阅读说明：本技术 耐腐蚀玻璃组合物及制备方法 (Corrosion-resistant glass composition and preparation method thereof ) 是由 张新林 吴孝玮 于 2020-06-15 设计创作，主要内容包括：一种耐腐蚀玻璃组合物,其包含：59.0-63.0wt％SiO<Sub>2</Sub>；12.1-13.9wt％Al<Sub>2</Sub>O<Sub>3</Sub>；9.0-14.0wt％金属氧化物RO；10.0-13.9wt％碱金属氧化物R<Sub>2</Sub>O；0-0.59wt％铁的氧化物。还可以进一步包含0-2.0wt％TiO<Sub>2</Sub>；0-0.8wt％的F<Sup>-</Sup>；0-0.8wt％的CeO<Sub>2</Sub>；0-2.0wt％的Li<Sub>2</Sub>O；0-4.0wt％的ZrO<Sub>2</Sub>；0-2.0wt％的MnO<Sub>2</Sub>；0-2.0wt％的La<Sub>2</Sub>O<Sub>3</Sub>。该组合物可以一种制得兼具耐酸、耐碱性能的低成本可纤维化玻璃,其玻璃成型温度比液相温度高80℃以上,且具有良好的纤维抽丝成型性。(A corrosion resistant glass composition comprising: 59.0-63.0 wt% SiO 2 ；12.1‑13.9wt％Al 2 O 3 (ii) a 9.0-14.0 wt% metal oxide RO; 10.0 to 13.9 wt% of an alkali metal oxide R 2 O; 0-0.59 wt% iron oxide. May further comprise 0-2.0 wt% of TiO 2 (ii) a 0-0.8 wt% of F ‑ (ii) a 0-0.8 wt% of CeO 2 (ii) a 0-2.0 wt% of Li 2 O; 0-4.0 wt% of ZrO 2 (ii) a 0-2.0 wt% MnO 2 (ii) a 0-2.0 wt% of La 2 O 3 . The composition can be used for preparing low-cost fiberizable glass with acid resistance and alkali resistance, the glass forming temperature of the fiberizable glass is higher than the liquid phase temperature by more than 80 ℃, and the fiberizable glass has good fiber drawing formability.)

1. A corrosion resistant glass composition, comprising:

59.0-63.0wt％SiO₂；

12.1-13.9wt％Al₂O₃；

9.0-14.0 wt% metal oxide RO;

10.0 to 13.9 wt% of an alkali metal oxide R₂O；

0-0.59 wt% iron oxide.

2. A corrosion resistant glass composition, comprising:

59.0-63.0wt％SiO₂；

12.1-13.9wt％Al₂O₃；

9.0-14.0 wt% of metal oxide CaO + MgO;

10.0-13.9 wt% of alkali metal oxide Na₂O+K₂O；

0-2.0wt％TiO₂(ii) a And

0-0.59 wt% iron oxide.

3. A corrosion resistant glass composition, comprising:

59.0-63.0wt％SiO₂；

12.1-13.9wt％Al₂O₃；

9.0-14.0 wt% of metal oxide CaO + MgO;

10.0-13.9 wt% of alkali metal oxide Na₂O+K₂O；

0-0.59 wt% of an oxide of iron;

0-0.8 wt% of F^-；

0-0.8 wt% of CeO₂；

0-2.0 wt% of alkali metal oxide Li₂O；

0-4.0 wt% of ZrO₂；

0-2.0 wt% MnO₂；

0-2.0 wt% of La₂O₃。

4. The corrosion-resistant glass composition of claim 1, wherein said metal oxide RO comprises one or more of CaO, MgO, SrO, and ZnO.

5. The corrosion-resistant glass composition of any of claims 1 to 3, wherein the metal oxide has a MgO content of 0 to 3.0 wt.%.

6. The corrosion-resistant glass composition of any of claims 1 to 3, wherein the alkali metal oxide comprises 0 to 3.0 wt.% K₂O。

7. The corrosion-resistant glass composition of any of claims 1 to 3, wherein the iron oxide/Al₂O₃Is less than 0.045.

8. The corrosion-resistant glass composition of any of claims 1-3, wherein Al is₂O₃The content ratio of the alkali metal oxide is between 0.9 and 1.1.

