High modulus glass fiber with excellent alkali resistance and preparation method thereof
Technical Field
The invention relates to the field of glass fiber manufacturing, in particular to high-modulus glass fiber with excellent alkali resistance and a manufacturing method thereof.
Background
The high modulus glass fiber is a composite inorganic fiber material with excellent performance, and has wide application in various fields such as aerospace, automobile manufacturing, electronic equipment and the like.
SiO2-Al2O3-ZrO2Glass-based fibers are the most commonly used high modulus glass fibers. In such high modulus glass fibers, SiO2As a main body of the skeleton structure, Al is added2O3Al in (1)3+Of tetrahedral and octahedral coordination structure of (A) to (B), so that SiO2The skeleton structure is communicated, and the high-temperature viscosity and the chemical stability of the glass are improved. ZrO (ZrO)2It is an essential component for improving alkali resistance of the glass fiber and ensuring high modulus, hardness, viscosity, etc.
However, because of ZrO2Too high a melting point of (b), too much ZrO2The addition of (2) will increase the liquidus temperature of the glass, and further the forming temperature of the glass fiber has to be increased, otherwise crystallization is easy to generate in the forming process, a bushing nozzle is blocked, and the breakage (or filament breakage) of the glass fiber is easy to occur. However, the higher the temperature for spinning the glass fiber, the higher the requirements for bushing devices, the more difficult the production and the higher the cost.
The addition of B to glass fibers was proposed by Nanjing glass fiber research and design institute at home and Japan electric glass Kaisha at abroad2O3、TiO2The components are used for reducing the liquidus temperature of the glass so as to realize the realization of the glass fiber under the condition of not increasing the spinning forming temperatureAnd (6) spinning and forming. However, the introduction of these components tends to cause segregation and inhomogeneity of the components in the glass fiber (i.e., glass), which in turn affects the modulus level of the glass fiber.
The addition of Y to glass fibers has also been proposed by the national Jushi group2O3、Nd2O3The rare earth oxides can improve the elastic modulus of the glass, can also obviously reduce the liquidus temperature, the clarification temperature and the forming temperature of the glass, and are beneficial to improving the efficiency of the spinning forming process of the glass fiber. However, the solution is to reduce or even eliminate the use of ZrO2The alkali resistance of the prepared glass fiber is insufficient.
For this purpose, the invention is based on SiO2-Al2O3-ZrO2Based on glass fiber with excellent alkali resistance, high modulus glass fiber with excellent alkali resistance and a preparation method thereof are provided.
Disclosure of Invention
A high modulus glass fiber composition having excellent alkali resistance, comprising the following components, wherein each component is represented by weight percent:
SiO2 55-60%
Al2O3 15-20%
YSZ 12-18%
Y2O3+Nd2O3+CeO2 0.5-2%
CaO+MgO 5-8%
Li2O+ Na2O+ K2O ≤2%
Fe3O4 ≤1%
TiO2 ≤1%
wherein 0.5-2% of Y2O3+Nd2O3+CeO2Represents Y2O3、Nd2O3、CeO2The total weight percentage of one, any two or three of the three components is 0.5-2%, for Y2O3、Nd2O3、CeO2The individual content of (A) is not limited at all, and may be any value of 0 to 2%; similarly, ≦ 2% Li2O+ Na2O+ K2O represents Li2O、 Na2O、K2The total weight percentage of one, any two or three of the three components of O is less than or equal to 2 percent, for Li2O、 Na2O、K2The individual content of O is not limited at all, and may be any value from 0 to 2%.
Wherein YSZ used in the invention is a shell-core structure of yttria-coated zirconia, Y: the mass ratio of Zr is 1: (10-20).
In the present invention, the zirconia is replaced with YSZ, and the inventors have found that the addition of YSZ to a glass composition for glass fibers also increases the liquidus temperature of the glass fiber composition, but to a lesser extent than the addition of the same amount of ZrO2The liquid phase temperature is increased. This facilitates the use of high levels of YSZ in the glass fiber composition without undue concern for elevated forming temperatures due to excessive liquidus temperatures and high requirements for bushing assemblies. Furthermore, the effect of YSZ on improving the alkali resistance of glass fibers and ZrO2The effect of improving the alkali resistance of the glass fiber is similar. Therefore, the use of YSZ in place of zirconia in the present invention is advantageous for preparing a glass fiber composition excellent in alkali resistance.
