CN113929299A

CN113929299A - High modulus glass composition, high modulus glass fiber and composite material

Info

Publication number: CN113929299A
Application number: CN202111225903.6A
Authority: CN
Inventors: 唐志尧; 李永艳; 徐东芝; 王加芳; 杜凤玲; 赵俊; 刘晓斌
Original assignee: Taishan Fiberglass Inc
Current assignee: Taishan Fiberglass Inc
Priority date: 2021-10-21
Filing date: 2021-10-21
Publication date: 2022-01-14
Anticipated expiration: 2041-10-21
Also published as: CN113929299B

Abstract

The invention relates to a high modulus glass composition, high modulus glass fiber and composite material. The high modulus glass composition comprises SiO₂、Al₂O₃、MgO、CaO、ZrO₂And a rare earth oxide fining agent. SiO in high modulus glass compositions₂Is contained in an amount of 53.0 to 63.0 parts by mass of Al₂O₃Is 17.0 to 22.0 parts by mass, MgO is 8.5 to 13.5 parts by mass, CaO is 0.1 to 4.5 parts by mass, ZrO is contained₂The rare earth oxide clarifier is 0.1 to 2.0 parts by mass, and the rare earth oxide clarifier is 3.0 to 15.0 parts by mass. According to the invention, through the limitation of the mass parts, the high-modulus glass material prepared from the high-modulus glass composition has high strength and high modulus, and simultaneously the high-modulus glass is enhancedThe acid resistance of the glass material is reduced, the thermal expansion coefficient of the high modulus glass material is reduced, and the service performance of the high modulus glass fiber and the related composite material is improved.

Description

High modulus glass composition, high modulus glass fiber and composite material

Technical Field

The invention relates to the technical field of inorganic non-metallic materials, in particular to a high-modulus glass composition, high-modulus glass fiber and a composite material.

Background

The high-strength high-modulus glass fiber is used as a reinforcing base material of an advanced composite material, has excellent performances of high tensile strength, high elastic modulus, good chemical stability, good temperature resistance and the like compared with common glass fiber, and is widely applied in the field of national defense, such as aviation, aerospace, weaponry and the like. Meanwhile, high-strength and high-modulus glass fibers are also widely used in civil fields such as pressure vessels, ships, wind blades and the like.

The earliest manufacturers of high strength, high modulus Glass fibers were the Owens-Illinois Glass Company in the United states, the most representative of which was S-2 Glass fiber. Specifically, SiO in S-2 glass fiber₂Is 65 parts by mass of Al₂O₃The content of (b) is 25 parts by mass and the content of MgO is 10 parts by mass. The S-2 glass fiber produced by the components has the tensile modulus of 90-92 gigapascals, namely 90000-92000 megapascals, the melting temperature of 1650 ℃, the molding temperature of 1470 ℃ and the liquid phase temperature of 1465 ℃. Therefore, the S-2 glass fiber is higher in melting temperature, the melting can be carried out only by using the electric kiln with the full platinum as the lining, the service life of the bushing plate of the electric kiln is shortened due to the high temperature, and the production cost is increased.

In the fifties and sixties of the 20 th century, the Saint gobain group of france (english name: Saint-gobain) developed an R glass fiber. Specifically, SiO in R glass fiber₂58 to 60 parts by mass of Al₂O₃The content of (A) is 23.5 to 25.5 parts by mass, and the total content of CaO and MgOIs 14 to 17 parts by mass. The R glass fiber produced by the components has the tensile modulus of 89 gigapascal to 90 gigapascal, namely 89000 megapascals to 90000 megapascals, the forming temperature is higher than 1350 ℃, the liquidus temperature is very close to the forming temperature, the devitrification phenomenon of glass is easily caused in the drawing process, the production difficulty is high, and the tank-kiln production is difficult.

In China, the glass fiber research institute of Nanjing China developed HS high-strength and high-modulus glass fibers, the HS2 glass fibers were developed in the 70 th century, and the HS4 glass fibers were developed in the 90 th century on the basis of the HS2 glass fibers. The HS glass fiber, the HS2 glass fiber and the HS4 glass fiber belong to silicon-aluminum-magnesium three-phase glass. For example, the HS4 glass fiber comprises 50 to 60 parts by mass of SiO₂23.5 to 26.5 parts by mass of Al₂O₃10 to 19.5 parts by mass of MgO. The HS4 glass fiber produced by the components with the content has the elastic modulus of 96 gigapascals, namely 96000 megapascals, the forming temperature is about 1320 ℃, the liquid phase temperature is about 1420 ℃, and the forming temperature is lower than the crystallization temperature, so that the common tank furnace wire drawing process is difficult to realize, needs to be realized by adopting a special production process, has higher production cost, and is mainly applied to the field of military industry.

Therefore, the S-2 glass fiber, the R glass fiber and the HS4 glass fiber have high production difficulty, high production cost and extremely harsh drawing process, and are not suitable for large-scale tank furnace production.

Application No. 201810305746.1 discloses a high modulus glass fiber composition and glass fiber comprising 56.0 to 60.0 parts by mass of SiO₂20.1 to 24.0 parts by mass of Al₂O₃0.2 to 1.5 parts by mass of TiO₂0 to 2.0 parts by mass of ZnO, 0 to 2.0 parts by mass of ZrO₂5.0 to 9.0 parts by mass of CaO, 9.0 to 15.0 parts by mass of MgO, and 0 to 2.5 parts by mass of Li₂O, the high modulus glass fiber obtained by the patent has low production difficulty, but the components contain relatively high alkali metal and alkaline earth metal, so that the expansion coefficient of the glass fiber is increased, and the glass fiber is not favorableThe comprehensive performance is improved.

Application No. 201911171452.5 discloses a high performance fiber glass composition having an improved modulus of elasticity comprising 50.0 parts by mass to 65.0 parts by mass of SiO₂18.0 to 23.0 parts by mass of Al₂O₃1.0 to 5.0 parts by mass of CaO, 9.0 to 14.0 parts by mass of MgO, and 1.0 to 4.0 parts by mass of Li₂O, 0 to 2.5 parts by mass of TiO₂0 to 10.0 parts by mass of Y₂O₃0 to 10.0 parts by mass of La₂O₃The glass fiber has high modulus of 88000 MPa to 115000 MPa, the patent is published in a too wide range, and the technical goal of elastic modulus of more than 94000 MPa is difficult to be easily realized by personnel in the industry through the technical scheme. The patented composition contains relatively high Li₂And O, the expansion coefficient of the glass fiber is increased, and the improvement of the comprehensive performance of the glass fiber is not facilitated.

