阅读说明：本技术 耐碱性良好的低成本玻璃纤维组合物及玻璃纤维 (Low-cost glass fiber composition with good alkali resistance and glass fiber ) 是由 唐志尧 李永艳 于 2020-09-03 设计创作，主要内容包括：本发明属于玻璃纤维技术领域,具体涉及一种耐碱性良好的低成本玻璃纤维组合物及玻璃纤维。所述组合物各组分含量如下：SiO<Sub>2</Sub>：60.0-70.0wt.％,CaO：8.0-10.0wt.％,MgO：5.0-8.0wt.％,Al<Sub>2</Sub>O<Sub>3</Sub>：0-5.0wt.％,TiO<Sub>2</Sub>：0-3.0wt.％,Fe<Sub>2</Sub>O<Sub>3</Sub>：0-1.0wt.％,Na<Sub>2</Sub>O：18.0-20.0wt.％,K<Sub>2</Sub>O：0-1.0wt.％,ZrO<Sub>2</Sub>：0.1-0.5wt.％,余量为杂质。本发明同时提供耐碱性良好的低成本玻璃纤维。将本发明的玻璃纤维制成纱线,得到的纱线耐碱性良好,机械强度高,成品毛羽量少,且成本较低,可以用于生产通用型外墙网格布或高耐碱性的其它复合材料基体。(The invention belongs to the technical field of glass fiber, and particularly relates to a low-cost glass fiber composition with good alkali resistance and glass fiber. The composition comprises the following components in percentage by weight: SiO 2 2 ：60.0‑70.0wt.％，CaO：8.0‑10.0wt.％，MgO：5.0‑8.0wt.％，Al 2 O 3 ：0‑5.0wt.％，TiO 2 ：0‑3.0wt.％，Fe 2 O 3 ：0‑1.0wt.％，Na 2 O：18.0‑20.0wt.％，K 2 O：0‑1.0wt.％，ZrO 2 : 0.1-0.5 wt.%, with the balance impurities. The invention also provides a low-cost glass fiber with good alkali resistance. The yarn prepared from the glass fiber has the advantages of good alkali resistance, high mechanical strength, less hairiness of a finished product and lower cost, and can be used for producing general outer wall mesh cloth or other high alkali resistance composite material matrixes.)

1. A low-cost glass fiber composition with good alkali resistance, which is characterized in that: the weight percentage of each component is as follows: SiO 2₂：60.0-70.0wt.％，CaO：8.0-10.0wt.％，MgO：5.0-8.0wt.％，Al₂O₃：0-5.0wt.％，TiO₂：0-3.0wt.％，Fe₂O₃：0-1.0wt.％，Na₂O：18.0-20.0wt.％，K₂O：0-1.0wt.％，ZrO₂: 0.1-0.5 wt.%, with the balance impurities.

2. The well-alkali-resistant, low-cost glass fiber composition of claim 1, wherein: MgO and Na₂MgO/Na in terms of the mass percentage of O₂O is 0.25-0.45.

3. The well-alkali-resistant, low-cost glass fiber composition of claim 1, wherein: the mass percentage of MgO to CaO is 0.5-1.0.

4. The well-alkali-resistant, low-cost glass fiber composition of claim 1, wherein: the weight percentage of each component is as follows: SiO 2₂：63.0-67.0wt.％，CaO：8.0-9.0wt.％，MgO：5.0-8.0wt.％，Al₂O₃：0.5-3.0wt.％，TiO₂：0.2-3.0wt.％，Fe₂O₃：0.2-1.0wt.％，Na₂O：18.5-19.5wt.％，K₂O：0.05-1.0wt.％，ZrO₂: 0.1-0.5 wt.%, with the balance impurities.

5. The well-alkali-resistant, low-cost glass fiber composition of claim 1, wherein: the fiber forming temperature of the glass fiber composition is 1200-1300 ℃, and the liquidus temperature is 1100-1250 ℃.

6. The well-alkali-resistant, low-cost glass fiber composition of claim 5, wherein: the difference delta T between the fiber forming temperature and the liquidus temperature is 50-120 ℃.

