CN106477898A - A kind of high-modulus glass fiber composition - Google Patents
A kind of high-modulus glass fiber composition Download PDFInfo
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- CN106477898A CN106477898A CN201610885514.9A CN201610885514A CN106477898A CN 106477898 A CN106477898 A CN 106477898A CN 201610885514 A CN201610885514 A CN 201610885514A CN 106477898 A CN106477898 A CN 106477898A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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Abstract
The present invention relates to a kind of high-modulus glass fiber composition, the glass fiber compound contains following components, and the content of each component is expressed as follows in parts by weight：SiO259～62 parts；Al2O313～15.5 parts；12.5～18.5 parts of CaO；4～8.5 parts of MgO；TiO21.5～4 parts and Li20.1～0.6 part of O；Or the glass fiber compound contains following components, the content of each component is expressed as follows in parts by weight：SiO261～62 parts；Al2O314～15 parts；13～14 parts of CaO；7～8 parts of MgO；Li20.4～0.6 part and B of O2O30.8～0.9 part.It is an advantage of the current invention that：By the formula of the present invention, it is possible to obtain meet requirement on cost and environmentally and the elastic modelling quantity of glass fiber compound can be improved, significantly reduce the glass fiber compound of liquidus temperature and mechanical performance.
Description
Technical field
The present invention relates to a kind of glass composition, more particularly to a kind of high-modulus glass fiber composition, are mainly used in wind
Electric blade and remote power transmission line field, it may also be used for the defence and military such as Aeronautics and Astronautics, weapons field.
Background technology
With the development of wind power technology, low-coat scale development is inexorable trend, and the development of wind-powered electricity generation low-coat scaleization
Key is the technology for solving large scale wind electricity blade, as with the increase of length of blade, the strength and stiffness to material are proposed
Requirements at the higher level, therefore, the strength and stiffness problems for solving blade material are to solve the key problem in technology that wind electricity blade maximizes.For
This, wind-powered electricity generation developed country all assaults the main target the research and development of high-strength high-modulus glass fiber as solve wind electricity blade maximization one
Direction.Foreign countries, OCV corporation in 2006 develop Hiper-texTMGlass, its intensity and modular ratio E glass be respectively increased 30 parts and
17 parts；AGY company develops S-1 glass in 2008, and its intensity and modular ratio E glass are respectively increased 45 parts and 20 parts, with tradition
High-strength glass fibre is compared, and these fibrous mechanical properties quite, but are produced and stablized, and price is low.The big glass giant of China three in order to
Wind electricity blade market is seized, also emphasis puts into and researched and developed, and between 2009～2010 years, successively have developed TM, Vipro, GMG
Deng the glass of the trade mark, compared with E glass fibre, the intensity of these fibers improves 15～30 parts, and modulus improves 10～17 parts.
Find that 103172267 A of patent CN discloses a kind of high strength glass fiber, including following component systems through retrieval
Become：SiO253～57wt part；Al2O323～26 wt parts；MgO 11.5～14.5wt part；B2O32～4wt part；Fe2O30.2
～1.0wt part；CeO20.2～1.0wt part；Li2O 0.2～0.8wt part；TiO20～1.0wt part；ZrO2、Y2O3And other chemical combination
Thing, and ZrO2、Y2O3And other compounds are less than 1wt part.The advantage of the high strength glass fiber is that good mechanical property i.e. monofilament draws
Stretch intensity and reach 4540～4720MPa, tensile modulus of elasticity and 85～87GPa is reached, glass fiber density is suitable with E glass, with
Traditional E glass fibre is compared more than 30 parts of monofilament tensile strength raising, tensile modulus of elasticity and improves more than 18 parts；Some special necks
Domain, the glass fibre modulus of needs are higher, but the modulus of the glass fibre can not meet；And the liquidus temperature of the glass fibre
Higher, cause production difficulty big, and the performance of glass composition is had a certain impact.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of high-modulus glass fiber composition, and said composition can be notable
The elastic modelling quantity of glass fibre is improved, on this basis, overcomes traditional high-modulus glass liquidus temperature higher, it is difficult to carry out
The problem of high efficiency tank furnace production, can significantly reduce the liquidus temperature of high-modulus glass.
For solving above-mentioned technical problem, the technical scheme is that：A kind of high-modulus glass fiber composition, its innovation
Point is：The glass fiber compound contains following components, and the content of each component is expressed as follows in parts by weight：SiO259～
62 parts；Al2O313～15.5 parts；12.5～18.5 parts of CaO；4～8.5 parts of MgO；TiO21.5～4 parts and Li2O 0.1～0.6
Part.
Further, the glass fiber compound also includes following components, and the content of each component represents in parts by weight
As follows：Fe2O30.2～0.3 part；K20.2～0.4 part and Na of O20.1～0.4 part of O.
Another technical scheme of the present invention is：A kind of high-modulus glass fiber composition, its innovative point are：The glass
Fiber composition contains following components, and the content of each component is expressed as follows in parts by weight：SiO261～62 parts；Al2O314～
15 parts；13～14 parts of CaO；7～8 parts of MgO；Li20.4～0.6 part and B of O2O30.8～0.9 part.
Further, the glass fiber compound also includes following components, and the content of each component represents in parts by weight
As follows：Fe2O30.2～0.3 part；K20.2～0.4 part of O, Na20.1～0.4 part and TiO of O20.4～0.6 part.
The high-modulus glass fiber composition of technical solution of the present invention one, in formula, SiO2It is the master to form glass skeleton
Oxide is wanted, and plays a part of to stablize each component, in the glass composition of the present invention, limit SiO2Weight portion content model
Enclose for 59～62 parts, on the basis of mechanical performance is ensured, in order to not increase the clarification difficulty of glass, specially by oxygen in the present invention
SiClx content controls in not high level.
Al2O3And the oxide of glass skeleton is formed, with SiO2In conjunction with when can play substance to the mechanical performance of glass
Effect, and play an important role in terms of glass phase-separating and water-resistance is prevented, and the glass fiber compound in the present invention
In, limit Al2O3Weight portion content range be 13～15.5 parts, if the relatively low meeting of its content cannot obtain sufficiently high mechanicalness
Energy, especially modulus；If the too high risk that glass phase-separating is easily significantly increased of its content.
CaO is the network modifying oxide of glass, can both adjust glass viscosity, control devitrification of glass, it is also possible to improve
The chemical stability and mechanical strength of glass, the CaO content scope limited by the present invention is as 12.5～18.5 parts, if its content is too
Low above-mentioned effect is not notable, if its too high levels, can increase the tendency towards devitrification of glass, causes to separate out anorthite, silicon from glass
The danger of the crystal such as lime stone.
MgO belongs to the outer component of network, can effectively reduce the high temperature viscosity of glass, has founded certain benefit to glass,
The content of MgO scope limited by the present invention is as 4～8.5 parts, if its content is too high, can promote the crystallization of glass, improve glass
Recrystallization temperature, if its content is too low, it is difficult to play due effect.
TiO in technical solution of the present invention one2, not only there is fluxing action, moreover it is possible to significantly improve the high resiliency of glass fibre
Modulus and the compactness of raising glass network structure, but due to TiO2Middle Ti4+Can excessively make glass that inappropriate coloring is produced, draw
Enter amount unsuitable excessive, therefore the present invention is strictly by TiO2Content range controls at 1.5～4 parts.
And in technical solution of the present invention one, also introduce a small amount of Li2O, Li2O significantly more can reduce glass viscosity,
So as to improve glass smelting performance, and the mechanical performance to improving glass has substantially help.
But in actual production process, can also there is Fe2O3、K2O and Na2O, although these impurity are to glass composition
There is certain impact in performance, but while also have certain facilitation.
K2O and Na2O can all reduce glass viscosity, be good cosolvent, but both introduction volumes are all unsuitable many, to keep away
Exempt to reduce intensity and the chemical stability of glass.
A small amount of Fe2O3（0.4 part of ＜）Introducing advantageously reduce the forming temperature of glass, improve the crystallization property of glass, but
Improvement to other performances is not obvious.But as iron ion and ferrous ion have pigmentation, product colour be had strictly to
Ask, Fe2O3Unsuitable many, the Fe limited by the present invention of introduction volume2O3Content range is 0.2～0.3 part.
