High-alkali-resistance and high-strength glass as well as preparation method and application thereof

Abstract

The invention discloses high-alkali-resistance and high-strength glass, which comprises the following basic raw materials in percentage by mass: 54-61% of SiO2; 19% to 23% of Al2O3; caO: 7%-14%; 1%-7% of MgO; 1 to 8 percent of Na2O; 0%-6% of B2O3; 0%-1% of Li2O; 0%-3% of CeO2; the preparation method comprises the following steps: weighing the raw materials according to the formula of the base glass, uniformly mixing and grinding, heating to 1500-1580 DEG C, melting at high temperature for 2-3 hours, homogenizing and clarifying, and pouring into a mold for molding to obtain the base glass; and annealing at 630-670 DEG C for 2-3 hours to obtain the high-alkali-resistance high-strength glass The alkali-resistant glass fiber has excellent alkali resistance, breaking strength and hardness, and more importantly, the alkali-resistant glass fiber has relatively low wire drawing temperature, and has relatively great advantages when being applied to manufacturing of glass fibers.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and specifically relates to a highly alkali-resistant and high-strength glass and its preparation method and application. Background Art

[0002] Glass fiber is an inorganic fiber material drawn from molten glass. Compared with general chemical fibers, glass fiber has excellent mechanical properties, high-temperature resistance, and good chemical stability, and is widely used in fields such as construction, energy transportation, electronic communication, and aerospace. Glass fiber can be used as a filtering material for purifying air and filtering liquids; glass fiber can also be used as a reinforcing material to improve the strength and crack resistance of composite materials, such as glass fiber-reinforced cement-based composites. Although glass fiber itself has good chemical stability, glass fiber will also be corroded to a certain extent in an alkaline working environment, resulting in a reduction in the mechanical properties of glass fiber. Therefore, glass fiber is required to have high alkali resistance and excellent mechanical properties at the same time.

[0003] Patent (CN116253521A) invented an alkali-resistant SiO2-Al2O3-ZrO2-based glass fiber, and the alkali-resistant mass retention rate of its glass block is 99.1-99.5% (alkali resistance detection: immersed in a solution obtained by mixing 1 mol / L NaOH and 0.5 mol / L Na2CO3 in equal volumes for 24 h, and the temperature is maintained at 80 °C). The glass fiber invented in this patent has good alkali resistance, but the zirconium content in the composition is relatively high, and excessive use will significantly increase the melting temperature of the glass, making it easier to crystallize during the fiber drawing process, increasing the production difficulty of the fiber, and the expensive ZrO2 also increases the cost of alkali-resistant glass fiber.

[0004] Patent (CN117800609A) invented an SiO2-CaO-Na2O-based glass fiber with good alkali resistance, and its alkali-resistant mass retention rate is 90.1-93.0% (the alkali-resistant mass retention rate test method is measured by accelerating aging in a 5% NaOH solution at 96 °C for 24 h); Patent (CN112811824A) invented an alkali-resistant SiO2-Al2O3-CaO-MgO-based glass fiber, and its alkali-resistant mass retention rate is 86-88% (alkali resistance detection: soaking in a 5% NaOH solution at 80-90 °C for 80-90 h at a constant temperature). Although the glass fibers invented in the above patents (CN117800609A) and (CN112811824A) have relatively low drawing temperatures, their alkali resistance is still somewhat different from that of the glass fiber invented in patent (CN116253521A).

[0005] Although the above-mentioned glass fibers all have certain alkali corrosion resistance, the glass fibers will still be corroded when they are in an alkaline environment for a long time, which reduces the mechanical properties of the glass fibers. Therefore, the alkali resistance of the glass fibers still needs to be improved to prevent the premature failure of the materials. How to maintain a relatively low drawing temperature while ensuring extremely high alkali resistance and excellent mechanical properties has become a technical problem to be solved urgently. Summary of the Invention

[0006] The object of the present invention is to provide a highly alkali-resistant and high-strength glass for glass fibers and a preparation method thereof. This glass not only has excellent alkali resistance, flexural strength, and hardness, but more importantly, it has a relatively low drawing temperature, which has great advantages in the manufacture of glass fibers.

[0007] To achieve the above object, the following technical solutions are adopted:

[0008] A highly alkali-resistant and high-strength glass, the basic raw materials are calculated by mass percentage: SiO2: 54% - 61%; Al2O3: 19% - 23%; CaO: 7% - 14%; MgO: 1% - 7%; Na2O: 1 - 8%; B2O3: 0% - 6%; Li2O: 0% - 1%; CeO2: 0% - 3%.