9. The corrosion-resistant glass composition of any of claims 4 to 8, wherein the iron oxide comprises FeO and Fe₂O₃。

10. A method of making a corrosion resistant glass composition according to any of claims 1 to 3, comprising the steps of:

weighing the raw materials according to the required dosage proportion, stirring and mixing, putting the mixture into a furnace kiln for melting, wherein the depth of a melting pool is more than 1.5m, and the highest temperature of glass liquid in the kiln is controlled at 1400-1460 ℃; the bottom of the highest temperature zone of the glass metal in the furnace is provided with bubbling pipes, and each bubbling pipe blows N into the furnace at 80-160 ml/min₂Gas to make N₂The gas forms bubbles, takes away small bubbles in the molten glass in the rising process and stirs the molten glass to promote the homogenization and clarification of the molten glass; the homogenized glass liquid enters the main passage through the sinking type throat and then flows into the operation passage, the temperature of the operation passage is controlled to be 1260-1320 ℃, a platinum-rhodium alloy bushing plate containing 10 wt% of rhodium is installed below the operation passage, the bushing plate is electrified and heated, and the temperature of the bushing plate is accurately controlled to be 1190-1220 ℃.

The technical field is as follows:

the present invention relates to glass compositions, and in particular to corrosion resistant glass compositions useful in fiber production.

Background art:

glass fibers are produced commercially by melting a batch material consisting essentially of crystalline or amorphous minerals to form liquid glass, flowing at a temperature from a bushing orifice, drawing at high speed through a wire drawing machine while cooling to filaments.

The glass fiber is used as a composite material reinforced base material, and as the application range of the glass fiber is continuously expanded, the requirements on various performances of the glass fiber are developed towards differentiation and individuation; among them, corrosion resistance is an important aspect.

The alkali-resistant glass (AR glass) defined in the Chinese building material standard JC 935-2004 comprises the following components: 59.2-60.8 wt% SiO₂13.9-16.1 wt% of R₂O,13.7-15.3 wt% ZrO,5.5-6.5 wt% TiO₂4.0-5.0 wt% CaO, not more than 1 wt% Al₂O₃Wherein 2.2-2.8 wt% of K₂O, and not more than 0.5 wt% Fe₂O₃(ii) a AR glass has strong acid-base corrosion resistance, but because the glass component contains a large amount of ZrO and TiO₂The molding temperature reaches 1300 ℃, and the comprehensive cost of manufacturing the fiber is more than 3 times of that of the common ECR glass fiber, thereby limiting the application of the fiber.

The medium alkali glass (C glass) defined by the Chinese building material standard JC 935-2004 comprises the following components: 66.5 to 67.5 percent of SiO₂5.8-6.6 wt% of Al₂O₃9.2-9.8 wt% CaO, 3.9-4.5 wt% MgO, 11.6-12.4 wt% R₂O, wherein K₂0.4 wt% or less of O and not more than 0.4 wt% of Fe₂O₃(ii) a The C glass has better acid resistance but poor alkali resistance, and the water resistance of the C glass is also poor because alkali metal ions are easy to separate out in a humid environment to form corrosion in an alkali environment. The C glass belongs to sodium-calcium-aluminum-silicon quaternary glass, the content of silicon oxide and alkali metal oxide is relatively high, the viscosity-temperature curve is gentler than that of alkali-free glass, the hardening speed is slow, and large bushing and high-flow stable spinning cannot be realized.

The glass composition described in the patent publication CN201080034381.5 is improved on the basis of C glass, and some examples show better acid resistance and alkali resistance, but because of the broad definition of each oxide, the alkali resistance of some examples is not improved significantly, and is also worse than that of C glass; in addition, the batch composition required to form the glass composition must contain at least 50% vitreous minerals, which places high demands on the raw materials.

