阅读说明：本技术 一种硅酸盐玻璃纤维的化学强化方法 (Chemical strengthening method of silicate glass fiber ) 是由 康俊峰 王兴陶 徐赵志 岳云龙 屈雅 侯延升 于 2021-09-27 设计创作，主要内容包括：本发明属于无机材料制备领域,具体涉及一种硅酸盐玻璃纤维的化学强化方法。该方法通过以下步骤实现：将玻璃纤维烘干处理后进行预热,然后将玻璃纤维浸入到熔盐当中进行离子交换处理；将熔盐处理后的玻璃纤维取出,清洗、烘干后,涂抹浸润剂即可。本发明首先对玻璃纤维进行预热,使得玻璃纤维在熔盐中盐浴时不会因为急剧变化的温度而造成破坏；本发明提供的预热温度,能够避免玻璃在高温过程中发生变化；通过化学强化,能够提升硅酸盐玻璃纤维的机械性能,使得硅酸盐玻璃纤维的应用领域得到增广。(The invention belongs to the field of inorganic material preparation, and particularly relates to a chemical strengthening method of silicate glass fibers. The method is realized by the following steps: preheating the glass fiber after drying treatment, and then immersing the glass fiber into molten salt for ion exchange treatment; and taking out the glass fiber after molten salt treatment, cleaning, drying and coating the impregnating compound. The method comprises the following steps of preheating the glass fiber, so that the glass fiber is not damaged due to the rapidly changed temperature when the glass fiber is subjected to salt bath in the molten salt; the preheating temperature provided by the invention can avoid the change of glass in the high-temperature process; through chemical strengthening, the mechanical property of the silicate glass fiber can be improved, so that the application field of the silicate glass fiber is widened.)

1. A chemical strengthening method of silicate glass fiber is characterized by comprising the following steps:

(1) cleaning and drying: drying the silicate glass fiber with the surface cleaned with dust and impurities;

(2) preheating: preheating the glass fiber;

(3) salt bath: immersing the glass fiber into molten salt for ion exchange treatment;

(4) cleaning: and taking out the glass fiber after molten salt treatment, cleaning, drying and coating the impregnating compound.

2. The chemical strengthening method according to claim 1, wherein the silicate glass fiber has a diameter of 5 to 80 μm.

3. The chemical strengthening method according to claim 2, wherein the silicate glass fiber is a high borosilicate glass fiber or a soda-lime silicate glass fiber;

the high borosilicate glass fiber comprises the following components in percentage by mass: SiO2₂ 55%-85%；Al₂O₃ 0-10%；B₂O₃ 15-25%；Li₂O+Na₂O+K₂O 2%-15%；MgO+CaO 5%-15%；TiO₂ 0-5%；

The soda-lime-silicate glass fiber comprises the following components in percentage by mass: SiO2₂ 60%~75%、Al₂O₃ 0~7%、MgO 0~11%、CaO 7%~20% 、Na₂O 10%~22% 、P₂O₅ 0~10%。

4. The chemical strengthening method according to claim 1 or 3, wherein in the step (1), the temperature of the drying treatment is 40-60 ℃, and the drying time is controlled to be 0.5-2 h.

5. The chemical strengthening method as claimed in claim 4, wherein in the step (2), the preheating temperature is 350-450 ℃ and the preheating time is 0.1-2 h.

6. The chemical strengthening method of claim 1, wherein in the step (3), the ion exchange treatment is performed by performing salt bath treatment on the glass fiber at a temperature of 350-450 ℃, and the salt bath time is controlled to be 0.1-6 h.

7. The chemical strengthening method of claim 6, wherein the molten salt used in the salt bath process is a mixed molten salt of potassium nitrate, potassium hydroxide, potassium sulfate and diatomite, wherein the content of the molten salt potassium nitrate is as follows: 80-88%, and the contents of potassium hydroxide and potassium nitrate are as follows: 8-18%, and the content of diatomite is as follows: 2 to 6 percent.