With the continuous adjustment of the national macro policy, various industries also put higher quality requirements on the glass fiber. For example, in the field of wind power, the production of domestic wind blades has been gradually changed from increasing the production capacity to pursuing the quantity to moderately shrinking and strictly controlling the quality, and longer, larger and long-service-life wind blades need to be continuously developed. As the load and the weight of the wind blade are continuously increased, the wind blade has the advantages of light weight, high strength, good chemical stability and low cost, and becomes the development direction of the future wind blade, and is also the development and research direction of the glass fiber industry.

In view of the above disadvantages in the related art, it is necessary to develop a high-strength and high-modulus glass fiber, which has low density and excellent indexes, can be produced industrially, reduces the production cost, provides a favorable guarantee for the increasing market demand, and provides a powerful support for the development of domestic high-performance composite materials.

Disclosure of Invention

The present invention is directed to solving at least one of the above problems.

To this end, a first object of the present invention is to provide a high modulus glass composition.

A second object of the present invention is to provide a high modulus glass fiber.

A third object of the present invention is to provide a composite material.

To achieve the first object of the present invention, the invention provides a high modulus glass composition comprising 53.0 to 63.0 parts by mass of SiO₂(ii) a 17.0 to 22.0 parts by mass of Al₂O₃(ii) a 8.5 to 13.5 parts by mass of MgO; 0.1 to 4.5 parts by mass of CaO; 0.1 to 2.0 parts by mass of ZrO₂(ii) a 3.0 to 15.0 parts by mass of a rare earth oxide clarifier.

In addition, the technical scheme provided by the invention can also have the following additional technical characteristics:

the high modulus glass composition in the above technical solution comprises 56.0 to 62.5 parts by mass of SiO₂(ii) a 17.5 to 21.5 parts by mass of Al₂O₃(ii) a 9.5 to 13.5 parts by mass of MgO; 0.1 to 3.0 parts by mass of CaO; 0.5 to 1.5 parts by mass of ZrO₂(ii) a 3.0 to 10.0 parts by mass of a rare earth oxide clarifier.

In any of the above embodiments, the rare earth oxide fining agent comprises Y₂O₃The mass ratio of the high modulus glass composition is more than or equal to 3.0 percent; sm₂O₃The mass ratio of the glass composition in the high modulus glass composition is less than or equal to 4.0 percent; CeO (CeO)₂The mass ratio of the glass composition in the high modulus glass composition is less than or equal to 2.0 percent.

In any of the above technical solutions, CeO₂Is added in an amount of Sm₂O₃The ratio of the addition amount of (b) is in the range of 0.25 to 0.55.

In any of the above embodiments, the high modulus glass composition further comprises Fe₂O₃，Fe₂O₃The mass ratio of the glass composition in the high modulus glass composition is less than or equal to 1.0 percent; and/or alkali metal oxide, the mass ratio of the alkali metal oxide in the high modulus glass composition is less than or equal to 1.0%, and the alkali metal oxide comprises at least one of the following or the combination thereof: li₂O、Na₂O、K₂O。

In any of the above technical solutions, Al₂O₃And MgO are added, and the mass ratio of the sum in the high modulus glass composition is more than or equal to 29 percent; and/or the ratio of the addition amount of CaO to the addition amount of MgO ranges less than or equal to 0.37; and/or Al₂O₃The proportion range of the addition amount of the rare earth oxide clarifier to the sum of the addition amounts of CaO, MgO and rare earth oxide clarifier is 0.85 to 1.15; and/or rare earth oxide fining agent is added in an amount compared with Al₂O₃The ratio of the amount of MgO to the sum of the amounts of MgO added is in the range of 0.1 to 0.4. The high modulus glass composition further comprises ZrO₂，ZrO₂In a proportion range of 0.08 or more in comparison with the addition amount of the rare earth oxide clarifier.

In any of the above technical solutions, the density of the high modulus glass material prepared from the high modulus glass composition is less than or equal to 2.7 g/cc; and/or the molding temperature of the high-modulus glass material is less than or equal to 1340 ℃; and/or the liquidus temperature range of the high modulus glass material is 1245 ℃ to 1290 ℃; and/or the difference between the forming temperature and the liquidus temperature of the high modulus glass material is greater than or equal to 50 ℃; and/or the high modulus glass material has a coefficient of thermal expansion less than or equal to 4.2 x 10-6/degree celsius.

In order to achieve the second object of the present invention, the present invention provides a high modulus glass fiber obtained from the high modulus glass composition according to any one of the above aspects. In any of the above technical solutions, the elastic modulus of the high modulus glass fiber ranges from 94000 mpa to 101000 mpa; and/or the acid-resistant mass retention of the high modulus glass fiber is greater than or equal to 93%; and/or the high modulus glass fiber has a mechanical strength of 3200 MPa or greater.

In order to achieve the third object of the present invention, the technical scheme of the present invention provides a composite material, wherein the composite material is obtained by using the high modulus glass composition according to any one of the technical schemes, and the composite material has the advantages of high strength, good dimensional stability and strong aging resistance.

Compared with the related technology, the invention has the advantages that: the high modulus glass material produced by the high modulus glass composition of the raw material components avoids crystallization of the high modulus glass material, enhances the chemical stability of the high modulus glass material, reduces the thermal expansion coefficient of the high modulus glass material, reduces the density of the high modulus glass material, improves the service performance of the high modulus glass fiber and reduces the production cost of the high modulus glass fiber while ensuring that the high modulus glass material has high strength and high modulus.

Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.

Drawings

The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

FIG. 1 is one of a flow chart of steps in some embodiments of the invention.

Detailed Description

In order that the above objects, features and advantages of the present invention may be more clearly understood, a more particular description of the invention will be rendered by reference to fig. 1, which is illustrated in the appended drawings. It should be noted that the technical solutions and features in the technical solutions of the present application may be combined with each other without conflict.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific techniques disclosed below.

The technical solutions of the present invention will be described below with reference to specific embodiments, and the described embodiments are only a part of embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person skilled in the art on the basis of the present invention shall fall within the scope of protection of the present invention without making any creative effort.