7. The well-alkali-resistant, low-cost glass fiber composition of claim 1, wherein: the feed is prepared from the following raw materials: coal series kaolin, quartz powder, quicklime, magnesium oxide, albite, anhydrous sodium sulphate and zircon powder, wherein the average particle size is 100-200 mu m.

8. A low cost glass fiber with good alkali resistance made from the composition of claim 1, wherein: the preparation process comprises the following steps:

(1) weighing raw materials of the glass fiber composition according to a ratio, and mixing to obtain a uniform batch;

(2) melting the batch to obtain glass liquid;

(3) and drawing the glass liquid into fibers through a bushing, cooling, coating a sizing agent, and conditioning to obtain the low-cost glass fiber with good alkali resistance.

9. The low-cost glass fiber with good alkali resistance according to claim 8, wherein: the melting temperature is 1450-1500 ℃, and the bushing temperature is 1150-1250 ℃.

10. The low-cost glass fiber with good alkali resistance according to claim 8, wherein: the conditioning temperature is 28-30 ℃, and the conditioning time is 16-18 h; the humidity during conditioning is 65-70%.

Technical Field

The invention belongs to the technical field of glass fiber, and particularly relates to a low-cost glass fiber composition with good alkali resistance and glass fiber.

Background

The glass fiber is an inorganic non-metallic material with the largest use amount and the widest application range in the composite material reinforced base material, and has wide application in the fields of new energy, traffic, industry, construction, environment and the like. With the rapid development of glass fibers, especially the requirements in the field of glass fibers with high alkali resistance, aging resistance and the like are continuously increased, and ordinary medium-alkali glass fibers and alkali-free glass fibers cannot meet the market demands. In order to improve the alkali resistance of glass fibers, high-strength glass fibers have been successfully developedThe alkali-resistant glass fiber of zirconium has better alkali resistance, and the general ZrO in the alkali-resistant fiber₂Not less than 14.5 percent, and ZrO is introduced₂The raw material of the alkali-resistant glass is zircon powder, and the required raw material of the zircon powder is expensive, so that the alkali-resistant glass has high cost and relatively poor mechanical property. Therefore, there is a need in the art to develop a glass fiber with high alkali resistance and low cost.

Chinese patent CN102050572A discloses a boron-free neutral glass, which comprises the following components in percentage by mass: 65-72% SiO₂、11-17％Al₂O₃、0.1-8％Na₂O, 3-8% MgO, 4-12% CaO and 0-10% ZnO, the neutral glass having a first resistance to hydrolysis according to DIN ISO719, and a second resistance to acid according to DIN12116 and a second resistance to alkali according to DIN ISO 695. The glass component is only suitable for the production of neutral glass, the production process of the neutral glass is completely different from the manufacturing process of glass fiber, and the component is not suitable for the production of continuous glass fiber.

Chinese patent CN103787593A discloses a method for preparing alkali-resistant glass fiber, which is mainly to remove the wetting agent on the surface of the glass fiber by baking, then to perform surface treatment on the glass fiber, and to obtain alkali-resistant glass fiber by post-treatment. The patent does not provide the alkali resistant glass fiber composition.

Chinese patent CN105753330A discloses an alkali-resistant glass fiber composition, alkali-resistant glass fibers and a preparation method of the alkali-resistant glass fibers. The glass fiber composition contains the following components: SiO 2₂50-65％，CaO 10-24％，Al₂O₃0.5-14％，MgO 2-7％，Na₂O+K₂O 0-15％，ZrO₂0-15％，TiO₂0.1-0.9%, iron oxide 0.1-0.5%, and other 0-0.5%, wherein "0" means that the content is infinitely close to 0 but not 0.

Chinese patent CN105800943A discloses a glass fiber composition using red mud and blast furnace slag as raw materials, alkali-resistant glass fiber and a preparation method of the alkali-resistant glass fiber. The glass fiber composition contains the following components: SiO 2₂48-62％、CaO 5-20％、Al₂O₃6-18％、MgO 0.2-6％、ZrO₂0-14.5％、Li₂O+Na₂O+K₂O 0.5-6.5％、TiO₂0.01-2%, iron oxide 5-15%, and others 0-0.5%.

The technical problems solved by the two patents are that solid wastes are effectively recycled.