8. The chemical strengthening method of claim 1, wherein in the step (4), the composition of the impregnating agent is as follows: 6 to 12 percent of polyester resin emulsion, 3 to 10 percent of epoxy resin such as liquid, 1 to 5 percent of dialdehyde starch, 0.1 to 0.8 percent of lubricant, 0.1 to 0.5 percent of defoaming agent, 0.1 to 0.6 percent of antistatic agent, 0.1 to 0.5 percent of PH value regulator and the balance of water.

Technical Field

The invention belongs to the field of inorganic material preparation, and particularly relates to a chemical strengthening method of silicate glass fibers.

Background

The glass fiber is the most widely used inorganic non-metallic material with the largest dosage in the composite material reinforced base material. The glass fiber can be used for increasing the rigidity, hardness and toughness of the material, and the strength and rigidity can be increased like the plastic added with the glass fiber; the nylon added with the glass fiber can improve the heat resistance. In addition, the glass fiber also has the effects of reducing material shrinkage, deformation, surface gloss and the like in the composite material. In actual production, most researchers and enterprises adjust components to improve the performance of the glass fiber. However, the improvement of the mechanical strength of the glass fiber is difficult to realize only by adjusting the components, so that the strength of the composite material formed by the glass fiber and other materials is difficult to improve, and the composite material is difficult to apply to scenes with higher performance requirements. In order to solve the technical problems, a new production process is needed to improve the mechanical property of the glass fiber and ensure the light weight and high performance of the composite material.

With the increasing application fields of glass fibers, the requirements on the properties of high-boron or soda-lime-silica glass fibers are higher and higher, and the requirements on the properties of the high-boron-silica glass fibers, such as bending strength, tensile strength and strength, are higher and higher, so that how to enhance the mechanical properties of the high-boron-silica glass fibers becomes a hot point of research.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a chemical strengthening method of silicate glass fibers, and the silicate glass specifically comprises high borosilicate glass and soda-lime silicate glass.

The technical scheme adopted by the invention for realizing the purpose is as follows:

the invention provides a chemical strengthening method of silicate glass fiber, which comprises the following steps:

(1) cleaning and drying: drying the silicate glass fiber with the surface cleaned with dust and impurities;

(2) preheating: preheating the glass fiber;

(3) salt bath: immersing the glass fiber into molten salt for ion exchange treatment;

(4) cleaning: and taking out the glass fiber after molten salt treatment, cleaning, drying and coating the impregnating compound.

Further, the diameter of the silicate glass fiber is 5-80 μm.

The chemically strengthened silicate glass fiber is high borosilicate glass fiber or soda-lime silicate glass fiber;

the high borosilicate glass fiber comprises the following components in percentage by mass: 255-85% of SiO; al2O 30-10%; 315-25% of B2O; li2O + Na2O + K2O 2% -15%; 5% -15% of MgO + CaO; 78-5% of TiO 20; the soda-lime-silicate glass fiber comprises the following components in percentage by mass: 260-75% of SiO, 0-11% of Al2O 30-7%, 0-11% of MgO, 7-20% of CaO, 10-22% of Na2O 10, and 50-10% of P2O.

Further, in the step (1), the drying temperature is 40-60 ℃, and the drying time is controlled to be 0.5-2 h.

Further, in the step (2), the preheating temperature is 350-450 ℃, and the preheating time is 0.1-2 h.

Further, in the step (3), the ion exchange treatment is to perform salt bath on the glass fiber at the temperature of 350-450 ℃, and the salt bath time is controlled to be 0.1-6 h.

The molten salt used in the salt bath process is mixed molten salt of potassium nitrate, potassium hydroxide, potassium sulfate and diatomite, wherein the content of the molten salt potassium nitrate is as follows: 80-88%, and the contents of potassium hydroxide and potassium nitrate are as follows: 8-18%, and the content of diatomite is as follows: 2 to 6 percent.

