CN109052971A - A kind of high-performance glass fiber composition and glass fibre being easy to large-scale production - Google Patents
A kind of high-performance glass fiber composition and glass fibre being easy to large-scale production Download PDFInfo
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- CN109052971A CN109052971A CN201811055775.3A CN201811055775A CN109052971A CN 109052971 A CN109052971 A CN 109052971A CN 201811055775 A CN201811055775 A CN 201811055775A CN 109052971 A CN109052971 A CN 109052971A
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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
Abstract
The present invention provides a kind of high-performance glass fiber compositions and glass fibre for being easy to large-scale production, and the composition includes following component: SiO258.2wt%~60.4wt%；Al2O316.5wt%~19.8wt%；SiO2With Al2O3Total content 76wt%~79wt%；Al2O3/SiO2Mass fraction ratio 0.27~0.34；CaO 9wt%~10.5wt%；MgO 10.1wt%~11.6wt%；Total content 20.1wt%~21.5wt% of CaO and MgO；MgO/CaO mass fraction ratio 1.01~1.27；B2O30~3.0wt%；B2O3With SiO2Total content 58.5wt%~62.2wt%；TiO20.2wt%~1.5wt%；Fe2O30.1wt%~0.5wt%；Na2O、K2O and Li2Total content 0.2wt%~1.0wt% of O；Remaining impurity composition total content is no more than 1wt%.The present invention by definitely define glass composition at be grouped as and constituent part between particular association relationship; a kind of high-performance glass fiber for being easy to large-scale production is obtained; it has excellent mechanical property and lower production difficulty, lower cost can accomplish scale production under prior art conditions.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials more particularly to a kind of high-performance glass fibers.
Background technique
Glass fibre belongs to inorganic non-metallic material, it has, and high mechanical strength, electrical insulating property is good, heat resistance is strong, physics
Many advantages, such as chemical property is stablized, it is many to be widely used in aerospace, automobile, ship, petrochemical industry, the energy, electric power, building etc.
Field is the maximum inorfil reinforcing material of current application amount.Due to being mainly used as enhancing base materials, the mechanical property of glass fibre
It can just be particularly important, therefore, it is more and more excellent while being also easy to the glass accomplished scale production develop mechanical property
Fiber composition is the pursuit of vast industry technology personnel always.
Based on silicate glass basic theories, the glass fibre of excellent in mechanical performance can be divided into S glass and R glass from component
Glass two major classes.S glass belongs to SiO2-Al2O3- MgO system, typical case's composition are as follows: the SiO of 65wt%2, the Al of 25wt%2O3,
The MgO of 10wt%.S glass fibre theory filament strength is up to 4500MPa, and elasticity modulus is more than 85GPa, and mechanical property is very excellent
It is different.But its forming temperature has been more than 1470 DEG C, and easily crystallization, and production difficulty is very big, and big rule are difficult to realize under present condition
Mould promotes and applies.R glass belongs to SiO2-Al2O3- CaO-MgO system, alkali-metal-oxide content is higher, is generally acknowledged to
It is a kind of compromise of production difficulty and mechanical property, compared with S glass, although having more large-scale production feasibility, mechanical property
It can decrease.
Application No. is the patents of CN200480015986.4 to disclose a kind of glass fiber compound, and it contains 50~
The SiO of 65wt%2, the Al of 12~20wt%2O3, the B of the MgO of the CaO of 13~16wt%, 6~12wt%, 0~3wt%2O3, 0
The TiO of~3wt%2, the K of 0~2wt%2O+Na2O.The glass fibre belongs to R grades of glass, by controlling Al2O3It is obtained with CaO content
Obtained preferable mechanical property and meltdown property.But CaO content is higher in the patent, and content of MgO is relatively low, and specific modulus is caused to only have
35-36MPa.kg-1.m3, it is difficult to meet the needs of higher performance.
Application No. is the patents of CN201080070857.0 to disclose a kind of high strength glass fiber, and its composition includes:
The SiO of 56~61wt%2, the Al of 16~23wt%2O3, the CaO of the MgO of 8~12wt%, 6~10wt%, 0~2wt%'s
Na2O, the Li less than 1wt%2O, and the transition metal oxide less than 2wt%.The glass fibre obtains good really
Mechanical performance, but can be seen from its preferred embodiment and practical embodiments, in order to balance its production difficulty, it, which joined, is more than
1% Na2O, and advocate to contain only a kind of alkali metal oxide, (natural minerals original is difficult to realize in this aspect actual production
Often contain a certain amount of K in material simultaneously2O and Na2O), the excessively high Na of another aspect2Chemical stability of the O to glass fibre
Have negative effect.
Application No. is the patents of CN201180028428.1 to also disclose a kind of high strength glass fiber, its composition packet
Contain: the SiO of 57~63wt%2, the Al of 19~23wt%2O3, the CaO of the MgO of 10~15wt%, 4~11wt%, and SiO2、
Al2O3, CaO, MgO total content 99.5wt% or more.Glass fibre elasticity modulus is up to 96GPa or more in the patent, but same
When patent requirements SiO2、Al2O3, CaO, MgO total content must also mean that Fe in 99.5wt% or more2O3, alkali gold
Belong to oxide content and other impurities total content must be controlled 0.5% hereinafter, high (the common mineral of so not only cost of material
Material purity is unable to reach requirement), there is also larger difficulty for devitrification problem and Melting Problem.
Application No. is 201710413847.6 patents to provide a kind of high-modulus glass fiber composition, including such as the following group
Point: SiO250wt%~58wt%；Al2O318wt%~24wt%；SiO2With Al2O3Total content 72.5wt%~
79.5wt%；Al2O3/SiO2Mass fraction ratio 0.34~0.45；TiO20.2wt%~1.5wt%；ZnO 0~
2.0wt%；ZrO20~2.0wt%；Fe2O30.1wt%~0.6wt%；CaO 9.2wt%~11wt%；MgO 9wt%~
12wt%；Total content 18.2wt%~22wt% of CaO and MgO；MgO/CaO mass fraction ratio 1.0~1.3；Na2O、K2O with
Li2Total content 0.2wt%~1.0wt% of O；Said components amount to 100%.This glass fiber compound can get good
Elasticity modulus, but forming temperature and clean temperature drift, and TLiquidIt is bigger than normal, it is easy to devitrification problem and wire drawing difficult problem occur.
Summary of the invention
In view of this, the present invention can not be simultaneous in order to solve excellent mechanical property and lower fusion temperature and molding difficulty
The problem of obtaining, provides a kind of high-performance glass fiber composition and glass fibre for being easy to large-scale production.
Technical scheme is as follows:
A kind of high-performance glass fiber composition being easy to large-scale production, it is characterised in that including following component:
Preferably, the SiO2Content is 59wt%~59.9wt%；The Al2O3Content be 16.8wt%~
18.9wt%；The SiO2With Al2O3Total content be 76.8wt%~78.8wt%.
Preferably, the CaO content is 9wt%~9.9wt%；The content of MgO is 10.2wt%~11.4wt%；Institute
The total content for stating CaO and MgO is 20.1wt%~21.3wt%；The MgO/CaO mass fraction ratio is 1.01~1.23.
Preferably, the B2O3Content is 0.3wt%~2.0wt%.
It is further preferred that the B2O3Content is 0.3wt%~1.0wt%.
It is further preferred that the Na2O、K2O and Li2Total content 0.2wt%~0.8wt% of O.
A kind of high-performance glass fiber being easy to large-scale production, is prepared by combinations of the above object.
The present invention is guaranteeing by adjusting constituent content and the whole content and proportional region of accurate control section component
Processing performance is significantly improved on the basis of mechanical property, so that glass fibre not only springform with higher
Amount, while melt drawing performance and crystallization temperature significantly reduce.
Wherein, the silica (SiO2) it is to form one of main oxides of glass network, it mainly plays raising glass
The effect of the mechanical strength, chemical stability and thermal stability of glass, but too high levels will increase the viscosity and fusion temperature of glass,
Cause glass fibre molding difficulty and production cost higher.The present invention tests discovery, by SiO2Content is controlled in 58.2-
Between 60.4wt%, while cooperating the restriction of other components, glass fibre can either obtain lower molding difficulty, and can protect
Stay excellent mechanical strength.Further preferably 59~60.2wt%.
Aluminium oxide (Al2O3) be also form one of main oxides of glass network, it to improve chemical durability of glass and
Mechanical strength has positive effect, but excessively high Al2O3Content will increase glass fibre tendency towards devitrification and wire-drawing shape difficulty, especially
It is in SiO2Content is also in higher situation.Therefore, Al in the present composition2O3Content is 16.5wt%~19.8wt%, excellent
It is selected as 16.8wt%~19.5wt%.
In addition, in SiO2-Al2O3In-CaO-MgO system, Al2O3And SiO2It is the main body for constituting glass network structure,
Total content is higher, and glass network structure is more complete, and glass mechanical property is higher, but production difficulty is also higher simultaneously.Therefore, this hair
Bright restriction SiO2With Al2O3Total content be 76wt%~79wt%, preferably 76.8wt%~78.8wt%.Al2O3/SiO2Matter
Measuring score ratio is 0.27~0.34, it is preferred that the Al2O3/SiO2Mass fraction ratio is 0.28~0.33.The ratio model
Enclosing can guarantee that glass fibre has fabulous elasticity modulus and optimal melting behaviour and wire-drawing shape performance.
Calcium oxide (CaO) and magnesia (MgO) are oxide of the same clan, all have filling network empty in glass network structure
Gap, the effect for improving glass melting at high temperature performance and devitrification of glass tendency.Wherein MgO ionic radius is less than CaO, and field strength is bigger,
Thus MgO ratio is kept to be suitably above CaO content, contribute to form finer and close glass network structure, promotes glass fibre power
Learn performance.Therefore, CaO content of the present invention is limited to 9wt%~10.5wt%, it is preferred that CaO content be 9wt%~
9.9wt%, content of MgO are 10.1wt%~11.6wt%, preferably 10.2wt%~11.4wt%；The total content of CaO and MgO
For 20.1wt%~21.5wt%, preferably 20.1wt%~21.3wt%.MgO/CaO mass fraction ratio be 1.01~
1.27, it is preferred that the MgO/CaO mass fraction ratio is 1.01~1.23.
The present invention is special, and a certain amount of boron oxide (B can be also added in the glass fiber compound2O3).Largely
Experiment discovery, a small amount of B2O3Strengthens network intensity in glass network can not only be entered, to improve glass mechanical property, together
When it also have significantly reduce high temperature viscosity of glass, accelerate clarification, improve the effect of devitrification of glass tendency.In the present invention, even more
It was found that and SiO2The content cooperation of preferred total content and other materials, so that overall mechanical properties remain to be maintained at compared with Gao Shui
It is flat.
Titanium dioxide (TiO2) ionic radius is small, field strength is big, plays the role of centainly assembling glass network.Thus contain in glass
There is a small amount of titanium dioxide (TiO2) help to improve glass temperature flowing and tendency towards devitrification, improve Fiberglass machine performance and
Corrosion resistance.But otherwise the content of titanium dioxide can significantly affect glass colour no more than 1.5wt%.In the present invention
TiO2Content be limited to 0.2wt%~1.5wt%.
Due to iron oxide (Fe2O3) be widely present in various raw mineral materials, a small amount of Fe in glass2O3Bring into be can not
It avoids, and is no more than the Fe of 0.5wt%2O3On glass fibre performance influence very little, for as far as possible reduce raw mineral materials buying at
This, iron oxide content of the present invention is limited to 0.1wt%~0.5wt%.
Li2O、Na2O and K2O can damage the chemical stability of alumina silicate glass as alkali metal oxide, too high levels
And mechanical property, it is general it is not recommended that special addition.Li in glass fiber compound of the present invention2O、Na2O and K2O is mine
Raw material Impure forms are brought or are adjusted the saltcake used when furnace atmosphere into and bring into, and a small amount of said components also have certain reduction
Glass viscosity improves the positive effect of devitrification of glass tendency.Therefore, it is examined from cost of material and glass fiber quality angle synthesis
Consider, