A basalt continuous fiber glass with low degree of crystallization and a method of making

Abstract

The application belongs to the technical field of basalt glass preparation, and particularly relates to a low-crystallization-degree basalt continuous fiber glass and a preparation method thereof. The basalt continuous fiber glass is composed of main glass raw materials and special glass raw materials. The main glass raw materials include 50-56 parts of SiO2, 12-15 parts of Al2O3, 9-12 parts of Fe2O3+FeO, 5-8 parts of CaO, 4-7 parts of MgO, 3-7 parts of Na2O+K2O, 0-0.3 parts of P2O5 and 0-0.5 parts of TiO2 according to weight. The special glass raw materials include 0-3 parts of B2O3, 0-1 parts of BaO and 0-0.2 parts of NaCl. The basalt continuous fiber glass and the preparation method thereof can reduce the crystallization ability of the glass, the high-temperature viscosity and the surface tension of the glass during melting, and make the glass melt easy to clarify and homogenize.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of basalt glass preparation, and particularly relates to a low-crystallization-degree basalt continuous fiber glass and a preparation method. BACKGROUND

[0002] The basalt glass is a continuous fiber made by high-speed drawing after natural basalt ore is melted at high temperature, and has many advantages such as high strength modulus, high temperature resistance, chemical corrosion resistance, etc., and is widely used in the fields of aerospace, military industry, automobile manufacturing, building reinforcement, petroleum chemical industry, environmental protection and sports equipment.

[0003] In the prior art, the prominent problem in the manufacturing process of the basalt glass is low continuity of the fiber, which further affects the product quality and the production cost. The crystallization of the glass melt seriously affects the continuity of the fiber, and the crystallization degree of the glass melt is affected by the melting temperature, homogeneity, fluidity and network structure strength of the glass melt, thereby affecting the continuity of the fiber during high-speed drawing. In addition, excessive TiO2 may affect the corrosion behavior of the basalt glass under alkaline conditions, leading to uneven corrosion; excessive P2O5 may increase the brittleness of the fiber, thereby reducing its mechanical strength. Therefore, how to reduce the melting temperature of the basalt glass, improve the homogeneity and fluidity of the glass melt, improve the network structure strength of the glass melt, and ensure the corrosion resistance and mechanical strength of the basalt glass has become a problem to be solved. SUMMARY

[0004] The application aims to solve the above problems, and provides a low-crystallization-degree basalt continuous fiber glass and a preparation method.

[0005] The application relates to a low-crystallization-degree basalt continuous fiber glass which is composed of main glass raw materials and special glass raw materials; the main glass raw materials include 50-56 parts of SiO2, 12-15 parts of Al2O3, 9-12 parts of Fe2O3+FeO, 5-8 parts of CaO, 4-7 parts of MgO, 3-7 parts of Na2O+K2O, 0-0.3 parts of P2O5 and 0-0.5 parts of TiO2 according to weight fractions, and the special glass raw materials include 0-3 parts of B2O3, 0-1 parts of BaO and 0-0.2 parts of NaCl.

[0006] As preferred, the main glass raw materials include 50-53 parts of SiO2, 13-15 parts of Al2O3, 9-12 parts of Fe2O3+FeO, 5-7 parts of CaO, 4-6 parts of MgO, 3-7 parts of Na2O+K2O, 0-0.2 parts of P2O5 and 0-0.5 parts of TiO2, and the special glass raw materials include 1-3 parts of B2O3, 0-1 parts of BaO and 0-0.2 parts of NaCl.

[0007] As preferred, the main glass raw materials include 50-53 parts of SiO2, 13-15 parts of Al2O3, 9-12 parts of Fe2O3+FeO, 5-6 parts of CaO, 4-5 parts of MgO, 3-6 parts of Na2O+K2O, 0-0.2 parts of P2O5 and 0-0.5 parts of TiO2, and the special glass raw materials include 2-3 parts of B2O3, 0.5-1 parts of BaO and 0-0.2 parts of NaCl.

[0008] As preferred, the natural basalt raw materials are mixed with industrial chemical raw materials.

[0009] As preferred, the natural basalt raw materials account for 80-90% of the total weight of the raw materials.

[0010] The present application also relates to a preparation method of the low-crystallization basalt continuous fiber glass.

[0011] Step one: the raw materials are weighed and mixed uniformly to obtain the mixed materials;

[0012] Step two: the mixed materials are put into a crucible, the crucible is placed in a furnace for temperature rising, stirring and heat preservation, and then static heat preservation is performed to obtain the initial glass liquid;

[0013] Step three: the initial glass liquid is poured into a water bath in the form of a thin stream to form fine glass particles, and the glass particles are dried;

[0014] Step four: the dried glass particles are put into a crucible, the crucible is placed in a furnace for temperature rising, stirring and heat preservation, and then static heat preservation is performed to obtain the final glass liquid;

[0015] Step five: the final glass liquid is rapidly drawn through a bushing to form continuous basalt fibers.

[0016] As preferred, in step two, the temperature is raised to 1480-1540℃, stirring and heat preservation are performed for 16-20h, and then static heat preservation is performed for 5-8h.

[0017] Preferably, in step four, the temperature is raised to 1500-1560℃ for melting, and after stirring and holding for 3-6h, the glass is held for 1-2h.

[0018] Preferably, in step five, the annealing temperature is 700-750℃.

[0019] Preferably, the melting furnace is a molybdenum electrode heated kiln.

[0020] The glass raw material of the present application is analyzed as follows:

[0021] 1) The characteristic glass raw material of the present application includes B2O3, which can form a uniform glass structure with SiO2. The main glass raw material Na2O provides free oxygen for B2O3, which converts the boron oxygen triangle into a boron oxygen tetrahedron, and the structure of boron is converted from a layer to a frame. B2O3 enters the glass structure in the form of a boron oxygen triangle or a boron oxygen tetrahedron, especially when it forms a uniform structure network with SiO2, which increases the network integrity and tightness, thereby improving the thermal stability, chemical stability, and mechanical strength of the glass melt, and reducing the likelihood of crystallization.

[0022] The characteristic glass raw material B2O3 contains polar boron oxygen bonds, which are enriched on the surface of the glass melt, increasing the polarity of the surface layer and helping to reduce the surface tension. At the same time, B2O3 may undergo adsorption on the surface of the glass melt, and the adsorption of its molecules or ions on the surface changes the composition of the surface, weakening the intermolecular forces of the surface layer and resulting in a reduction in surface tension.

[0023] 2) The characteristic glass raw material of the present application also includes BaO, which forms a stable barium silicate network structure with SiO2, thereby improving the stability and mechanical strength of the glass and reducing the likelihood of crystallization. The addition of BaO can also reduce the transition temperature and crystallization temperature of the glass, reducing the formation of crystal nuclei due to temperature changes during cooling and thereby reducing the likelihood of crystallization.

[0024] The main glass raw material SiO2 reacts with Na2O, K2O, CaO, or MgO to form silicates, and the characteristic glass raw material BaO can form new compounds with the above silicates. The melting point of the new compounds is lower than that of the original silicates, thereby reducing the melting temperature and vitrification temperature of the glass, allowing the glass to be melted and formed at a lower temperature, and reducing the opportunity for crystallization and nucleation at high temperatures.

[0025] The characteristic glass raw material BaO interacts with B2O3 to generate barium orthoborate and barium metaborate, which can be used as a network former of the glass to increase the stability and mechanical strength of the glass; barium orthoborate and barium metaborate generated by the reaction of BaO and B2O3 have a high crystallization temperature; therefore, barium orthoborate, barium metaborate and barium orthoborate generated are all beneficial to reduce the crystallization possibility of the glass.

[0026] 3) The characteristic glass raw material in the application further comprises NaCl, which reacts with the main glass raw material SiO2 to form sodium silicate, thereby reducing the overall melting temperature and enabling the glass to reach a molten state at a lower temperature; since viscosity is closely related to temperature, the lower melting temperature helps to reduce the viscosity of the glass melt, thereby improving the flowability of the glass melt.

[0027] 4) In the application, the addition amount of the main glass raw material P2O5 is controlled to be 0-0.2 parts, and the addition amount of the main glass raw material TiO2 is controlled to be 0-0.5 parts; when the natural basalt raw material is selected, the content of P2O5 and TiO2 is strictly controlled to avoid the influence of TiO2 on the corrosion behavior of basalt glass under alkaline conditions, which leads to uneven corrosion, and to avoid the increase of the brittleness of fibers caused by P2O5, thereby reducing the mechanical strength of basalt glass.

[0028] Compared with the prior art, the application has the following advantages and positive effects:

[0029] Compared with the prior art, the low-crystallization basalt continuous fiber glass and the preparation method can reduce the crystallization ability of the glass, improve the glassification ability, and reduce the high-temperature viscosity and surface tension of the glass melt during melting, so that the glass melt is easily clarified and homogenized, thereby improving the continuity of the glass fiber and the qualified rate of the product; the low melting temperature of the low-crystallization basalt continuous fiber glass can reduce energy consumption and prolong the service life of the kiln, thereby reducing the equipment investment cost. DETAILED DESCRIPTION

[0030] In order to more clearly understand the above-mentioned purposes, features and advantages of the application, the application will be further described below in conjunction with examples.

[0031] In the following description, many specific details are set forth in order to provide a thorough understanding of the application, but the application can also be practiced without the specific details described herein, and therefore, the application is not limited to the specific embodiments disclosed in the following description.

[0032] Example 1

[0033] The raw materials were weighed according to Table 1, mixed uniformly to obtain a mixture, and then the mixture was placed in a crucible. The crucible was placed in a kiln heated by a molybdenum electrode, and the temperature was raised to 1480℃. After stirring and holding for 20h, the initial glass liquid was obtained by holding for 5h. The initial glass liquid was poured into a water bath in the form of a fine stream to form fine glass particles, and the glass particles were dried. The dried glass particles were placed in a crucible, and the crucible was placed in a kiln heated by a molybdenum electrode. The temperature was raised to 1500℃ for melting. After stirring and holding for 6h, the final glass liquid was obtained by holding for 1h. The final glass liquid was rapidly drawn through a bushing to form continuous basalt fibers. The proportion of natural basalt raw material in the total weight of raw materials was 90%.