Further, in the step (4), the composition of the impregnating compound is as follows: 6 to 12 percent of polyester resin emulsion, 3 to 10 percent of epoxy resin such as liquid, 1 to 5 percent of dialdehyde starch, 0.1 to 0.8 percent of lubricant, 0.1 to 0.5 percent of defoaming agent, 0.1 to 0.6 percent of antistatic agent, 0.1 to 0.5 percent of PH value regulator and the balance of water.

The invention carries out surface cleaning on the high boron or soda-lime silicate glass fiber by using deionized water or industrial water. The advantage of using deionized water or industrial water is that new impurity ions are prevented from being brought in while impurities are cleaned;

in the salt bath process, potassium ions in the molten salt and sodium ions of the high-boron or sodium-calcium silicate glass fiber are subjected to ion exchange, so that a certain compressive stress is formed on the surface layer of the glass fiber, when an external force is applied to the chemically strengthened glass fiber, the compressive stress layer can counteract a part of the external force, the performance of the high-boron or sodium-calcium silicate glass fiber is enhanced, and the purpose of chemically strengthening the high-boron or sodium-calcium silicate glass fiber is achieved.

In the salt bath, the glass fibers are immersed in the mixed molten salt in a temperature range below the glass transition temperature point, and K is in the molten salt⁺Alkali metal ion Na having a radius larger than that of the surface of the silicate glass fiber⁺Radius, ion exchange in molten salt, K in molten salt⁺Na bound to the surface of the glass fiber⁺Exchange is carried out so that K⁺And the glass fiber surface layer is filled with the silicate glass fiber, so that a certain compressive stress and stress depth are formed on the glass fiber surface layer, and when an external force is applied to the chemically strengthened silicate glass fiber, part of the external force can be offset by the stress layer, so that the purpose of enhancing the mechanical property of the silicate glass fiber is achieved.

The invention has the beneficial effects that:

(1) the method comprises the following steps of preheating the glass fiber, so that the glass fiber is not damaged due to the rapidly changed temperature when the glass fiber is subjected to salt bath in the molten salt; the preheating temperature provided by the invention can avoid the change of glass in the high-temperature process.

(2) The invention can improve the mechanical property of the silicate glass fiber, and broadens the application field of the silicate glass fiber.

(3) According to the invention, through chemical strengthening, the bending strength of the strengthened high borosilicate glass fiber is 980-1400MPa, which is increased by 27-48% compared with that of the precursor fiber; the tensile strength is 1550-; the bending strength of the soda-lime-silicate glass fiber is 850-1400 MPa, which is increased by 21-41% compared with the original fiber; the tensile strength is 1530-1900MPa, which is increased by 15-28% compared with the original yarn.

Detailed Description

The technical solutions and the technical effects achieved by the present invention will be described below with reference to the embodiments of the present invention.

The glass fiber used in the invention is prepared by a tank furnace wire drawing method, the raw materials are melted in a tank furnace to be made into glass liquid, the glass liquid is conveyed to a porous bushing plate after air bubbles are removed, and the glass fiber is obtained by high-speed drawing.

The chemical strengthening method provided by the invention comprises the following steps:

the method comprises the following steps of cleaning the surface of the glass fiber, wherein deionized water or industrial water is adopted for cleaning the glass fiber, and the deionized water or the industrial water has the advantage of avoiding bringing new impurity ions while cleaning impurities;

drying the glass fiber, wherein the drying time is 40-60 ℃, and is controlled to be 0.5-2h, so that the glass fiber is prevented from being influenced by the presence of water when the glass fiber is preheated or subjected to salt bath;

preheating the glass fiber, wherein the preheating temperature of the glass fiber is 350-450 ℃, and the preheating time is controlled to be 0.1-2h, so that the glass fiber is preheated, and the method has the advantage that the glass fiber cannot be damaged due to the rapidly changed temperature when the glass fiber is subjected to salt bath in molten salt;

the salt bath temperature of the high borosilicate glass fiber is controlled to be 350-450 ℃, the salt bath time is controlled to be 0.1-6h, and the salt bath temperature is lower than the glass transition temperature, so that the glass is prevented from changing in the high-temperature process;

the method has the advantages that when the residual salt on the surface of the glass fiber is cleaned, new impurity ions cannot be brought;

in the chemical strengthening method disclosed by the invention, the diameter of the strengthened silicate glass fiber is 5-80 μm. Before chemical strengthening is carried out on silicate glass fibers, the silicate glass fibers need to be subjected to surface cleaning and drying, dust and other impurities on the surfaces of the glass fibers are cleaned, and deionized water or industrial water is adopted in the cleaning process, so that the impurities brought to the surfaces of the glass fibers are avoided. And after cleaning, drying the glass fiber at 40-60 deg.C, optionally at 44 deg.C, 48 deg.C, 52 deg.C, 56 deg.C, 60 deg.C for 0.5-2h, optionally 0.5h, 1h, 1.5h, 2h, etc.

In order to realize the chemical strengthening of the silicate glass fiber, the used mixed molten salt needs to be treated, and the mixed molten salt is heated to enable the solid mixed molten salt to be processed into liquid state at high temperature, wherein the temperature is controlled at 350-450 ℃, the temperature can not exceed the glass transition temperature point, and can be selected from 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃ and the like.

The glass fiber needs to be preheated before being chemically strengthened, the preheating temperature is set to be 350-450 ℃, the preheating temperature can be set to be 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃ and the like, the preheating time is controlled to be 0.1-2h, and can be selected to be 0.1h, 0.5h, 0.9h, 1.3h, 1.7h and the like, so that the glass fiber does not crack or generate micro cracks due to rapid temperature change when the glass fiber is in salt bath.

After preheating is finished, chemical strengthening of the glass fiber can be carried out, the glass fiber is immersed into the molten mixed molten salt at the temperature of 350-450 ℃, the strengthening temperature can be set to be 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃ and the like, the salt bath time is controlled to be 0-6h, the salt bath time can be set to be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h and the like, so that K in the molten salt can be further strengthened⁺Na with glass surface⁺Exchange is performed so that K is large in ionic radius⁺Replacing Na with small ionic radius⁺Enter the surface of the glass fiber, thereby forming certain stress intensity and stress depth on the surface layer of the glass fiber, and when external force is applied to the glass fiber, the pressure stress can offset a part of the external force, thereby showing the enhancement of the performance of the silicate glass fiber.

The invention will be described in further detail below with reference to specific examples, which were analyzed using commercially available high boron or soda-lime silicate glass fibers of 5-80 μm.

Example 1

(1) According to the high borosilicate glass fiber composition: SiO2₂ 62.0%；Al₂O₃ 3.0%；B₂O₃ 19.0%；Li₂O 0.2%；Na₂O 10.0%；K₂O 3.0%；MgO 5.0%；CaO 0.3%；TiO₂0.2 percent of the glass fiber, and the glass fiber is prepared into glass fiber with the diameter of 5 to 80 mu m after being mixed;

(2) cleaning high borosilicate glass fibers, cleaning dust and impurities on the surfaces of the glass fibers by using deionized water or industrial water, carrying out heat preservation and drying on the glass fibers at the temperature of 60 ℃ for 1h after cleaning, and then preheating, wherein the preheating temperature is controlled at 400 ℃ and the preheating time is controlled at 1 h; carrying out salt bath on high borosilicate glass fibers at the temperature of 400 ℃ by using preheated glass and melted mixed molten salt, controlling the salt bath time to be 4h, carrying out surface cleaning on the high borosilicate glass fibers after the salt bath, cleaning residual potassium nitrate, potassium hydroxide and potassium sulfate on the surfaces of the glass fibers after the salt bath by using deionized water or industrial water, drying the glass fibers for 1h at the temperature of 60 ℃, and coating a layer of reinforced textile size on the surfaces of the glass fibers after the drying is finished.

Through chemical strengthening, the bending strength of the strengthened high borosilicate glass fiber is increased to 983MPa, and is increased by 33% compared with protofilament; the tensile strength reaches 1656MPa, which is increased by 28% compared with the original yarn.

Example 2

(1) According to the high borosilicate glass fiber composition: SiO2₂ 60.0%；Al₂O₃ 3.0%；B₂O₃ 15.0%；Li₂O 1.0%；Na₂O 10.0%；K₂O 2.0%；MgO 7.0%；CaO 1.5%；TiO₂0.5 percent of the glass fiber, and the glass fiber is prepared into glass fiber with the diameter of 5 to 80 mu m after being mixed;

(2) cleaning high borosilicate glass fibers, cleaning dust and impurities on the surfaces of the glass fibers by using deionized water or industrial water, performing heat preservation and drying on the glass fibers at the temperature of 60 ℃ for 1h after cleaning, then preheating, controlling the preheating temperature at 430 ℃, controlling the preheating time at 1h, performing salt bath on the high borosilicate glass fibers by using preheated glass and molten mixed molten salt at the temperature of 430 ℃, controlling the salt bath time at 5h, performing surface cleaning on the high borosilicate glass fibers after the salt bath, cleaning residual potassium nitrate, potassium hydroxide and potassium sulfate on the surfaces of the glass fibers after the salt bath by using deionized water or industrial water, drying for 1h at 60 ℃, and coating a layer of reinforced textile impregnating compound on the surfaces of the glass fibers after drying.

Through chemical strengthening, the bending strength of the strengthened high borosilicate glass fiber reaches 1056MPa, and is increased by 36 percent compared with the protofilament; the tensile strength reaches 1704MPa, which is increased by 30 percent compared with the original filament.

Example 3

(1) According to the high borosilicate glass fiber composition: SiO2₂ 55.0%；Al₂O₃ 8.0%；B₂O₃ 17.0%；Li₂O 0.5%；Na₂O 10.0%；K₂O 0.5%；MgO 6.0%；CaO 2.0%；TiO₂1.0 percent of the glass fiber, and the glass fiber is prepared into glass fiber with the diameter of 5 to 80 mu m after being mixed;

(2) cleaning high borosilicate glass fibers, cleaning the high borosilicate glass fibers, cleaning dust and impurities on the surfaces of the glass fibers by using deionized water or industrial water, performing heat preservation and drying on the glass fibers at the temperature of 60 ℃ for 1h after cleaning, then preheating, controlling the preheating temperature to be 450 ℃, controlling the preheating time to be 1h, performing salt bath on the high borosilicate glass fibers by using preheated glass and melted mixed molten salt at the temperature of 450 ℃, controlling the salt bath time to be 6h, cleaning the surfaces of the high borosilicate glass fibers after the salt bath, cleaning residual potassium nitrate, potassium hydroxide and potassium sulfate on the surfaces of the glass fibers after the salt bath by using deionized water or industrial water, drying the high borosilicate glass fibers for 1h at the temperature of 60 ℃, and coating a layer of reinforcing textile type impregnating agent on the surfaces of the glass fibers after drying.

Through chemical strengthening, the bending strength of the strengthened high borosilicate glass fiber reaches 1179MPa, and is increased by 45% compared with the protofilament; the tensile strength reaches 1853MPa, which is increased by 37% compared with the original yarn.