For the control of the formability and elastic modulus of glass fibers, Y is used in the present invention2O3、Nd2O3、CeO2、Fe3O4、TiO2CaO, MgO and the like.
Wherein, Y2O3、Nd2O3、CeO2All belong to rare earth oxides, and have similar effect on improving the elastic modulus of the glass fiber. Y is3+、Nd3+、Ce4+Ions with large radii are difficult to enter the glass network, usually in placeBetween the pores of the glass network. The rare earth metal ions have high coordination number and high charge, can be matched with free oxygen to form a coordination structure, fill the pores of the glass network among the pores of the glass network, and improve the structural stability of the glass network, thereby improving the modulus of the glass fiber. Y is3+、Nd3+、Ce4+The coordination structure with oxygen is octahedral hexa-coordination structure, and can be well matched with SiO2As the skeleton structure, Al is added3+The gaps of the glass network with the tetrahedral and octahedral coordination structure improve the stability of the structure, and meanwhile, the metal rare earth ions with large ionic radius and the coordination structure thereof generate great obstruction for the movement of other ions among the glass network structures, so that the component segregation and crystallization in the glass fiber composition are effectively inhibited, and the clarification effect of the glass is improved.
Fe3O4Can improve the crystallization performance of the glass fiber composition. For glass fiber compositions containing high levels of Al and Zr, the liquidus temperature is relatively high, Fe3O4The introduction of the glass fiber is beneficial to the temperature uniformity of the glass fiber composition in the processes of temperature rising and temperature lowering, and the local crystallization rate of the glass is improved.
TiO less than or equal to 1 percent2The water resistance and the alkali resistance of the glass fiber can be properly improved, the spinning forming temperature and the liquid phase temperature can be effectively reduced, and the formability of the glass fiber is improved. CaO and MgO can effectively adjust the meltability and viscosity of the glass and control the crystallization of the glass.
Detailed Description
The invention is further illustrated below with reference to specific examples.
The high modulus glass fiber composition with excellent alkali resistance contains the following components:
SiO2 55-60%
Al2O3 15-20%
YSZ 12-18%
Y2O3+Nd2O3+CeO2 0.5-2%
CaO+MgO 5-8%
Li2O+ Na2O+ K2O ≤2%
Fe3O4 ≤1%
TiO2 ≤1%。
the spinning temperature of the glass fiber composition is about 1200-1300 ℃, and the spinning temperature does not exceed 1300 ℃; the liquidus temperature of the glass fiber composition is about 1090-1145 ℃; the temperature difference between the spinning temperature and the liquid phase temperature is about 110-.
First, a glass fiber composition raw material in a desired ratio is charged into a glass melting furnace, and subjected to vitrification and melting treatment. The melting temperature is preferably 1400-1600 ℃ in order to obtain a homogenized glass melt. Then, the molten glass was supplied to a bushing device and spun to obtain glass fibers.
Examples 1 to 7
The specific components and corresponding properties of examples 1-7 listed in this invention are given in table 1. Of these, Nos. 1 to 3 and 5 to 6 are preferred examples of the present invention, and Nos. 4 and 7 are comparative examples. In the performance test, the liquidus temperature, elastic modulus, alkali resistance, water resistance of the glass fiber composition and the glass fiber prepared therefrom are mainly tested, and a proper spinning temperature and a corresponding temperature difference between the spinning temperature and the liquidus temperature are set.
TABLE 1
As can be seen from Table 1, the substitution of YSZ for zirconia in the present invention is effective in reducing the liquidus temperature of the glass fiber composition, thereby reducing the desired proper spinning temperature. Meanwhile, the substitution between YSZ and zirconia does not affect the alkali resistance of the glass fiber. I.e., YSZ can alsoEffectively improves the alkali resistance of the glass fiber. For rare earth oxides, e.g. Y2O3、Nd2O3、CeO2The use of (2) can obviously improve the modulus strength of the glass fiber. Small amount of TiO2The water resistance and the alkali resistance of the glass fiber can be properly improved, the spinning forming temperature and the liquid phase temperature can be effectively reduced, and the formability of the glass fiber is improved.
The liquid phase temperature of the glass fiber composition is 1090-1145 ℃, and the required proper spinning temperature can be selected from 1200-1300 ℃ and is not higher than 1300 ℃.