[0034] Example 2

[0035] The difference between this example and Example 1 is that the mixture was placed in a crucible, and the crucible was placed in a kiln heated by a molybdenum electrode. The temperature was raised to 1540℃. After stirring and holding for 16h, the initial glass liquid was obtained by holding for 8h. The dried glass particles were placed in a crucible, and the crucible was placed in a kiln heated by a molybdenum electrode. The temperature was raised to 1560℃ for melting. After stirring and holding for 3h, the final glass liquid was obtained by holding for 2h. The proportion of natural basalt raw material in the total weight of raw materials was 85%.

[0036] Example 3

[0037] The difference between this example and Example 1 is that the mixture was placed in a crucible, and the crucible was placed in a kiln heated by a molybdenum electrode. The temperature was raised to 1500℃. After stirring and holding for 18h, the initial glass liquid was obtained by holding for 6h. The dried glass particles were placed in a crucible, and the crucible was placed in a kiln heated by a molybdenum electrode. The temperature was raised to 1540℃ for melting. After stirring and holding for 5h, the final glass liquid was obtained by holding for 1.5h. The proportion of natural basalt raw material in the total weight of raw materials was 88%.

[0038] Comparative Example 1-2

[0039] The difference between this example and Example 1 is that it does not contain the characteristic glass raw materials B2O3, BaO and NaCl.

[0040] Table 1. Proportion of each raw material in Examples 1-3 and Comparative Examples 1-2

[0041]

[0042] Performance test

[0043] The crystallization upper limit temperature and glass Young's modulus of the glasses of Examples 1-3 and Comparative Examples 1-2 were detected, and the bubble number and crystallization condition were observed, and the results are shown in Table 2.

[0044] Table 2. Performance test results of the glasses of Examples 1-3 and Comparative Examples 1-2

[0045]

[0046] From Table 2, it can be seen that the glasses of Examples 1-3 have lower crystallization upper limit temperature, higher Young's modulus, and no bubbles and crystallization, compared to Comparative Examples 1-2, proving that the low-crystallinity basalt continuous fiber glass of the present application has low crystallization ability, high mechanical strength, and low crystallization upper limit temperature, thereby reducing the viscosity of the glass melt, improving the flowability of the glass melt, making the glass melt easy to clarify and homogenize.

[0047] The above description is only the preferred embodiment of the present application, and is not intended to limit the present application in other forms. Any person skilled in the art can modify or change the above-mentioned technical content into equivalent embodiments applied to other fields, but any simple modification, equivalent change, or application of the above-mentioned embodiments without departing from the technical scheme of the present application, according to the technical essence of the present application, still belongs to the protection scope of the technical scheme of the present application.

Claims

1. A low-crystallinity basalt continuous fiber glass, characterized by, The main glass raw material and the characteristic glass raw material; the main glass raw material comprises 50-53 parts of SiO2, 13-15 parts of Al2O3, 9-12 parts of Fe2O3+FeO, 5-6 parts of CaO, 4-5 parts of MgO, 3-6 parts of Na2O+K2O, 0-0.2 parts of P2O5 and 0-0.5 parts of TiO2 by weight; the characteristic glass raw material comprises 2-3 parts of B2O3, 0.5-1 parts of BaO and 0-0.2 parts of NaCl.

2. The low-crystallized basalt continuous fiber glass according to claim 1, characterized by, The total raw material is mixed by natural basalt raw material and industrial chemical raw material.

3. The low-crystallized basalt continuous fiber glass according to claim 2, characterized by, The natural basalt raw material accounts for 80-90% of the total weight of the raw material.

4. A method of producing a low-crystallinity basalt continuous fiber glass, characterized by, The preparation of the low-crystallization basalt continuous fiber glass of any one of claims 1-3 comprises the following steps: Step one: the raw materials are weighed and mixed uniformly to obtain a mixture; Step two: the mixture is placed in a crucible, the crucible is placed in a furnace for heating, stirring and heat preservation, and then static heat preservation to obtain an initial glass liquid; Step three: the initial glass liquid is poured into a water bath in the form of a fine stream to form fine glass particles, and the glass particles are dried; Step four: the dried glass particles are placed in a crucible, the crucible is placed in a furnace for heating, stirring and heat preservation, and then static heat preservation to obtain a final glass liquid; Step five: the final glass liquid is quickly drawn through a bushing to form continuous basalt fibers.

5. The method of claim 4, wherein the low-crystallinity basalt continuous fiber glass is characterized by, In step two, the temperature is raised to 1480-1540 DEG C, stirring and heat preservation for 16-20 h, and then static heat preservation for 5-8 h.

6. The method of claim 5, wherein the basalt continuous fiber glass having a low degree of crystallization is characterized by, In step four, the temperature is raised to 1500-1560 DEG C for melting, stirring and heat preservation for 3-6 h, and then static heat preservation for 1-2 h.

7. The method of claim 6, wherein the basalt continuous fiber glass having a low degree of crystallization is characterized by, The furnace is a molybdenum electrode heated kiln.

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