Example 4

(1) According to sodium calcium silicateSalt glass fiber composition: SiO2₂（67%）、Al₂O₃（5%）、MgO（9%）、CaO（5%）、Na₂O（11%）、P₂O₅(3%) preparing the mixture into glass fiber with the diameter of 5-80 μm after batching;

(2) cleaning the soda-lime silicate glass fiber, cleaning the dust and impurities on the surface of the glass fiber by using deionized water or industrial water, performing heat preservation and drying on the glass fiber at the temperature of 60 ℃ for 1h after cleaning, then preheating, controlling the preheating temperature to be 380 ℃, controlling the preheating time to be 1h, performing salt bath on the soda-lime silicate glass fiber by using the preheated glass and the molten mixed molten salt at the temperature of 380 ℃, controlling the salt bath time to be 0.5h, cleaning the surface of the soda-lime silicate glass fiber after the salt bath, cleaning potassium nitrate, potassium hydroxide and potassium sulfate remained on the surface of the glass fiber after the salt bath by using deionized water or industrial water, drying the cleaned soda-lime silicate glass fiber at the temperature of 60 ℃ for 1h, and coating a layer of a reinforced textile type impregnating compound on the surface of the glass fiber after drying.

Through chemical strengthening, the bending strength of the strengthened soda-lime-silicate glass fiber reaches 1040 MPa; compared with the protofilament, the tensile strength is increased by 41 percent, the tensile strength reaches 1882MPa, and compared with the protofilament, the tensile strength is increased by 35 percent.

Example 5

(1) According to the composition of the soda-lime-silicate glass fiber: the glass fiber comprises the following components: SiO2₂（65%）、Al₂O₃（6%）、MgO（8%）、CaO（6%）、Na₂O（13%）、P₂O₅(2%) preparing the mixture into glass fiber with the diameter of 5-80 μm after batching;

(2) cleaning the soda-lime silicate glass fiber, cleaning the dust and impurities on the surface of the glass fiber by using deionized water or industrial water, performing heat preservation and drying on the glass fiber at the temperature of 60 ℃ for 1h after cleaning, then preheating, controlling the preheating temperature to be 420 ℃, controlling the preheating time to be 1h, performing salt bath on the preheated glass fiber and the molten mixed molten salt at the temperature of 420 ℃, controlling the salt bath time to be 0.5h, cleaning the surface of the soda-lime silicate glass fiber after the salt bath, cleaning potassium nitrate, potassium hydroxide and potassium sulfate remained on the surface of the glass fiber after the salt bath by using deionized water or industrial water, drying the glass fiber after the salt bath, drying the glass fiber for 1h at the temperature of 60 ℃, and coating a layer of reinforced textile type impregnating compound on the surface of the glass fiber after drying.

Through chemical strengthening, the bending strength of the strengthened soda-lime-silicate glass fiber reaches 986MPa, and is increased by 39% compared with the protofilament; the tensile strength reaches 1762MPa, which is increased by 30 percent compared with the original yarn.

Example 6

(1) According to the composition of the soda-lime-silicate glass fiber: the glass fiber comprises the following components: SiO2₂（70%）、Al₂O₃（4%）、MgO（5%）、CaO（4%）、Na₂O（15%）、P₂O₅(2%) preparing the mixture into glass fiber with the diameter of 5-80 μm after batching;

(2) cleaning the soda-lime silicate glass fiber, cleaning the dust and impurities on the surface of the glass fiber by using deionized water or industrial water, performing heat preservation and drying on the glass fiber at the temperature of 60 ℃ for 1h after cleaning, then preheating, controlling the preheating temperature to be 420 ℃, controlling the preheating time to be 1h, performing salt bath on the preheated glass fiber and the molten mixed molten salt at the temperature of 420 ℃, controlling the salt bath time to be 0.8h, cleaning the surface of the soda-lime silicate glass fiber after the salt bath, cleaning potassium nitrate, potassium hydroxide and potassium sulfate remained on the surface of the glass fiber after the salt bath by using deionized water or industrial water, drying the glass fiber after the salt bath, drying the glass fiber for 1h at the temperature of 60 ℃, and coating a layer of reinforced textile type impregnating compound on the surface of the glass fiber after drying.

Through chemical strengthening, the bending strength of the strengthened soda-lime-silicate glass fiber reaches 895MPa, and is increased by 33% compared with the original fiber; tensile strength reaches 1573MPa, which is increased by 26% compared with the original yarn.