic modulus and the chemical stability of the glass. In the invention, the ZnO content is 0-2.0 wt%, preferably, the ZnO content is not 0, and more preferably 0.2-0.9 wt%; ZrO (ZrO)₂The content is 0 to 2.0 wt%, preferably, the ZrO content is not 0, more preferably 0.2 wt% to 0.9 wt%.

A small amount of Fe contained therein₂O₃Is beneficial to the heat transfer of the tank furnace, but if the content is too high, the color of the glass fiber is improvedAnd heat transfer performance are adversely affected. The iron oxide content of the present invention is limited to 0.1 wt% to 0.6 wt%, preferably 0.2 wt% to 0.5 wt%.

The calcium oxide (CaO) and the magnesium oxide (MgO) have the functions of reducing the high-temperature viscosity of the glass and improving the devitrification tendency of the glass. The ionic radius of MgO is smaller than that of CaO, so that the higher MgO proportion is beneficial to forming a more compact glass network structure and improving the elastic modulus of the glass. However, if the MgO content is too high, the difficulty of production becomes unacceptable. The CaO content of the invention is 9.2 wt% to 11 wt%, preferably, the CaO content is 9.5 wt% to 11 wt%, more preferably 10.1 wt% to 11 wt%, and the MgO content is 9 wt% to 12 wt%, more preferably 10 wt% to 11.5 wt%. The total content of CaO and MgO is 18.2 wt% to 22 wt%, preferably 19.5 wt% to 21.8 wt%, and more preferably 20.1 wt% to 21.8 wt%. The MgO/CaO mass fraction ratio is 1.0-1.3, preferably 1.0-1.1.

In the present invention, preferably, Li is further added to the glass fiber composition₂O、Na₂O and K₂And O, which helps to reduce the viscosity of the glass and improve the devitrification tendency of the glass. However, the alkali metal content should not be too high, since the chemical stability of the glass is impaired. Glass composition Na of the invention₂O、K₂O and Li₂The total O content is 0.2 wt% to 1.0 wt%, more preferably 0.5 wt% to 0.8 wt%.

According to the invention, the glass fiber composition of the invention can preferably contain not more than 3 wt% of F for improving the glass fiber forming performance without affecting the mechanical properties of the glass fiber₂、B₂O₃、Y₂O₃、BaO、La₂O₃、CeO₂One or more of (a).

The invention controls Al precisely₂O₃/SiO₂And the ratio and respective content range of MgO/CaO, so that the glass fiber not only has extremely high elastic modulus, but also has melting wire drawing performance and crystallization temperature within acceptable ranges; adding Na in proper proportion₂O、K₂O and Li₂O content ofIs helpful to reduce the melting temperature of the glass and the production difficulty. And a small amount of ZnO and ZrO with small ionic radius and large electric field intensity are introduced₂And defining ZnO and ZrO₂The content can further inhibit the glass crystallization tendency and has positive effect on the elastic modulus of the glass; therefore, the glass fiber of the invention contains the components, and the content and the proportion of the components are accurately controlled, so that the glass fiber obtains excellent mechanical property and lower viscosity forming property.

The invention also provides a high modulus glass fiber prepared from the composition.

The method for preparing the glass fiber is not particularly limited, and the glass fiber can be prepared by a method well known to those skilled in the art, preferably by a tank furnace method, and can be prepared by the following method:

uniformly mixing various raw materials, putting the mixture into a tank furnace, and melting, clarifying and homogenizing the mixture to obtain molten glass;

and cooling, flowing out and drawing the molten glass to obtain the glass fiber.

Firstly, mixing various raw materials in a mixing tank, and conveying the raw materials to a tank furnace bin after the raw materials are uniformly mixed; then putting the mixture into a tank furnace bin, and melting, clarifying and homogenizing at 1400-1800 ℃ to obtain molten glass;

cooling the molten glass to 1250-1350 ℃, enabling the molten glass to flow out through a platinum bushing plate, and drawing the molten glass into glass wires with the diameter of 3-25 mu m under the traction of a drawing machine;

and carrying out spray cooling on the glass filaments, and coating a sizing agent to obtain the glass fiber.

After obtaining the glass fiber, the glass fiber was subjected to a performance test.

Experimental results show that the forming temperature of the glass fiber is not more than 1350 ℃, the upper limit crystallization temperature is lower than 1300 ℃, and the elastic modulus of the glass fiber is greater than 95 GPa.

Detailed Description

To further illustrate the present invention, the high modulus glass fiber composition and glass fibers provided by the present invention are described in detail below with reference to the examples.

Example 1

Conveying the raw materials to a mixing tank, uniformly mixing, and conveying the mixture to a tank furnace bin, wherein the content of each raw material is shown in table 1;

putting the mixture in a storage bin of the tank furnace into the tank furnace, melting the mixture into molten glass gradually at a high temperature of more than 1400 ℃ in the tank furnace, clarifying and homogenizing the molten glass, and feeding the stable and high-quality molten glass into a wire drawing operation channel;

cooling the glass liquid in the wire drawing operation channel to a proper temperature, then flowing out through a platinum bushing, rapidly drawing the glass liquid into glass wires with the diameter of 3-25 mu m by a wire drawing machine, and winding the glass wires into wire cakes on the wire drawing machine after the glass wires are subjected to spray cooling, impregnating compound coating and collecting;

and (4) twisting, weaving, performing surface treatment and the like on all the spinning cakes to obtain the glass fiber.

The glass fibers were subjected to performance tests, and the results are shown in table 1, where table 1 shows the formulations and properties of the glass fibers provided in the examples and comparative examples of the present invention.

Examples 2 to 6

The preparation method is the same as the example, except that the content of each raw material is changed, and the specific content is shown in table 1.

The glass fibers were subjected to performance tests, the results of which are shown in table 1, and table 1 is a table of formulations and performance data of the glass fibers provided in examples and comparative examples of the present invention.

Comparative examples 1 to 2

Conveying various raw materials to a mixing tank according to a formula shown in table 1, uniformly mixing, and conveying a mixture to a storage bin of a tank furnace, wherein the content of each raw material is shown in table 1;

The glass fibers were subjected to performance tests, and the results are shown in table 1, where table 1 is a table of formulations and performance data of the glass fibers provided in examples of the present invention and comparative examples.

TABLE 1 formulation and Performance data Table for glass fibers provided in examples and comparative examples

As can be seen from the above examples and comparative examples, the invention improves the comprehensive properties of the glass fiber by precisely adjusting various components and specific contents thereof.

The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims

1. A high modulus glass fiber composition comprising the following components:

2. the composition of claim 1, wherein the Al is₂O₃The content is 19 to 23.6 weight percent; the SiO₂With Al₂O₃The total content of (A) is 74.5 wt% -78.6 wt%; the Al is₂O₃/SiO₂The mass fraction ratio is 0.37-0.44.

3. The composition of claim 1, wherein the TiO is selected from the group consisting of₂The content is 0.2 wt% -1.0 wt%.

4. The composition according to claim 1, wherein the CaO content is 9.5-11 wt%; the total content of CaO and MgO is 19.5 wt% -21.8 wt%; the ratio of the MgO/CaO mass fraction is 1.0-1.1.

5. The composition according to claim 1, wherein the ZrO₂The content is 0.2 wt% -0.9 wt%.

6. The composition as claimed in claim 1, further comprising: not more than 3 wt% of F₂、B₂O₃、Y₂O₃、BaO、La₂O₃And CeO₂One or more of (a).

7. A high modulus glass fiber prepared from the composition of any one of claims 1 to 6.