Chinese patent CN104261686A discloses an alkali-resistant glass fiber composition, which comprises the following components in percentage by weight: SiO 2₂59.0-63.0％，ZrO₂14.5-16.5％，CaO 4.0-5.5％，R₂O＝Li₂O+Na₂O+K₂O 14.9-17.0％，Fe₂O₃0-1.0％，TiO₂0 to 0.5 percent; wherein, K is₂The weight percentage of O is 0.1-1.4%, and the Li₂The weight percentage content of O is 0.1-1.0%, and the ratio C1 ═ Li₂O+Na₂O+K₂O)/ZrO₂Is 0.89-1.05. The alkali-resistant glass fiber composition of the patent has a high zirconium content, which increases the cost.

Disclosure of Invention

The invention aims to provide a low-cost glass fiber composition with good alkali resistance and simultaneously provide a low-cost glass fiber with good alkali resistance, and yarns made of the glass fiber have good alkali resistance, high mechanical strength, less hairiness of finished products and lower cost.

The low-cost glass fiber composition with good alkali resistance comprises the following components in percentage by mass: SiO 2₂：60.0-70.0wt.％，CaO：8.0-10.0wt.％，MgO：5.0-8.0wt.％，Al₂O₃：0-5.0wt.％，TiO₂：0-3.0wt.％，Fe₂O₃：0-1.0wt.％，Na₂O：18.0-20.0wt.％，K₂O：0-1.0wt.％，ZrO₂: 0.1-0.5 wt.%, with the balance impurities.

Wherein:

MgO and Na₂MgO/Na in terms of the mass percentage of O₂O is 0.25 to 0.45; the mass percentage of MgO to CaO is 0.5-1.0.

The fiber forming temperature of the glass fiber composition is 1200-1300 ℃, and the liquidus temperature is 1100-1250 ℃.

The difference delta T between the fiber forming temperature and the liquidus temperature is 50-120 ℃, has good fiber forming process requirements, and can be continuously produced in large scale so as to meet market requirements.

Preferably, the low-cost glass fiber composition with good alkali resistance comprises the following components in percentage by mass: SiO 2₂：63.0-67.0wt.％，CaO：8.0-9.0wt.％，MgO：5.0-8.0wt.％，Al₂O₃：0.5-3.0wt.％，TiO₂：0.2-3.0wt.％，Fe₂O₃：0.2-1.0wt.％，Na₂O：18.5-19.5wt.％，K₂O：0.05-1.0wt.％，ZrO₂: 0.1-0.5 wt.%, with the balance impurities.

The low-cost glass fiber composition with good alkali resistance of the invention does not contain LiO₂Fluorine-free, boron-free.

The invention relates to a low-cost glass fiber composition with good alkali resistance, which is prepared from the following raw materials: coal series kaolin, quartz powder, quicklime, magnesium oxide, albite, anhydrous sodium sulphate and zircon powder; the raw materials are common and the cost is low. Wherein: the average grain diameters of the coal-series kaolin, the quartz powder, the quicklime, the magnesia, the albite, the anhydrous sodium sulphate and the zircon powder are all 100-plus-200 mu m.

The low-cost glass fiber with good alkali resistance prepared by the composition of the invention has the following preparation process:

(1) firstly, weighing raw materials of the glass fiber composition according to a ratio, and then mechanically mixing the raw materials to obtain a uniform batch;

(2) melting the batch to obtain glass liquid;

(3) and drawing the glass liquid into fibers through a bushing, cooling, coating a sizing agent, and conditioning to obtain the low-cost glass fiber with good alkali resistance.

Wherein:

the melting temperature is 1450-1500 ℃, and the bushing temperature is 1150-1250 ℃.

The conditioning temperature is 28-30 ℃, and the conditioning time is 16-18 h; the humidity during conditioning is 65-70%.

The application of the sizing and the conditioning steps are carried out according to the usual procedures of a person skilled in the art, the sizing being a commercially available product.

The glass fiber is made into yarn, the hairiness amount of the yarn is small, and the hairiness amount of a single yarn is less than or equal to 3; the strength of the SIC test is kept above 500 MPa.

The low-cost glass fiber with good alkali resistance prepared by the composition can be used for producing general outer wall mesh cloth or other composite material matrixes with high alkali resistance.