[0009] A highly alkali-resistant and high-strength glass, the basic raw materials are calculated by mass percentage: SiO2: 55% - 60%; Al2O3: 20% - 22%; CaO: 8% - 13%; MgO: 2% - 6%; Na2O: 2 - 7%; B2O3: 1% - 6%; Li2O: 0.1% - 1%; CeO2: 0.1% - 3%.

[0010] A highly alkali-resistant and high-strength glass, the basic raw materials are calculated by mass percentage: SiO2: 56% - 58%; Al2O3: 20% - 22%; CaO: 9% - 12%; MgO: 3% - 5%; Na2O: 3 - 6%; B2O3: 2% - 4%; Li2O: 0.2% - 0.6%; CeO2: 0.5% - 2%.

[0011] According to the above scheme, the alkali mass loss rate of the highly alkali-resistant and high-strength glass is in the range of 0.381 - 0.455%.

[0012] According to the above scheme, the flexural strength of the highly alkali-resistant and high-strength glass is in the range of 124.7 - 144.9 MPa.

[0013] According to the above scheme, the forming temperature of the highly alkali-resistant and high-strength glass is in the range of 1154 - 1167 °C.

[0014] According to the above scheme, the hardness of the highly alkali-resistant and high-strength glass is in the range of 6.42 - 6.65 GPa.

[0015] According to the above solution, the density of the high alkali-resistant and high-strength glass is 2.52 - 2.56 g / cm 3 .

[0016] The preparation method of the above high alkali-resistant and high-strength glass includes the following steps:

[0017] 1) Weigh raw materials according to the basic glass formula, mix and grind them evenly, then heat them to 1500 - 1580 °C for high-temperature melting for 2 - 3 h, homogenize and clarify, and then pour them into a mold for shaping to obtain the basic glass;

[0018] 2) Anneal at 630 - 670 °C for 2 - 3 h to obtain the high alkali-resistant and high-strength glass.

[0019] The application of the above high alkali-resistant and high-strength glass in drawing glass fibers.

[0020] A kind of glass fiber is drawn from the above alkali-resistant and high-strength glass.

[0021] A high-temperature flue gas dust removal filter material is made of the glass fiber drawn from the above alkali-resistant and high-strength glass.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] The high alkali-resistant and high-strength glass of the present invention does not contain Fe2O3 and F - , and at the same time, the present invention is kept at a constant temperature in a 10 wt.% NaOH solution at 90 °C for 6 h. After XRD analysis, a calcium silicate hydrate (Ca1.5SiO3.5xH2O) is formed on its surface; through SEM morphology analysis, the formed calcium silicate hydrate is flaky and can also adhere well to the glass surface.

[0024] For the high alkali-resistant and high-strength glass for glass fibers provided by the present invention, SiO2 is used as the glass network skeleton, and its content has a great influence on the performance of the glass. If the SiO2 content is too low, the mechanical properties of the glass will deteriorate, but if the content is too high, the forming temperature and drawing temperature of the glass will also be higher. To balance the performance of the glass fiber and the requirements of the drawing process, the SiO2 content of the present invention is controlled at 54 - 61 wt.%.

[0025] Adding B2O3 can play a role in promoting melting to reduce the melting temperature, drawing temperature and crystallization tendency. Adding an appropriate amount of Al2O3 can improve the mechanical properties of the glass, reduce the crystallization tendency and improve the chemical stability.

[0026] Both CaO and Na2O are network modifiers in the glass, providing sufficient free oxygen in the glass structure. CaO and Na2O form a mixed alkali effect, which has a positive effect on improving the chemical stability, mechanical properties, protecting the glass skeleton, and reducing the high-temperature viscosity of the glass. The SiO2 and CaO components in the glass will react with OH in the alkaline environment - to form insoluble calcium silicate hydrate, which adheres to the glass surface and prevents OH - from further eroding the silicon-oxygen skeleton, thereby improving the alkali resistance of the glass.

[0027] Introducing CeO2 accelerates the clarification of the glass melt at high temperatures, improves the glass density, and simultaneously produces a synergistic effect with Li2O, improving the mechanical properties and corrosion resistance.

[0028] The high alkali-resistant and high-strength glass for glass fibers prepared by the present invention has an alkali-resistant mass loss rate of 0.381 - 0.455%. In addition, the flexural strength and hardness of the high alkali-resistant and high-strength glass for glass fibers are 124.7 - 144.9 MPa and 6.42 - 6.65 GPa respectively; the forming temperature is 1154 - 1167 °C. Compared with the prior art, the alkali resistance and strength of the glass are significantly improved, and at the same time, it has a lower drawing temperature, which is beneficial to the preparation of glass fibers. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 : Test results of the alkali resistance of the high alkali-resistant and high-strength glass in Examples 1 - 4.