The technical scheme of the invention provides a high modulus glass composition which comprises SiO₂、Al₂O₃、MgO、ZrO₂CaO and rare earth oxide fining agents. Wherein SiO is₂The content is 53.0 parts by mass to 63.0 parts by mass. Al (Al)₂O₃The content is 17.0 to 22.0 parts by mass. The MgO content is 8.5 to 13.5 parts by mass. ZrO (ZrO)₂The content is 0.1 to 2.0 parts by mass. The CaO content is 0.1 to 4.5 parts by mass. The content of the rare earth oxide clarifier is 3.0 to 15.0 parts by mass.

By limiting the components by mass, the high modulus glass composition improves the mechanical strength and the elastic modulus of the high modulus glass material, avoids crystallization of the high modulus glass material, enhances the chemical stability of the high modulus glass material while ensuring the high strength and the high modulus of the high modulus glass material, reduces the thermal expansion coefficient of the high modulus glass material, and improves the service performance of the high modulus glass fiber.

The high modulus glass composition of the present invention comprises SiO₂、Al₂O₃、CaO、MgO、ZrO₂And a rare earth oxide fining agent. In particular, SiO₂Is a whole body of a framework formed by the high modulus glass composition, in the technical scheme, SiO₂Mainly in the form of a silicon-oxygen tetrahedron, i.e. consisting of a central silicon atom and four oxygen atoms surrounding it. It will be appreciated that the form of the silicon-oxygen tetrahedron need not be geometrically regular tetrahedron, and will often have different forms of distortion. The strength of the silica single bond is high, so that the mechanical strength and the elastic modulus of the high-modulus glass material are improved, the chemical stability of the high-modulus glass material is improved, and the thermal expansion coefficient and the density of the high-modulus glass material are reduced.

The technical proposal further limits the SiO₂The content is 53.0 to 63.0 parts by mass when SiO₂When the content is less than 53.0 parts by mass, the strength and the elastic modulus of the high modulus glass material are poor, and the service performance of the high modulus glass fiber is reduced. When SiO is present₂When the content is more than 63.0 parts by mass, melting and refining of the high modulus glass material are not facilitated. The technical proposal is realized by limiting SiO₂The content of (a) further ensures the strength and the elastic modulus of the high-modulus glass material, and realizes the high strength of the high-modulus glass fiberAnd (4) high modulus.

In some embodiments of the present disclosure, SiO₂The content of (b) may be 53.0%, 56.4%, 56.7%, 57.2%, 59.0%, 60.4%, 62.0%, or the like.

In the technical scheme, the high modulus glass composition also comprises Al₂O₃. The aluminum oxide is a common intermediate oxide, and when sufficient free oxygen exists, the positive trivalent aluminum ions can generate coordination change, and the coordination change is changed from six coordination to four coordination, so that the positive trivalent aluminum ions enter the high modulus glass material framework, the high modulus glass material is more compact in structure, and the strength and the elastic modulus of the high modulus glass material are improved.

The technical proposal further limits Al₂O₃The content is 17.0 to 22.0 parts by mass when Al is present₂O₃When the content is less than 17.0 parts by mass, the mechanical strength and the elastic modulus of the high modulus glass material are low, and the service performance of the high modulus glass fiber is reduced. When Al is present₂O₃When the content is more than 22.0 parts by mass, the crystallization temperature of the high-modulus glass material is increased, the crystallization rate is accelerated, the crystallization tendency of the high-modulus glass material is increased, and the production difficulty is increased. The technical proposal is realized by limiting Al₂O₃The content of (a) avoids crystallization of the high modulus glass material and improves the service performance of the high modulus glass fiber on the premise of ensuring high strength and high elastic modulus of the high modulus glass material.

In some embodiments of the present disclosure, Al₂O₃The content of (b) may be 17.0%, 18.3%, 19.5%, 20.7%, 21.5%, or the like.

In the technical scheme, the high-modulus glass composition also comprises MgO and CaO. Specifically, MgO and CaO can adjust the crystallization and forming temperatures of the high-modulus glass material. It is understood that the effect of the divalent alkaline earth metal on the properties of the high modulus glass material substantially follows the ionic radius size law, and as the atomic number and atomic radius increase, the elastic modulus of the high modulus glass material decreases. The atomic radius of magnesium ions is smaller than that of calcium ions, so that the influence of MgO on the elastic modulus of a high modulus glass material is greater than that of CaO.

However, when a plurality of divalent alkaline earth metal oxides are added to the high modulus glass composition, the tendency of the high modulus glass material to devitrify is reduced. And MgO and CaO can provide free oxygen required by coordination change for trivalent aluminum ions, so that various performances of the high-modulus glass material, such as mechanical strength, elastic modulus, melting temperature and the like, are fully considered, the technical scheme limits the content of MgO to 8.5 parts by mass to 13.5 parts by mass and the content of CaO to 0.1 part by mass to 4.5 parts by mass, and the crystallization condition of the high-modulus glass material is reduced on the basis of ensuring the high strength and high elastic modulus of the high-modulus glass material.

In some embodiments of the present disclosure, the content of MgO may be 8.5%, 9.5%, 10.5%, 11.0%, 12.3%, 13.0%, or the like.

In other embodiments of the present disclosure, the CaO content may be 0.8%, 1.0%, 1.3%, 2.0%, 2.6%, or 3.0%, etc.

In other embodiments of the present disclosure, ZrO₂The content of (b) may be 0.5 to 2.0 parts by mass.

In the technical scheme, the high modulus glass composition also comprises a rare earth oxide clarifier. It is understood that the rare earth oxide fining agent can include Y₂O₃、Sm₂O₃、CeO₂、La₂O₃、Pr₂O₃Or Eu₂O₃And the like. On one hand, the rare earth oxide clarifier in the technical scheme is used as a network exosome oxide, and can provide free oxygen in a high-modulus glass material structure, so that trivalent aluminum ions are subjected to coordination change and enter a high-modulus glass framework, and the function of network supplement is achieved. On the other hand, the rare earth oxide clarifier in the technical scheme can clarify a high-modulus glass material and improve the transparency of the high-modulus glass material. However, the existence of excessive free oxygen can reduce the connection degree of the network structure of the high modulus glass material, and the cost of the rare earth oxide fining agent is higher, so the technical scheme further limits the content of the rare earth oxide fining agent to 3.0 parts by mass to 15.0 parts by mass, and further ensures the high strength and high modulus of the high modulus glass materialAnd simultaneously, the cost of the high-modulus glass material is reduced.

Rare earth oxide fining agents include Y₂O₃、Sm₂O₃And CeO₂. Wherein Y is₂O₃The mass ratio of the glass composition in the high modulus glass composition is greater than or equal to 3.0 percent. Sm₂O₃The mass ratio of the glass composition in the high modulus glass composition is less than or equal to 4.0 percent. CeO (CeO)₂The mass ratio of the high modulus glass component is less than or equal to 2.0 percent.

In the technical scheme, the rare earth oxide clarifier comprises Y₂O₃The positive trivalent yttrium ions are high in coordination number and high in magnetic field intensity, and the compactness of a high modulus glass network structure can be improved by the positive trivalent yttrium ions distributed in the gaps of the high modulus glass material network, so that the effect of improving the elastic modulus of the high modulus glass material is realized, and meanwhile, the crystallization of the high modulus glass material can be inhibited by the positive trivalent yttrium ions, and the performance of the high modulus glass fiber is further improved.

The technical proposal further limits Y₂O₃The mass ratio of the component in the high modulus glass is more than or equal to 3.0 percent, and Y is avoided₂O₃The content is too low to improve the strength and elastic modulus of the high-modulus glass material. Meanwhile, the mass ratio of more than or equal to 3.0 percent has obvious inhibition effect on crystallization of the high-modulus glass material, and further improves the performance of the high-modulus glass fiber.

Understandably, Y₂O₃The molar mass of the high modulus glass material is larger, the expansion coefficient of the high modulus glass material is increased along with the increase of the content, the dielectric property is reduced, and the density of the high modulus glass material is also greatly increased. Thus, in some embodiments of this aspect, Y₂O₃The content of Y in the high modulus glass composition is 7.0% or less₂O₃Too high content affects various properties of the high-modulus glass material, and particularly when the mass ratio exceeds 9.0%, the tendency of devitrification of the high-modulus glass material is rather increased, and the strength of the high-modulus glass material is remarkably lowered. Therefore, in this embodiment, Y may be defined₂O₃InThe mass ratio of the high modulus glass composition is more than or equal to 3.0% and less than or equal to 7.0%, so that the high modulus glass material has higher elastic modulus, the tensile strength of the high modulus glass fiber is improved, various performances such as the expansion coefficient and the dielectric property of the high modulus glass fiber are improved, and the production cost of the high modulus glass fiber is reduced.

In some embodiments of this aspect, Y₂O₃The content of (b) in the high modulus glass composition may be 3.0%, 4.0%, 5.3%, 6.5%, 7.0% or the like.

In the technical scheme, the rare earth oxide clarifier also comprises Sm₂O₃And CeO₂. The technical proposal is that Sm is added into the high modulus glass composition₂O₃And CeO₂The method has the advantages of clarifying the high-modulus glass material, improving the transparency of the high-modulus glass material, and further improving the melting performance of the high-modulus glass material and the application performance of the composite material.

In other embodiments of this embodiment, CeO₂The high modulus glass composition may be 0.2%, 0.5%, 1.0%, 1.9%, or the like by mass.

In the technical scheme, the rare earth oxide clarifier comprises Y₂O₃、Sm₂O₃And CeO₂And further define Y₂O₃Sm in an amount of 3.0% or more based on the mass of the high modulus glass composition₂O₃The mass ratio of the CeO in the high modulus glass composition is less than or equal to 4.0 percent₂The mass ratio of the high modulus glass composition is less than or equal to 2.0%, so that the three components have a good synergistic effect, the compactness of a network structure of the high modulus glass material is improved, the purposes of enhancing the mechanical strength and the elastic modulus of the high modulus glass material are realized, and the density of the high modulus glass material is reduced.

CeO₂Is added in an amount of Sm₂O₃The ratio of the addition amount of (b) is in the range of 0.25 to 0.55. In the technical scheme, CeO is limited₂In Sm₂O₃In the ratio of (2)The enclosure is 0.25 to 0.55, further ensuring CeO₂And Sm₂O₃The clarification effect of the high-modulus glass material is improved, the transparency of the high-modulus glass material is improved, and the melting performance and the application performance of the composite material of the high-modulus glass material are improved.

In some embodiments of this embodiment, CeO₂Is added in an amount of Sm₂O₃The ratio of the amount of (B) may be 0.25, 0.29, 0.35, 0.46, 0.54, or the like.

The high modulus glass composition further comprises Fe₂O₃Alkali metal oxide and ZrO₂。Fe₂O₃The mass ratio of the glass composition in the high modulus glass composition is less than or equal to 1.0 percent. The mass ratio of the alkali metal oxide in the high modulus glass composition is less than or equal to 1.0%. The alkali metal oxide includes Li₂O、Na₂O、K₂At least one of O or a combination thereof.

In the technical scheme, the high modulus glass composition also comprises Fe₂O₃，Fe₂O₃Coloring high modulus glass materials, Fe₂O₃The excessive content can cause the transparency of the high-modulus glass material to be reduced and the strength to be reduced, so the technical scheme further limits Fe₂O₃The mass ratio of the high modulus glass composition is less than or equal to 1.0 percent, and the transparency of the high modulus glass material is ensured. In some embodiments of this aspect, Fe₂O₃The mass ratio of the glass composition in the high modulus glass may be 0.3%.

The high modulus glass composition of the present invention further comprises an alkali metal oxide comprising Li₂O、Na₂O、K₂At least one of O or a combination thereof. The alkali metal oxide can improve the electric conductivity of the high-modulus glass material, and the proper alkali metal oxide is beneficial to melting the high-modulus glass liquid. However, the high modulus glass material has a low elastic modulus due to the excessive content of the alkali metal oxide, the expansion coefficient is remarkably increased, the difference between the forming temperature and the crystallization temperature is reduced, and the wire drawing operation is not facilitated. Therefore, the technical scheme limits the small mass ratio of the alkali metal oxide in the high modulus glass compositionLess than or equal to 1.0 percent, improves the electric conductivity of the high modulus glass material on the premise of ensuring the elastic modulus of the high modulus glass material, is beneficial to the tank furnace process assisted by electric boosting, and reduces the production cost of the high modulus glass fiber.

In some embodiments of the present invention, the alkali metal oxide accounts for 0.5%, 0.6%, 0.7%, or the like in the high modulus glass composition.

The high modulus glass composition of the technical scheme also comprises ZrO₂It is understood that ZrO is added to the high modulus glass composition₂On one hand, the compactness of the high-modulus glass material is increased, and the improvement of the elastic modulus of the high-modulus glass material is facilitated. On the other hand, ZrO₂Can be cooperated with a rare earth oxide clarifying agent, thereby remarkably improving the acid resistance of the high-modulus glass material. However, ZrO in high modulus glass materials₂Too high a content increases the viscosity and tendency to devitrify of the high modulus glass. Therefore, the technical scheme further limits ZrO₂The high modulus glass composition accounts for 1.0 to 2.0 parts by mass, improves the elastic modulus and the acid resistance of the high modulus glass material, avoids crystallization of the high modulus glass material, and reduces the production cost of the high modulus glass fiber.

In some embodiments of this aspect, ZrO₂The mass ratio of the high modulus glass fiber in the high modulus glass composition is more than or equal to 0.5 percent and less than or equal to 2.0 percent, the crystallization of the high modulus glass material is further avoided, and the high strength and high modulus of the high modulus glass fiber are ensured.

In other embodiments of the present disclosure, ZrO₂The mass ratio in the high modulus glass composition may be 0.7%, 0.8%, 1.0%, 1.7%, or the like.

In this embodiment, the high modulus glass composition comprises Fe₂O₃Alkali metal oxide and ZrO₂And further define Fe₂O₃The mass ratio of the alkali metal oxide in the high modulus glass composition is less than or equal to 1.0%, and ZrO₂The mass ratio of the glass composition in the high modulus glass composition is less than or equal to2.0 percent, avoids crystallization of high modulus glass materials, improves the strength and the elastic modulus of the high modulus glass fibers, improves the acid resistance of the high modulus glass fibers, and reduces the production cost of the high modulus glass fibers.

The technical scheme of the invention provides a high modulus glass composition, which further comprises the following technical characteristics in addition to the technical characteristics of any one of the technical schemes.

Al₂O₃And MgO are added in an amount such that the sum of the amounts of MgO and MgO accounts for 29% or more by mass of the high modulus glass composition. The ratio of the amount of CaO added to the amount of MgO added is less than or equal to 0.37. Al (Al)₂O₃The proportion of the addition amount of (B) to the sum of the addition amounts of CaO, MgO, and rare earth oxide clarifier is in the range of 0.85 to 1.15. The addition amount of the rare earth oxide clarifier is compared with that of Al₂O₃The ratio of the amount of MgO to the sum of the amounts of MgO added is in the range of 0.1 to 0.4. The high modulus glass composition further comprises ZrO₂，ZrO₂In a proportion range of 0.08 or more in comparison with the addition amount of the rare earth oxide clarifier.

In the technical scheme, Al₂O₃And the sum of the addition amount of MgO accounts for more than or equal to 29 percent of the mass ratio in the high modulus glass composition, so that the chemical stability and the strength of the high modulus glass material can be improved, and the elastic modulus of the high modulus glass material can be improved.

In the technical scheme, the proportion range of the addition amount of CaO compared with the addition amount of MgO is less than or equal to 0.37, the influence of calcium ions on the elastic modulus of the high-modulus glass material is reduced, the forming temperature of the high-modulus glass material is ensured, the high-modulus glass fiber is conveniently drawn, and the fiber forming performance of the high-modulus glass fiber is improved.

In the technical scheme, Al₂O₃The proportion range of the addition amount of the rare earth oxide clarifier to the sum of the addition amounts of CaO, MgO and the rare earth oxide clarifier is 0.85 to 1.15, and Al is reasonably controlled₂O₃The relation between the addition amount and the addition amounts of CaO, MgO and rare earth oxide clarifying agent plays a role in controlling the concentration of free oxygen, and further ensures the high-modulus glass materialThe high strength and high modulus of the material can improve the stability of the internal structure of the high modulus glass material and inhibit the crystallization of the high modulus glass material.

In the technical scheme, the addition amount of the rare earth oxide clarifier is compared with that of Al₂O₃The proportion of the MgO and the additive amount of the MgO is in the range of 0.1 to 0.4, so that the high strength of the high modulus glass material is further ensured, the chemical stability of the high modulus glass material is improved, the elastic modulus of the high modulus glass material is improved, and the crystallization of the high modulus glass material is inhibited.

In the technical scheme, the high modulus glass composition also comprises ZrO₂，ZrO₂The proportion range of the addition amount of the rare earth oxide clarifier is more than or equal to 0.08, so that the high modulus and the low density are ensured, and the acid resistance of the high modulus glass material is further improved.

The high modulus glass material has a density of less than or equal to 2.7 grams per cubic centimeter. The forming temperature of the high-modulus glass material is less than or equal to 1340 ℃. The liquidus temperature range of the high modulus glass material is 1245 degrees celsius to 1290 degrees celsius. The difference between the forming temperature and the liquidus temperature of the high-modulus glass material is greater than or equal to 50 degrees celsius. The high modulus glass material has a modulus of elasticity in the range of 94000 mpa to 101000 mpa. The high modulus glass material has a coefficient of thermal expansion of less than or equal to 4.2 x 10^-6In degrees Celsius. The retention of acid-resistant quality of the high modulus glass material is greater than or equal to 93%. The high modulus glass fiber has a mechanical strength of 3200 MPa or more.

In the technical scheme, the density of the high-modulus glass material is less than or equal to 2.7 g/cubic centimeter, so that the high-modulus glass material is lighter in weight, and the applicability of the high-modulus glass material is improved. The forming temperature of the high-modulus glass material is less than or equal to 1340 ℃, so that the high-modulus glass material can be conveniently processed and formed, and the production cost of the high-modulus glass material is reduced. The liquidus temperature range of the high-modulus glass material is 1245-1290 ℃, so that the high-modulus glass material can be conveniently melted, and the production cost of the high-modulus glass fiber is reduced. The difference between the forming temperature and the liquidus temperature of the high-modulus glass material is greater than or equal to 50 ℃, so that the process range in the forming process of the high-modulus glass material is wider, andthe method helps to prevent the devitrification of the high-modulus glass in the melting and fiberizing processes, and is convenient for the wire drawing processing of the high-modulus glass material. The elastic modulus of the high-modulus glass material ranges from 94000 MPa to 101000 MPa, the elastic modulus of the high-modulus glass material is increased, and the service performance of the high-modulus glass fiber and related composite materials is improved. The retention rate of the acid-resistant quality of the high-modulus glass material is greater than or equal to 93%, the acid resistance of the high-modulus glass material is improved, and the service life of the high-modulus glass fiber and the related composite material is prolonged. The mechanical strength of the high-modulus glass fiber is more than or equal to 3200 MPa, so that the mechanical strength of the high-modulus glass fiber is improved, and the service performance of the high-modulus glass fiber is further improved. The high modulus glass material has a coefficient of thermal expansion of less than or equal to 4.2 x 10^-6The temperature per centigrade is reduced, the thermal expansion coefficient of the high-modulus glass material is reduced, the high-modulus glass material is prevented from being heated to generate expansion deformation, the dimensional stability of the high-modulus glass fiber and the related composite material is further improved, and the service performance is improved.

The high modulus glass composition may also include TeO₂And GeO₂。TeO₂And GeO₂The amount of addition can be selected and adjusted by a person skilled in the art.

In order to further improve the performance of the high modulus glass material of the technical scheme of the invention, TeO is further added into the raw materials of the high modulus glass composition₂And GeO₂。TeO₂And GeO₂Large ionic radius and high ionic polarizability, so TeO₂And GeO₂The addition of (2) enables the phonon energy of the glass material to be low, and can improve the refractive index of the high-mode glass material. Furthermore, TeO₂And GeO₂The forming temperature and the liquidus temperature of the high-modulus glass material can be reduced, and the difference range between the forming temperature and the liquidus temperature can be increased. Also, TeO₂The forming temperature and the liquidus temperature of the high-modulus glass material can be reduced to a large extent, but the addition of the high-modulus glass material can increase the brittleness of the high-modulus glass material to a certain extent and reduce the mechanical strength of the high-modulus glass material. Therefore, the technical scheme is to TeO₂The addition amount of (A) is controlled, and GeO is added in an auxiliary manner₂。GeO₂Can reduce the viscosity of high-modulus glass. Thus, TeO₂The drawing difficulty of the high-modulus glass fiber can be reduced, and the quality and the performance of the high-modulus glass fiber are improved.

As can be appreciated, the properties of high modulus glass materials include: the molding temperature, the liquidus temperature and the difference therebetween. The forming temperature of the high-modulus glass material means a temperature at which the viscosity of the high-modulus glass material is 1000 pas, and the liquidus temperature is the highest temperature at which a balance exists between the liquidus high-modulus glass and its main crystal phase. When the production is carried out in the step furnace, the highest temperature at which crystals are present is considered to be the liquidus temperature, and at all temperatures above the liquidus temperature, the high-modulus glass material has no crystals present in its essential phase, and below the liquidus temperature, crystals may be formed. The larger the difference between the forming temperature and the liquidus temperature, the wider the process range during the forming of the high-modulus glass material, which is a coefficient of linear expansion in the temperature range from 20 to 300 degrees celsius, and helps prevent devitrification of the high-modulus glass during melting and fiberization.

As shown in fig. 1, in order to implement the present invention, there is provided a preparation step of a high modulus glass material, comprising:

step S101, weighing raw materials according to the raw material components of the high modulus glass composition of any one of the technical schemes and uniformly mixing;

step S102, melting the raw materials to obtain high-modulus molten glass;

and step S103, forming and cooling the high-modulus molten glass to obtain the high-modulus glass material.

According to the preparation steps of the high modulus glass composition, the raw materials are weighed and uniformly mixed according to the high modulus glass composition of any one of the technical schemes, the raw materials are melted to obtain the high modulus glass liquid, and the high modulus glass liquid is cooled to obtain the high modulus glass material.

Example 1:

57.20 parts by mass of SiO were weighed₂21.5 parts by mass of Al₂O₃2.60 parts by mass of CaO, 9.50 parts by mass of MgO, 4.0 parts by mass of Y₂O₃，2.70 parts by mass of Sm₂O₃1.0 part by mass of CeO₂0.3 parts by mass of Fe₂O₃0.60 parts by mass of Na₂O, 0.60 part by mass of ZrO₂Mixing the raw materials, melting the mixture in a melting furnace by using a platinum crucible to obtain high-modulus glass liquid, cooling and forming the high-modulus glass liquid to obtain a high-modulus glass material, and detecting various performance parameters of the high-modulus glass material.

Specifically, the high-modulus glass material obtained by mixing and melting the raw materials in parts by mass has a molding temperature of 1330 ℃, a liquidus temperature of 1269 ℃, a difference between the molding temperature and the liquidus temperature of 61 ℃, an elastic modulus of 98100 MPa, a density of 2.67 g/cc and an acid-resistant mass retention rate of 95.0%.

In the present embodiment, the modulus of elasticity of the high modulus glass material is measured according to ASTM E1876 standard, and the density of the high modulus glass material is measured according to GB/T5432-2008 standard. The method for measuring the retention rate of the acid-resistant quality of the high-modulus glass material comprises the steps of weighing a certain amount of high-modulus glass material, soaking the high-modulus glass material in a sulfuric acid solution with the temperature of 96 ℃ and the concentration of 10% for 96 hours, and calculating the ratio of the mass of the residual high-modulus glass material to the mass of the original high-modulus glass material.

Example 2:

60.4 parts by mass of SiO are weighed₂19.50 parts by mass of Al₂O₃1.10 parts by mass of CaO, 11.00 parts by mass of MgO, and 5.30 parts by mass of Y₂O₃0.80 parts by mass of Sm₂O₃0.20 parts by mass of CeO₂0.30 parts by mass of Fe₂O₃0.70 parts by mass of Na₂O, 0.70 part by mass of ZrO₂Mixing the raw materials, melting the mixture in a melting furnace by using a platinum crucible to obtain high-modulus glass liquid, cooling and forming the high-modulus glass liquid to obtain a high-modulus glass material, and detecting various performance parameters of the high-modulus glass material.

Specifically, the high-modulus glass material obtained by mixing and melting the raw materials in parts by mass has a molding temperature of 1320 ℃, a liquidus temperature of 1250 ℃, a difference between the molding temperature and the liquidus temperature of 70 ℃, an elastic modulus of 99200 MPa, a density of 2.68 g/cc and an acid-resistant mass retention rate of 95.7%.

Example 3:

59.00 parts by mass of SiO are weighed₂19.10 parts by mass of Al₂O₃2.00 parts by mass of CaO, 10.50 parts by mass of MgO, and 5.80 parts by mass of Y₂O₃1.30 parts by mass of Sm₂O₃0.60 parts by mass of CeO₂0.30 parts by mass of Fe₂O₃0.70 parts by mass of Na₂O, 0.70 part by mass of ZrO₂Mixing the raw materials, melting the mixture in a melting furnace by using a platinum crucible to obtain high-modulus glass liquid, cooling and forming the high-modulus glass liquid to obtain a high-modulus glass material, and detecting various performance parameters of the high-modulus glass material.

Specifically, the high-modulus glass material obtained by mixing and melting the raw materials in parts by mass has a molding temperature of 1326 ℃, a liquidus temperature of 1266 ℃, a difference between the molding temperature and the liquidus temperature of 60 ℃, an elastic modulus of 97300 MPa, a density of 2.68 g/cc and an acid-resistant mass retention rate of 95.8%.

Example 4:

60.40 parts by mass of SiO are weighed₂18.30 parts by mass of Al₂O₃0.80 parts by mass of CaO, 10.80 parts by mass of MgO, and 5.40 parts by mass of Y₂O₃2.00 parts by mass of Sm₂O₃0.50 parts by mass of CeO₂0.30 parts by mass of Fe₂O₃0.70 parts by mass of Na₂O, 0.80 part by mass of ZrO₂Mixing the raw materials, melting the mixture in a melting furnace by using a platinum crucible to obtain high-modulus glass liquid, cooling and forming the high-modulus glass liquid to obtain a high-modulus glass material, and detecting various performance parameters of the high-modulus glass material.

Specifically, the high-modulus glass material obtained by mixing and melting the raw materials in parts by mass has a molding temperature of 1334 ℃, a liquidus temperature of 1272 ℃, a difference between the molding temperature and the liquidus temperature of 62 ℃, an elastic modulus of 95700 MPa, a density of 2.67 g/cc and an acid-resistant mass retention rate of 96.2%.

Example 5:

56.40 parts by mass of SiO are weighed₂20.70 parts by mass of Al₂O₃3.0 parts by mass of CaO, 8.50 parts by mass of MgO, and 7.00 parts by mass of Y₂O₃2.00 parts by mass of Sm₂O₃0.70 parts by mass of CeO₂0.30 parts by mass of Fe₂O₃0.50 parts by mass of Na₂O, 0.90 parts by mass of ZrO₂Mixing the raw materials, melting the mixture in a melting furnace by using a platinum crucible to obtain high-modulus glass liquid, cooling and forming the high-modulus glass liquid to obtain a high-modulus glass material, and detecting various performance parameters of the high-modulus glass material.

Specifically, the high-modulus glass material obtained by mixing and melting the raw materials in parts by mass has a molding temperature of 1323 ℃, a liquidus temperature of 1273 ℃, a difference between the molding temperature and the liquidus temperature of 50 ℃, an elastic modulus of 95100 MPa, a density of 2.67 g/cc and an acid-resistant mass retention rate of 96.5%.

Example 6:

56.70 parts by mass of SiO are weighed₂20.90 parts by mass of Al₂O₃1.30 parts by mass of CaO, 9.80 parts by mass of MgO, and 6.50 parts by mass of Y₂O₃2.30 parts by mass of Sm₂O₃0.80 parts by mass of CeO₂0.30 parts by mass of Fe₂O₃0.50 parts by mass of Na₂O, 0.90 parts by mass of ZrO₂Mixing the raw materials, melting the mixture in a melting furnace by using a platinum crucible to obtain high-modulus glass liquid, cooling and forming the high-modulus glass liquid to obtain a high-modulus glass material, and detecting various performance parameters of the high-modulus glass material.

Specifically, the high-modulus glass material obtained by mixing and melting the raw materials in parts by mass has a molding temperature of 1325 ℃, a liquidus temperature of 1275 ℃, a difference between the molding temperature and the liquidus temperature of 50 ℃, an elastic modulus of 98400 MPa, a density of 2.69 g/cc and an acid-resistant mass retention rate of 95.9%.

Example 7:

weighing 62.0 parts by mass of SiO₂17.0 parts by mass of Al₂O₃1.0 part by mass of CaO, 12.3 parts by mass of MgO, and 3.0 parts by mass of Y₂O₃1.4 parts by mass of Sm₂O₃0.4 parts by mass of CeO₂0.30 parts by mass of Fe₂O₃0.50 parts by mass of Na₂O, 1.70 parts by mass of ZrO₂0.20 parts by mass of TeO₂0.20 parts by mass of GeO₂Mixing the raw materials, melting the mixture in a melting furnace by using a platinum crucible to obtain high modulus glass liquid, and cooling and forming the high modulus glass liquid to obtain the high modulus glass material.

Specifically, the high-modulus glass material obtained by mixing and melting the raw materials in parts by mass has a molding temperature of 1320 ℃, a liquidus temperature of 1248 ℃, a difference between the molding temperature and the liquidus temperature of 72 ℃, an elastic modulus of 96800 MPa, a density of 2.68 g/cc and an acid-resistant mass retention rate of 95.7%.

Example 8:

weighing 53.00 parts by mass of SiO₂21.90 parts by mass of Al₂O₃0.50 parts by mass of CaO, 13.00 parts by mass of MgO, and 3.3 parts by mass of Y₂O₃3.50 parts by mass of Sm₂O₃1.9 parts by mass of CeO₂0.30 parts by mass of Fe₂O₃0.60 parts by mass of Na₂O, 1.0 part by mass of ZrO₂0.50 parts by mass of TeO₂0.50 parts by mass of GeO₂Mixing the raw materials, melting the mixture in a melting furnace by using a platinum crucible to obtain high modulus glass liquid, and cooling and forming the high modulus glass liquid to obtain the high modulus glass material.

Specifically, the high-modulus glass material obtained by mixing and melting the raw materials in parts by mass has a molding temperature of 1340 ℃, a liquidus temperature of 1268 ℃, a difference between the molding temperature and the liquidus temperature of 72 ℃, an elastic modulus of 95600 MPa, a density of 2.67 g/cc and an acid-resistant mass retention rate of 94.3%.

Comparative example 1:

comparative example 1 is a common TCR glass fiber with a relatively large amount used in the wind power field.

Weighing 60.00 parts by mass of SiO₂13.50 parts by mass of Al₂O₃22.50 parts by mass of CaO, 3.00 parts by mass of MgO, and 0.20 part by mass of Fe₂O₃0.50 parts by mass of Na₂And O, mixing the raw materials, melting to obtain glass liquid, cooling and molding the glass liquid to obtain a glass material, and detecting various performance parameters of the glass material.

Specifically, the glass material obtained by mixing and melting the raw materials in parts by mass has the molding temperature of 1286 ℃, the liquid phase temperature of 1180 ℃, the difference between the molding temperature and the liquid phase temperature of 106 ℃, the elastic modulus of 86000 MPa, the density of 2.66 g/cc and the acid-resistant mass retention rate of 93.00%.

The common TCR glass fiber has good acid resistance and lower elastic modulus, is not beneficial to processing longer and bigger wind power blades, and limits the application of the wind power market.

Comparative example 2:

comparative example 2 is a high modulus glass fiber with a relatively high usage in the wind power field.

58.60 parts by mass of SiO are weighed₂23.00 parts by mass of Al₂O₃8.50 parts by mass of CaO, 9.00 parts by mass of MgO, and 0.20 part by mass of Fe₂O₃0.50 parts by mass of Na₂And O, mixing the raw materials, melting to obtain glass liquid, cooling and molding the glass liquid to obtain a glass material, and detecting various performance parameters of the glass material.

Specifically, the glass material obtained by mixing and melting the raw materials in parts by mass has a molding temperature of 1337 ℃, a liquidus temperature of 1278 ℃, a difference between the molding temperature and the liquidus temperature of 59 ℃, an elastic modulus of 92000 MPa, a density of 2.60 g/cc, and an acid-resistant mass retention rate of 86.5%.

The elastic modulus of the high-modulus glass fiber in the comparative example 2 is obviously improved compared with that of the comparative example 1, the modulus is still low, the high-end market application cannot be met, the acid resistance is relatively poor, and the service life of a subsequent product is influenced.

Comparative example 3:

57.0 parts by mass of SiO were weighed₂20.50 parts by mass of Al₂O₃5.5 parts by mass of CaO, 11.0 parts by mass of MgO, and 5.0 parts by mass of Y₂O₃0.30 parts by mass of Fe₂O₃0.50 parts by mass of Na₂And O, mixing the raw materials, melting to obtain glass liquid, and cooling and molding the glass liquid to obtain the glass material. Then various performance parameters of the glass material are detected.

Specifically, the test result shows that the glass material obtained by mixing and melting the raw materials in parts by mass has the forming temperature of 1331 ℃, the liquid phase temperature of 1298 ℃, the difference between the forming temperature and the liquid phase temperature of 33 ℃, the elastic modulus of 92500 MPa, the density of 2.71 g/cc and the acid-resistant mass retention rate of 89.50%.

Comparative example 3 glass composition with addition of only one rare earth oxide Y₂O₃The content and the use ratio of each component are not reasonably controlled, the difference between the forming temperature and the liquid phase temperature is small, the production difficulty is high, and the elastic modulus and the acid resistance are difficult to achieve the technical aim of the invention.

Attached table:

the above is a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A high modulus glass composition, comprising:

SiO₂53.0 to 63.0 parts by mass;

Al₂O₃17.0 to 22.0 parts by mass;

8.5 to 13.5 parts by mass of MgO;

ZrO₂0.1 to 2.0 parts by mass;

0.1 to 4.5 parts by mass of CaO;

3.0 to 15.0 parts by mass of a rare earth oxide clarifier;

ZrO₂is added in a proportion range of 0.08 or more compared with the addition amount of the rare earth oxide clarifier.

2. The high modulus glass composition of claim 1, comprising:

SiO₂56.0 to 62.5 parts by mass;

Al₂O₃17.5 to 21.5 parts by mass;

9.5 to 13.5 parts by mass of MgO;

0.1 to 3.0 parts by mass of CaO;

ZrO₂0.5 to 2.0 parts by mass;

3.0 to 10.0 parts by mass of a rare earth oxide clarifier.

3. The high modulus glass composition of claim 1, wherein said rare earth oxide fining agent comprises:

Y₂O₃the mass ratio of the Y2O3 in the high modulus glass composition is more than or equal to 3.0 percent;

Sm₂O₃sm is the above-mentioned₂O₃The mass ratio of the glass composition in the high modulus glass composition is less than or equal to 4.0 percent;

CeO₂the said CeO₂In the high mode glassThe mass ratio of the composition is less than or equal to 2.0%.

4. The high modulus glass composition according to claim 3, wherein the CeO₂Is added in an amount of more than Sm₂O₃The ratio of the addition amount of (b) is in the range of 0.25 to 0.55.

5. The high modulus glass composition according to any of claims 1 to 4, further comprising:

Fe₂O₃said Fe₂O₃The mass ratio of the glass composition in the high modulus glass composition is less than or equal to 1.0 percent; and/or

An alkali metal oxide, wherein the mass ratio of the alkali metal oxide in the high modulus glass composition is less than or equal to 1.0%, and the alkali metal oxide comprises at least one of the following or a combination thereof: li₂O、Na₂O、K₂O。

6. The high modulus glass composition according to any of claims 1 to 4,

the Al is₂O₃And the sum of the addition amounts of MgO accounts for 29% or more of the mass ratio of the high modulus glass composition; and/or

The proportion range of the addition amount of CaO to the addition amount of MgO is less than or equal to 0.37; and/or

The Al is₂O₃In a proportion range of 0.85 to 1.15 in comparison with the sum of the additive amounts of the CaO, the MgO, and the rare earth oxide clarifier; and/or

The addition amount of the rare earth oxide clarifier is compared with that of Al₂O₃The ratio of the amount of MgO to the sum of the amounts of MgO added is in the range of 0.1 to 0.4.

7. The high modulus glass composition according to any of claims 1 to 4,

the high modulus glass composition can be used for preparing a high modulus glass material, wherein the density of the high modulus glass material is less than or equal to 2.7 g/cc; and/or

The forming temperature of the high-modulus glass material is less than or equal to 1340 ℃; and/or

The liquidus temperature range of the high-modulus glass material is 1245-1290 ℃; and/or

The difference range between the forming temperature and the liquidus temperature of the high-modulus glass material is greater than or equal to 50 ℃; and/or

The elastic modulus of the high-modulus glass material ranges from 94000 MPa to 101000 MPa; and/or

The acid-resistant mass retention rate of the high modulus glass material is greater than or equal to 93%; and/or

The mechanical strength of the high-modulus glass material is more than or equal to 3200 MPa; and/or

The high modulus glass material has a coefficient of thermal expansion of less than or equal to 4.2 x 10^-6In degrees Celsius.

8. A high modulus glass fiber obtained from the high modulus glass composition of any of claims 1 to 7.

9. A composite material, characterized in that it comprises a high modulus glass composition according to any of claims 1 to 7.