The invention has the following beneficial effects:

SiO₂is an acidic oxide and is easy to react with NaOH to generate sodium silicate and SiO₂Also a glass network former, which is the main component forming the glass, SiO₂The mechanical properties of the glass fibers with too low a content are poor, SiO₂The forming temperature of the glass with too high content is higher, and in order to give consideration to the good mechanical strength of the glass and the forming temperature of the fiber which allows the requirements of the tank furnace melting process, the SiO of the invention₂The content is controlled to 60.0-70.0 wt.%, and SiO is further preferred₂The content is 63.0-67.0 wt.%.

The alkaline earth metal oxide (RO) belongs to the external oxide of the network, CaO and MgO alkaline earth metals are selected from the glass components, BaO and SrO are not introduced, and the CaO and MgO mineral raw materials have wide sources and lower cost. The divalent alkaline earth metal basically follows the ionic radius size rule, when the amount of different ions reaches a certain proportion, the optimal stacking can be obtained, and the connection between the ions and the silica framework is firmer, which is also the reason for generating the mixed alkali effect. In the system, the content of MgO is increased, the alkali resistance of the glass can be obviously improved, the high-temperature viscosity of the glass can be effectively reduced by the MgO, the glass melting is facilitated, but the crystallization of the glass can be promoted when the introduced amount of the MgO is too high, the alkali resistance of the glass is not obviously improved when the content of the MgO is lower than 5.0 wt.%, and the glass has higher crystallization tendency when the content of the MgO is higher than 8.0 wt.%, so that the content of the MgO is controlled to be 5.0-8.0 wt.%. The alkali resistance of MgO is improved more than that of CaO, and when the weight ratio of MgO/CaO is 0.5-1.0, the alkali resistance of the glass is better. CaO can reduce the forming temperature, but the content of CaO is too high, so that the Delta T value becomes small and can not meet the process requirement, and the content of CaO in the invention is controlled to be 8.0-10.0 wt.%, and the content of CaO is further preferably 8.0-9.0 wt.%.

Na₂O has good alkali resistance, but is used as a network exo-oxide, Na₂The addition of O can break the network, and reduce the strength and chemical stability of the glass; with Na₂The increase in O content is good in alkali resistance but poor in water resistance. Na in glass₂When the O content is in a certain range, it can form uniform structural component in the network, and can make the glass forming range be enlarged, and can make the formed glass more stable, and in the invented system it is used as MgO/Na₂When the weight ratio of O is 0.25-0.45, the alkali resistance is better, and in order to ensure that each performance data is stable, the Na of the invention₂The O content is controlled to be 18.0-20.0 wt.%.

In order to ensure low cost, preferably, albite and other raw materials are used, and a certain amount of K is introduced into the raw materials₂O content, preferably K₂The O content is 0.0-1.0 wt.%. Li₂The cost of the O raw material is high, the advantage of alkali resistance is not obvious, and the invention is not specially introduced.

ZrO₂When eroded by alkali solution, ZrO₂Zirconium enrichment can occur, a layer of protective film is formed on the surface, the protective film can effectively protect the continuous dissolution of other components, the alkali resistance of the glass can be effectively improved, and when the content of other components is unreasonable, a proper amount of ZrO is added₂The alkali resistance desired in the present invention cannot be achieved. ZrO (ZrO)₂The excessive use amount can obviously improve the melting temperature of the glass, increase the devitrification, increase the operation difficulty of the fiber in production, and introduce ZrO₂The raw material of the high-temperature-resistant zirconia powder is zircon powder, and the price is high. The invention adds 0.1 to 0.5 weight percent of ZrO₂The alkali resistance can be improved, the melting temperature can be ensured, and the glass cost can not be increased too much.

TiO₂The enthalpy of dissolution in alkali liquor is larger, which is beneficial to improving the alkali resistance of glass, but titanium is also a coloring element, which affects the color of glass products, the price of raw materials is higher, and the titanium can be introduced properly according to the requirements, the TiO of the invention₂Content controlAt 0-3 wt.%.