[0030] Figure 2 : Test results of the flexural strength of the high alkali-resistant and high-strength glass in Examples 1 - 4.

[0031] Figure 3 : Test results of the forming temperature of the high alkali-resistant and high-strength glass in Examples 1 - 4.

[0032] Figure 4 : XRD test results of the high alkali-resistant and high-strength glass in Examples 1 - 4 after alkali corrosion.

[0033] Figure 5 : SEM images of the high alkali-resistant and high-strength glass in Example 1 after alkali corrosion. DETAILED DESCRIPTION OF THE INVENTION

[0034] The following examples further illustrate the technical solutions of the present invention, but do not limit the protection scope of the present invention.

[0035] The raw materials used in the specific implementation include SiO2, Al2O3, CaCO3, MgO, Na2CO3, H3BO3, Li2CO3, CeO2. The melting of the glass raw materials uses a high-temperature melting furnace, and the annealing of the base glass uses an annealing furnace.

[0036] Example 1

[0037] The selected glass formula includes, by oxides: SiO2: 56.4%; Al2O3: 20.3%; CaO: 12.5%; MgO: 2.1%; Na2O: 3.8%; B2O3: 3.2%; Li2O: 0.4%; CeO2: 1.3%.

[0038] Weigh various raw materials according to the above formula. Put the raw materials into an alumina ceramic mortar and mix and grind for 20 minutes to obtain a batch mixture. Put the batch mixture into a corundum crucible, heat it to 1580 °C at a heating rate of 5 °C / min, hold for 3 hours after the temperature reaches 1580 °C, obtain glass melt through high-temperature melting, homogenization and clarification, pour the glass melt into a stainless-steel mold for shaping, then put it into an annealing furnace at 670 °C and hold for 3 hours for annealing, and obtain a high alkali-resistant and high-strength base glass after cooling to room temperature with the furnace. Then perform performance tests on the base glass.

[0039] For the high alkali-resistant and high-strength glass prepared in this example, the alkali-resistant mass loss rate is 0.381%; the flexural strength is 124.7 MPa; the hardness is 6.65 GPa; the forming temperature is 1160 °C.

[0040] Example 2

[0041] The selected glass formula includes, by oxides: SiO2: 56.3%; Al2O3: 20.3%; CaO: 11.7%; MgO: 2.1%; Na2O: 4.7%; B2O3: 3.2%; Li2O: 0.4%; CeO2: 1.3%.

[0042] Weigh various raw materials according to the above formula. Put the raw materials into an alumina ceramic mortar and mix and grind for 20 minutes to obtain a batch mixture. Put the batch mixture into a corundum crucible, heat it to 1500 °C at a heating rate of 5 °C / min, hold for 3 hours after the temperature reaches 1500 °C, obtain glass melt through high-temperature melting, homogenization and clarification, pour the glass melt into a stainless-steel mold for shaping, then put it into an annealing furnace at 650 °C and hold for 2 hours for annealing, and obtain a high alkali-resistant and high-strength base glass after cooling to room temperature with the furnace. Then perform performance tests on the base glass.

[0043] For the high alkali-resistant and high-strength glass prepared in this example, the alkali-resistant mass loss rate is 0.402%; the flexural strength is 130.2 MPa; the hardness is 6.62 GPa; the forming temperature is 1154 °C.

[0044] Example 3

[0045] The selected glass formula, calculated on an oxide basis, includes: SiO2: 56.2%; Al2O3: 20.3%; CaO: 10.8%; MgO: 2.1%; Na2O: 5.7%; B2O3: 3.2%; Li2O: 0.4%; CeO2: 1.3%.

[0046] Weigh various raw materials according to the above formula. Put the raw materials into an alumina ceramic mortar and mix and grind them for 20 minutes to obtain a batch mixture. Put the batch mixture into a corundum crucible, heat it to 1580 °C at a heating rate of 5 °C / min. After the temperature reaches 1580 °C, hold it for 2 hours. After high-temperature melting, homogenization and clarification, a glass melt is obtained. Pour the glass melt into a stainless-steel mold for shaping, and then put it into an annealing furnace at 640 °C and hold it for 3 hours for annealing. After cooling to room temperature with the furnace, a high alkali-resistant and high-strength base glass is obtained. Subsequently, performance tests are carried out on the base glass.

[0047] For the high alkali-resistant and high-strength glass prepared in this example, the alkali-resistant mass loss rate is 0.411%; the flexural strength is 132.2 MPa; the hardness is 6.55 GPa; the forming temperature is 1167 °C.