Glass composition described in patent publication CN201810566742.9, Al thereof₂O₃The content of the iron oxide is increased to 9.0-14.0 wt%, and the corrosion resistance is improved compared with the C glass, but the content of the iron oxide is limited to 0.6-1.0 wt%, and Al₂O₃Also has a relatively wide content of wt%, iron oxide and Al₂O₃The content ratio of wt% can reach more than 0.1, Al₂O₃/R₂The Owt% content ratio can be as low as 0.57, which causes the structure of the glass composition to change due to valence change of iron oxide, which affects the corrosion resistance, and in addition, Al₂O₃/R₂When the Owt% content ratio is low, the non-bridging oxygen content in the glass composition structure is also increased, and the portion containing more non-bridging oxygen structure is easily corroded to fall off the glass composition, thereby reducing the corrosion resistance of the glass composition.

The invention content is as follows:

the invention aims to overcome the defects of the prior art and provide low-cost fiberizable glass with acid resistance and alkali resistance, wherein the glass forming temperature is higher than the liquid phase temperature by more than 80 ℃, and the fiberizable glass has good fiber drawing formability.

A corrosion resistant glass composition comprising:

59.0-63.0wt％SiO₂；

12.1-13.9wt％Al₂O₃；

9.0-14.0 wt% metal oxide RO;

10.0 to 13.9 wt% of an alkali metal oxide R₂O；

0-0.59 wt% iron oxide.

Also provided is a corrosion resistant glass composition comprising:

59.0-63.0wt％SiO₂；

12.1-13.9wt％Al₂O₃；

9.0-14.0 wt% of metal oxide CaO + MgO;

10.0-13.9 wt% of alkali metal oxide Na₂O+K₂O；

0-2.0wt％TiO₂(ii) a And

0-0.59 wt% iron oxide.

Also provided is a corrosion resistant glass composition comprising:

59.0-63.0wt％SiO₂；

12.1-13.9wt％Al₂O₃；

9.0-14.0 wt% of metal oxide CaO + MgO;

10.0-13.9 wt% of alkali metal oxide Na₂O+K₂O；

0-0.59 wt% of an oxide of iron;

0-0.8 wt% of F^-；

0-0.8 wt% of CeO₂；

0-2.0 wt% of Li₂O；

0-4.0 wt% of ZrO₂；

0-2.0 wt% MnO₂；

0-2.0 wt% of La₂O₃。

Further, the metal oxide RO comprises one or more of CaO, MgO, SrO, and ZnO.

Further, the content of MgO in the metal oxide is 0-3.0 wt%.

Further, the alkali metal oxide contains K in an amount of 0 to 3.0 wt%₂O。

Further, the weight% content ratio of iron oxide/alumina is less than 0.045.

Further, Al₂O₃The content ratio of the alkali metal oxide in wt% is 0.9-1.1.

Further, the iron oxide contains FeO and Fe₂O₃。

Meanwhile, the preparation method of the corrosion-resistant glass composition comprises the following steps:

weighing the raw materials according to the required dosage proportion, stirring and mixing, putting the mixture into a furnace kiln for melting, wherein the depth of a melting pool is more than 1.5m, and the highest temperature of glass liquid in the kiln is controlled at 1400-1460 ℃; the bottom of the highest temperature zone of the glass metal in the furnace is provided with bubbling pipes, and each bubbling pipe blows N into the furnace at 80-160 ml/min₂Gas to make N₂The gas forms bubbles, takes away small bubbles in the molten glass in the rising process and stirs the molten glass to promote homogenization and clarification of the molten glass. The homogenized glass liquid enters a main passage through a sinking type throat and then flows into an operation passage, the temperature of the operation passage is controlled to be 1260-1320 ℃, a platinum-rhodium alloy bushing containing 10 wt% of rhodium is installed below the operation passage, the metal material of the bushing can conduct electricity, the bushing is electrified and heated, the temperature of the bushing is accurately controlled to be 1190-1220 ℃, the temperature is 80-100 ℃ higher than the crystallization upper limit temperature of the glass composition, and continuous and stable wire drawing can be realized.