Al₂O₃Less enthalpy of dissolution in the lye, instability in the lye, Al₂O₃And an amphoteric oxide which reacts with both a base and an acid, so that Al₂O₃The content is not so large in the present invention, and a part of Al is added to the glass composition₂O₃The difference between the fiber forming temperature and the liquidus temperature can be optimized, and the devitrification tendency of the glass can be reduced. Al (Al)₂O₃When the content exceeds 5.0 wt%, the crystallization tendency is obviously increased, and in order to ensure that the glass fiber has higher alkali resistance and also give consideration to the process properties of glass forming, fiber forming and the like, the Al-based glass fiber has the advantages of high glass fiber strength, high glass forming property, high glass fiber strength and the like₂O₃The content is controlled to 0-5.0 wt.%, and Al is more preferable₂O₃The content is controlled at 0-3 wt.%.

Fe₂O₃Is a coloring element, has great influence on the heat transfer performance of glass color and glass, and the heat transmission performance of the glass can be influenced when the content is too high. In order to make the glass have good appearance, reduce the operation difficulty of the product in production and ensure the whiteness of the product, the invention provides Fe₂O₃The content is less than or equal to 1.0 wt.%.

The invention controls Al₂O₃Adjusting CaO, MgO and Na while adjusting the content₂The alkali resistance of the glass can be effectively improved only by properly adding zirconium and titanium according to the use proportion of the components O, and the alkali resistance of the glass cannot be obtained by singly adding a certain element or introducing the element in an improper proportion.

The invention is prepared by mixing Na₂O content is controlled to 18.0-20.0 wt.%, and MgO/Na₂The weight ratio of O is controlled to 0.25-0.45 while ZrO is added₂The content is controlled to be 0.1-0.5 wt.%, so that the alkali resistance of the glass fiber is excellent, and the stability of various properties of the glass fiber is ensured.

Invention Na₂The O content is controlled to be 18.0-20.0 wt.%. Generally, in most current products, Na is₂The O content is generally less than 18.0%, and it is impossible for the person skilled in the art to think of Na₂The O content continues to increase because of Na₂The content of O is too high, and although the alkali resistance is increased, the content of O is too highThe water resistance is affected. The present invention is prepared by mixing MgO/Na₂The weight ratio of O is controlled to 0.25-0.45 while ZrO is added₂The content is controlled to be 0.1-0.5 wt.%, so that the alkali resistance of the glass fiber is greatly improved, and the water resistance of the glass fiber is also ensured.

For ZrO₂In terms of the amount of ZrO in most of the products at present₂The content is generally higher to play a certain role, but the ZrO content is treated by the invention₂The usage amount of (A) is controlled to be 0.1-0.5 wt.%, and Na is compounded₂O content is controlled to 18.0-20.0 wt.%, and MgO/Na₂The weight ratio of O is controlled to be 0.25-0.45, and unexpected technical effects are obtained. The research shows that when ZrO is used₂Is used in an amount of more than 0.5 wt.%, which results in a product having poor water resistance. When the amount is less than 0.1 wt.%, ZrO cannot be developed₂The water resistance of the obtained product is also poor.

The invention greatly increases the alkali resistance of the glass fiber through the design idea of high sodium, medium magnesium and low zirconium, and has lower cost and excellent performance.

By optimizing the components, the glass fiber composition has the advantages of higher alkali resistance, lower liquidus temperature and fiber forming temperature, good process performance and relatively low energy consumption, and can be suitable for drawing refractory material in a tank furnace.

The glass fiber is made into yarn, the yarn hairiness amount is less, the hairiness amount is an important quality index of the glass yarn, the yarn is greatly influenced by a formula system, the hairiness amount is less, and the yarn is beneficial to the use of the subsequent procedures of grid cloth and the like.

The glass fiber can be used for preparing mesh cloth, and the mesh cloth production comprises three processes of warping, weaving and coating. If the amount of the used yarn hairiness is large, yarn breakage is easily caused, and the production efficiency is influenced. The yarn made of the glass fiber has less hairiness, less broken yarn, easy warping, high production efficiency, less woven grey cloth surface broken filaments, clear meshes in the coating process, no hole pasting, guaranteed glue-coated mesh quality and favorable penetration of cement mortar.

The yarn made of the glass fiber has good alkali resistance, and SIC (cement mortar) strength retention can reach more than 500 MPa.

Detailed Description

The present invention is further described below with reference to examples.