[0048] Example 4

[0049] The selected glass formula, calculated on an oxide basis, includes: SiO2: 56.1%; Al2O3: 20.2%; CaO: 9.1%; MgO: 2.1%; Na2O: 7.6%; B2O3: 3.2%; Li2O: 0.4%; CeO2: 1.3%.

[0050] Weigh various raw materials according to the above formula. Put the raw materials into an alumina ceramic mortar and mix and grind them for 20 minutes to obtain a batch mixture. Put the batch mixture into a corundum crucible, heat it to 1580 °C at a heating rate of 5 °C / min. After the temperature reaches 1580 °C, hold it for 3 hours. After high-temperature melting, homogenization and clarification, a glass melt is obtained. Pour the glass melt into a stainless-steel mold for shaping, and then put it into an annealing furnace at 630 °C and hold it for 3 hours for annealing. After cooling to room temperature with the furnace, a high alkali-resistant and high-strength base glass is obtained. Subsequently, performance tests are carried out on the base glass.

[0051] For the high alkali-resistant and high-strength glass prepared in this example, the alkali-resistant mass loss rate is 0.455%; the flexural strength is 144.9 MPa; the hardness is 6.42 GPa; the forming temperature is 1167 °C.

[0052] The experimental conditions for the alkali resistance of the glass in the specific examples are: constant temperature corrosion in a 10 wt.% NaOH solution at 90 °C for 6 hours, weigh the mass of the glass before and after corrosion, as shown in the attachment Figure 1 as shown

[0053] Use an electronic universal material testing machine to test the flexural strength of the base glass, as shown in the attachmentFigure 2 as shown

[0054] Use a high-temperature viscometer to test the viscosity-temperature curve of the base glass and determine the forming temperature of the glass fiber, as shown in the appendix Figure 3 as shown

[0055] Use a Vickers hardness tester to test the hardness of the base glass. Use an X-ray diffractometer and a scanning electron microscope to test the phase and surface morphology formed on the glass surface after alkali corrosion, as shown in the appendix Figure 4 and appendix Figure 5 as shown

Claims

1. A high alkali-resistant and high-strength glass, characterized in that The basic raw materials are calculated by mass percentage: SiO2: 54%~61%; Al2O3: 19%~23%; CaO: 7%~14%; MgO: 1%~7%; Na2O: 1~8%; B2O3: 0%~6%; Li2O: 0%~1%; CeO2: 0%~3%.

2. A high alkali-resistant and high-strength glass, characterized in that The basic raw materials are calculated by mass percentage: SiO2: 55%~60%; Al2O3: 20%~22%; CaO: 8%~13%; MgO: 2%~6%; Na2O: 2~7%; B2O3: 1%~6%; Li2O: 0.1%~1%; CeO2: 0.1%~3%.

3. A high alkali-resistant and high-strength glass, characterized in that The basic raw materials are calculated by mass percentage: SiO2: 56%~58%; Al2O3: 20%~22%; CaO: 9%~12%; MgO: 3%~5%; Na2O: 3~6%; B2O3: 2%~4%; Li2O: 0.2%~0.6%; CeO2: 0.5%~2%.

4. The high alkali-resistant and high-strength glass according to any one of claims 1, 2 and 3, characterized in that The alkali-resistant mass loss rate of the high-alkali-resistant and high-strength glass is in the range of 0.381 to 0.455%.

5. The high alkali-resistant and high-strength glass according to any one of claims 1, 2 and 3, characterized in that The flexural strength of the high alkali-resistant and high-strength glass is in the range of 124.7 to 144.9 MPa.

6. The high alkali-resistant and high-strength glass according to any one of claims 1, 2 and 3, characterized in that The forming temperature of the high alkali-resistant and high-strength glass is in the range of 1154-1167°C.

7. The high alkali-resistant and high-strength glass according to any one of claims 1, 2 and 3, characterized in that The hardness of the high alkali-resistant and high-strength glass is in the range of 6.42 to 6.65 GPa.

8. The high alkali-resistant and high-strength glass according to any one of claims 1, 2 and 3, characterized in that The density of the high alkali-resistant and high-strength glass is 2.52-2.56 g / cm 3 .

9. The method for preparing the high alkali-resistant and high-strength glass according to any one of claims 1, 2 and 3, characterized in that The following steps are involved: 1) Weighing the raw materials according to the basic glass formula, mixing and grinding them evenly, heating them to 1500-1580° C. and melting them at high temperature for 2-3 hours, homogenizing and clarifying them, and pouring them into a mold to obtain basic glass; 2) Annealing at 630-670℃ for 2-3h to obtain high alkali-resistant and high-strength glass.

10. A glass fiber obtained by drawing the high alkali-resistant and high-strength glass according to any one of claims 1, 2 and 3.

Images