The high-modulus glass fiber composition of technical solution of the present invention two, in formula, SiO2It is the master to form glass skeleton
Oxide is wanted, and plays a part of to stablize each component, in the glass composition of the present invention, limit SiO2Percentage by weight contain
Amount scope is 61～62 parts, on the basis of mechanical performance is ensured, in order to not increase the clarification difficulty of glass, in the present invention specially
Silica content is controlled in not high level.
Al2O3And the oxide of glass skeleton is formed, with SiO2In conjunction with when can play substance to the mechanical performance of glass
Effect, and play an important role in terms of glass phase-separating and water-resistance is prevented, and the glass fiber compound in the present invention
In, limit Al2O3Weight percent content scope be 14～15 parts, if the relatively low meeting of its content cannot obtain sufficiently high machinery
Performance, especially modulus；If the too high risk that glass phase-separating is easily significantly increased of its content.
CaO is the network modifying oxide of glass, can both adjust glass viscosity, control devitrification of glass, it is also possible to improve
The chemical stability and mechanical strength of glass, the CaO content scope limited by the present invention as 13～14 parts, if on its content is too low
State effect not notable, if its too high levels, the tendency towards devitrification of glass can be increased, cause anorthite, wollastonite is separated out from glass
Danger in crystal.
MgO belongs to the outer component of network, can effectively reduce the high temperature viscosity of glass, has founded certain benefit to glass,
The content of MgO scope limited by the present invention is as 7～8 parts, if its content is too high, can promote the crystallization of glass, improve the analysis of glass
Brilliant temperature, if its content is too low, it is difficult to play due effect.
B2O3With SiO2Composition, but will not be as SiO again it is constitute the composition of its skeleton in glass network structure2Composition
Increase the high temperature viscometrics of melten glass like that, there is effect on the contrary that decline high temperature viscometrics, advantageously reduce glass smelting
Temperature and the material of adjustment glass；But the present invention is by B2O3Content be strict controlled in 0.8～0.9 part, B2O3Introduction volume is unsuitable
Many, when content is excessive, acid resistance is easily deteriorated, so as to cause the split-phase in melten glass to be deteriorated.
A small amount of Li is also introduced in technical solution of the present invention two2O, Li2O can significantly more reduce glass viscosity, from
And improve glass smelting performance, and the mechanical performance to improving glass has substantially help.
But in actual production process, can also adulterate in formula K2O、Na2O、Fe2O3And TiO2,But these impurity can be to suitable
Performance for becoming the glass composition of fibre is present necessarily takes impact to, but while also has certain facilitation.
K2O and Na2O can all reduce glass viscosity, be good cosolvent, but both introduction volumes are all unsuitable many, to keep away
Exempt to reduce intensity and the chemical stability of glass.
A small amount of Fe2O3（0.4 part of ＜）Introducing advantageously reduce the forming temperature of glass, improve the crystallization property of glass, but
Improvement to other performances is not obvious.
A small amount of TiO2, not only there is fluxing action, moreover it is possible to significantly improve the high elastic modulus of glass fibre and improve glass
The compactness of glass network structure.
It is an advantage of the current invention that：High-modulus glass fiber composition of the present invention, compared with the prior art, by appropriate increasing
Plus SiO2And TiO2Consumption, relative reduce Al2O3, MgO, CaO and Li2The consumption of O, rationally controls impurity F e2O3、K2O and
Na2The consumption of O；Or increase SiO by appropriate2And the consumption of MgO, relative minimizing Al2O3、CaO 、Li2O and B2O3Consumption,
Rationally control impurity F e2O3、K2O、 Na2O and TiO2Consumption；Requirement on cost and environmentally and can is met to obtain
The elastic modelling quantity of glass fiber compound is improved, significantly reducing the glass fiber compound of liquidus temperature and mechanical performance；And
By technical scheme one, glass fiber compound can be made to have an elastic modelling quantity of 87～92GPa, 2500～
The intensity of 3000MPa, 2.60～2.65g/cm3Density；By technical scheme two, glass fiber compound can be made
Elastic modelling quantity with 85～87GPa, the intensity of 2500～3000MPa, 2.58～2.60g/cm3Density.
Specific embodiment
The following examples can make professional and technical personnel that the present invention is more fully understood, but not therefore by this
Bright it is limited among described scope of embodiments.
Embodiment
Table 1 is the embodiment of the high-modulus glass fiber composition of technical solution of the present invention one.
By the high-modulus glass fiber composition shown in table 1, the glass composition contains following components, the containing of each component
Amount is expressed as follows in parts by weight：SiO259～62 parts；Al2O313～15.5 parts；12.5～18.5 parts of CaO；MgO 4～8.5
Part；TiO21.5～4 parts and Li20.1～0.6 part of O.
When being embodied as, glass fiber compound also includes following components, and the content of each component represents such as in parts by weight
Under：Fe2O30.2～0.3 part；K20.2～0.4 part and Na of O20.1～0.4 part of O.
Table 1
Table 1（Continuous）
The method that the high-modulus glass fiber composition of technical solution of the present invention one prepares glass fibre, raw materials used mainly have height
Ridge soil, pyrophillite, lime stone, dolomite, titanium dioxide, spodumene and lithium carbonate are raw material, mix according to the ratio uniform in form
Close in the electric smelting type crucible furnace that traditional refractory material is made, liquid glass is fused at a temperature of 1480～1500 DEG C, all
Wire drawing is carried out by wire drawing machine after changing clarification.After wire drawing terminates, it is conventional to doff, impregnation, make impregnation bundle yarn, dry, become
Type process.The technique is common process, and here is not tired to be stated.
Above table includes the measured liquidus temperature (T of glass compositionL), liquidus temperature is surveyed by thermal gradient furnace
Fixed；Elastic modelling quantity, tensile strength and density including glass fibre, elastic modelling quantity, tensile strength are using impregnation yarn method according to GB/
T20310-2006 is tested, and density is according to ISO1183-1:2012 tests；Including glass fibre at 96 DEG C in given hydrochloric acid and
The mass loss rate of 24 hours is soaked in sulfuric acid；And the sample of comparative example 1-4 that lists in table 1 is the preferable ECR glass of acid resistance
Glass fiber.
After tested, elastic modelling quantity of the glass fibre that embodiment 1-5 glass composition is formed with 87～92GPa, 2500
The intensity of～3000MPa, 2.60～2.65g/cm3Density；The glass fibre that embodiment 6-10 glass composition is formed also has
There are the elastic modelling quantity of 87～92GPa, the intensity of 2500～3000MPa, 2.60～2.65g/cm3Density；But in actual life
In product, can adulterate in formula some impurity, but the addition of these impurity, remain to make the glass fiber compound of preparation to reach Gao Mo
The requirement of amount, typically for cost consideration, can bring some impurity in actual formula；Meanwhile, compared with comparative example, embodiment 1-
The glass fibre that 10 glass compositions are formed can significantly reduce liquidus temperature and improve acid resistance.
Table 2 is the embodiment of the high-modulus glass fiber composition of technical solution of the present invention two.
By the high-modulus glass fiber composition shown in table 2, the glass composition contains following components, the containing of each component
Amount is expressed as follows in parts by weight：SiO261～62 parts；Al2O314～15 parts；13～14 parts of CaO；7～8 parts of MgO；Li2O
0.4～0.6 part and B2O30.8～0.9 part.
When being embodied as, glass fiber compound also includes following components, and the content of each component represents such as in parts by weight
Under：Fe2O30.2～0.3 part；K20.2～0.4 part of O, Na20.1～0.4 part and TiO of O20.4～0.6 part.
Table 2
The method that the high-modulus glass fiber composition of technical solution of the present invention two prepares glass fibre, raw materials used mainly have height
Ridge soil, pyrophillite, lime stone, dolomite, bechilite, spodumene and lithium carbonate are raw material, mix according to the ratio uniform in form
Close in the electric smelting type crucible furnace that traditional refractory material is made, liquid glass is fused at a temperature of 1480～1500 DEG C, all
Wire drawing is carried out by wire drawing machine after changing clarification.After wire drawing terminates, it is conventional to doff, impregnation, make impregnation bundle yarn, dry, become
Type process.The technique is common process, and here is not tired to be stated.
Above table includes the measured liquidus temperature (T of glass compositionL), liquidus temperature is surveyed by thermal gradient furnace
Fixed；Elastic modelling quantity, tensile strength and density including glass fibre, elastic modelling quantity, tensile strength are using impregnation yarn method according to GB/
T20310-2006 is tested, and density is according to ISO1183-1:2012 tests；Including glass fibre at 96 DEG C in given hydrochloric acid and
The mass loss rate of 24 hours is soaked in sulfuric acid；And comparative example 1-2 that lists in table 1 is the high modulus fibre for simulating OC company,
Comparative example 3-4 is the high-modulus fiber for simulating PPG company.
After tested, the glass fibre that embodiment 1-2 glass composition is formed, and boron, liquidus curve temperature are added by purpose
Degree is lower than analog sample 10～40 DEG C, and modulus is high, the elastic modelling quantity with 85～87GPa, the intensity of 2500～3000MPa,
2.58～2.60g/cm3Density；The glass fibre that embodiment 3-4 glass composition is formed, it may have liquidus temperature compares mould
Intend sample low 10～40 DEG C, modulus is high, the elastic modelling quantity with 85～87GPa, the intensity of 2500～3000MPa, 2.58～
2.60g/cm3Density；But in actual production, can adulterate in formula some impurity, but the addition of these impurity, remain to make
The glass fiber compound of preparation reaches the requirement of high-modulus, typically for cost consideration, can bring some into miscellaneous in actual formula
Matter.
General principle and principal character and the advantages of the present invention of the present invention has been shown and described above.The skill of the industry
Simply explanation of the art personnel it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and specification
The principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these
Changes and improvements are both fallen within scope of the claimed invention.The claimed scope of the invention by appending claims and
Its equivalent thereof.
Claims (4)
1. a kind of high-modulus glass fiber composition, it is characterised in that：The glass fiber compound contains following components, each group
The content that divides is expressed as follows in parts by weight：SiO259～62 parts；Al2O313～15.5 parts；12.5～18.5 parts of CaO；MgO
4～8.5 parts；TiO21.5～4 parts and Li20.1～0.6 part of O.
2. high-modulus glass fiber composition according to claim 1, it is characterised in that：The glass fiber compound is also
Comprising following components, the content of each component is expressed as follows in parts by weight：Fe2O30.2～0.3 part；K20.2～0.4 part of O and
Na20.1～0.4 part of O.
3. a kind of high-modulus glass fiber composition, it is characterised in that：The glass fiber compound contains following components, each group
The content that divides is expressed as follows in parts by weight：SiO261～62 parts；Al2O314～15 parts；13～14 parts of CaO；MgO 7～8
Part；Li20.4～0.6 part and B of O2O30.8～0.9 part.
4. high-modulus glass fiber composition according to claim 3, it is characterised in that：The glass fiber compound is also
Comprising following components, the content of each component is expressed as follows in parts by weight：Fe2O30.2～0.3 part；K20.2～0.4 part of O,
Na20.1～0.4 part and TiO of O20.4～0.6 part.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107032598A (en) * | 2017-05-23 | 2017-08-11 | 武汉理工大学 | A kind of composite anti-foaming agent produced suitable for glass fibre |
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| CN101597140A (en) * | 2009-07-02 | 2009-12-09 | 重庆国际复合材料有限公司 | A kind of high-strength high-modulus glass fiber |
| CN101838110A (en) * | 2010-05-19 | 2010-09-22 | 巨石集团有限公司 | Composition for preparing high-performance glass fiber by tank furnace production |
| CN105174731A (en) * | 2015-09-08 | 2015-12-23 | 重庆国际复合材料有限公司 | High modulus glass fiber |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3876481A (en) * | 1972-10-18 | 1975-04-08 | Owens Corning Fiberglass Corp | Glass compositions, fibers and methods of making same |
| CN101597140A (en) * | 2009-07-02 | 2009-12-09 | 重庆国际复合材料有限公司 | A kind of high-strength high-modulus glass fiber |
| CN101838110A (en) * | 2010-05-19 | 2010-09-22 | 巨石集团有限公司 | Composition for preparing high-performance glass fiber by tank furnace production |
| CN105174731A (en) * | 2015-09-08 | 2015-12-23 | 重庆国际复合材料有限公司 | High modulus glass fiber |
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| CN107032598A (en) * | 2017-05-23 | 2017-08-11 | 武汉理工大学 | A kind of composite anti-foaming agent produced suitable for glass fibre |
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