The applicant has found, by study, that Al is present in the glass composition₂O₃When the content is controlled to be 12.1-13.9 wt%, Al is present in the glass relative to the medium alkali glass₂O₃The content is greatly improved, and a large amount of Al can be used₂O₃And natural mineral raw materials with higher alkali metal oxides, the raw materials have wider sources; al to CN201080034381.5₂O₃The content of wt% is optimized, and Al is added₂O₃The content ratio of the alkali metal oxide in wt% is limited between 0.9 and 1.1, so that the non-bridge oxygen ratio in the glass composition structure is reduced to a lower level, the glass composition structure is stable, and the corrosion resistance is optimized. Al to CN201810566742.9₂O₃Optimizing the content of wt%, reducing the content of wt% of iron oxide, and mixing the iron oxide with Al₂O₃The wt% content ratio is limited to not more than 0.045, which both reduces the proportion of non-bridging oxygen and does not change the structure of the glass composition due to the valence change of iron oxide, improving the corrosion resistance of the glass composition.

The content of iron oxide in the glass composition is 0-0.59 wt%, which is lower than CN201810566742.9, and the heat permeability of the glass composition is improved, namely the transmissivity of visible light and infrared ray is improved.

The glass composition of the present invention has an iron oxide/alumina content ratio of less than 0.045 to avoid excessive iron oxide that would alter the microstructure of the glass composition by changing valence, thereby resulting in changes in glass properties.

Drawings

FIG. 1 is a graph showing a comparison of water resistance of a glass composition

Wherein, A: example 2 of the present application; b: c, glass; c: CN201810566742.9 example 1; d: CN201810566742.9 example 4.

Detailed Description

The present invention provides glass compositions formed from mineral or chemical product batch compositions, particularly glass compositions used to make fibers.

In embodiments, the present invention provides glass compositions formed from batch compositions comprising sandstone, albite, limestone, dolomite, soda ash.

The glass composition of the present invention is fiberizable at a forming temperature (T)_F) At 1190-1220 deg.c and higher than the upper limit of crystallization temperature_L)80℃-100℃。T_FThe optimum forming temperature point for the manufacture of articles from the glass composite is indicated, which for glass drawing is the temperature at which the viscosity is 1000 poise, also known as the glass fiber forming temperature. T is_LRepresents the upper limit of the liquidus temperature of the glass, i.e., the devitrification temperature. Δ T represents T_F-T_LThe difference in (b) represents a molding range in the process of preparing a fiber from the glass composition. The viscosity of the glass composition is detected by a high-temperature viscometer manufactured by Orton company; the liquidus temperature of the glass composition was measured using an Orton Model gradient furnace.

When the fiber is prepared, the raw materials are weighed according to the required dosage proportion, stirred and mixed, and then put into a furnace kiln for melting, wherein the depth of a melting pool is more than 1.5m, and the highest temperature of glass liquid in the kiln is controlled at 1400-1460 ℃; the bottom of the highest temperature zone of the molten glass in the furnace is provided with bubbling pipes, and each bubbling pipe is 80 percent160 ml/min blowing N into the furnace₂Gas to make N₂The gas forms bubbles, takes away small bubbles in the molten glass in the rising process and stirs the molten glass to promote homogenization and clarification of the molten glass. The homogenized glass liquid enters a main passage through a sinking type throat and then flows into an operation passage, the temperature of the operation passage is controlled between 1260 ℃ and 1320 ℃, a platinum-rhodium alloy bushing containing 10 wt% of rhodium is installed below the operation passage, the metal material of the bushing can conduct electricity, the bushing is electrified and heated, the temperature of the bushing is accurately controlled between 1190 ℃ and 1220 ℃, the glass liquid flows out through the platinum-rhodium alloy bushing and is drawn into glass fibers with the diameter of 5-25 mu m.

In some embodiments, the metal oxide RO component contains ZnO and SrO or combinations thereof in addition to CaO and MgO.

In one embodiment, the present invention provides a glass composition comprising 62.0 wt.% SiO₂13.1 wt% of Al₂O₃12.0 wt% RO (CaO + MgO + ZnO), 12.7 wt% R₂O(K₂O+Na₂O) and 0.2 wt.% of iron oxide, iron oxide/Al₂O₃Is about 0.015. The iron oxide contains FeO and Fe₂O₃。

In another embodiment, the invention provides a glass composition comprising 59.0 wt.% SiO₂13.9 wt% of Al₂O₃13.8 wt% RO (CaO + MgO), 12.8 wt% R₂O(K₂O+Na₂O) and 0.59% by weight of iron oxide, iron oxide/Al₂O₃Is about 0.042. The iron oxide contains FeO and Fe₂O₃。

In another embodiment, the invention provides a glass composition comprising 63.0 wt.% SiO₂12.1 wt% of Al₂O₃13.0 wt% RO (CaO + MgO + SrO), 11.1 wt% R₂O(K₂O+Na₂O), 0.4 wt% Li₂O and 0.4 wt% iron oxide, wherein iron oxide/Al₂O₃Is about 0.033. The iron oxide contains FeO and Fe₂O₃。

In another embodiment, the invention provides a glass composition comprising 61.0 wt.% SiO₂13.7 wt% of Al₂O₃10.6 wt% RO (CaO + MgO), 13.85 wt% R₂O(K₂O+Na₂O), 0.7 wt.% of F^-And 0.15 wt% iron oxide, wherein iron oxide/Al₂O₃Is about 0.011. The iron oxide contains FeO and Fe₂O₃。

In another embodiment, the invention provides a glass composition comprising 62.2 wt.% SiO₂12.5 wt% of Al₂O₃10.5 wt% RO (CaO + MgO), 13.8 wt% R₂O(K₂O+Na₂O), 0.7 wt% of CeO₂And 0.30 wt% iron oxide, wherein iron oxide/Al₂O₃Is about 0.024. The iron oxide contains FeO and Fe₂O₃。

In an embodiment of the invention, the glass composition produced by the method of the invention has a tensile modulus between 71GPa and 74 GPa.

In the embodiment of the invention, the glass composition prepared by the method can be stably drawn on a platinum-rhodium bushing device with 400-2400 holes.

In an embodiment of the invention, the glass composition produced by the method of the invention has corrosion resistance, 25 micron diameter fibers uncoated with surface modifier, H at 1N₂SO₄(pH 0) soaking the solution at 100 deg.C for 1 hr to obtain a loss rate of 0.10% or less; the solution was immersed in 0.01N NaOH (pH 12) at 96 ℃ for 24 hours, and the loss rate was not more than 0.25%. (see Table 1 for data comparison)

In an embodiment of the present invention, the glass composition prepared by the method of the present invention has water resistance, and the loss rate of the fiber with the diameter of 25 microns and without being coated with the surface modifier is not more than 0.10 percent after being soaked in pure water with the pH value of 6.5-7.0 for 4 hours at the temperature of 100 ℃. (see Table 1 for data comparison)

In example 3 according to the invention, the glass composition produced by the process of the invention gave a 5mm thick clear glass sheet having a transmittance of 85% in the infrared at 1000nm, while the 5mm thick clear glass sheet produced in CN201810566742.9 example (reference example 2) gave a transmittance of 61% under the same conditions. (see Table 1 for data comparison)

In the embodiment of the present invention, the fiber strength retention of the fiber yarn formed by spinning the glass composition prepared by the method of the present invention is about 90% when the fiber yarn is placed in an environment with 100% relative humidity and 25 ℃ for 24 hours, the retention of the C glass fiber yarn under the same conditions is only 20%, and the retention of the glass composition prepared by CN201810566742.9 is greatly changed. (see figure 1 of the drawings of the specification).

In an embodiment of the invention, the glass composition produced by the method of the invention has a nascent filament strength of between 3000MPa and 3400 MPa.

TABLE 1 glass composition Components and partial physicochemical Properties data

Note: the oxide data in the table is wt%;

the reference example 1 is CN201080034381.5 embodiment 19, and the reference example 2 is CN201810566742.9 embodiment 4.

As can be seen from the comparison of the above examples with the reference examples, Al is optimized₂O₃Content in wt.%, oxide of limited iron/Al₂O₃Content ratio of wt% is not more than 0.045, Al₂O₃The content ratio of the alkali metal oxide in weight percent is 0.9-1.1, the corrosion resistance of the glass composition is obviously improved, particularly the water resistance is greatly improved, and the difference of the corrosion resistance of each embodiment is small.

The description illustrates aspects relevant to the invention and certain aspects that will be apparent to those skilled in the art have not been presented to simplify the description. While the present invention has been described in connection with certain embodiments, it is not intended to be limited to the specific embodiments disclosed, but rather, to provide an explanation of the invention as defined in the appended claims.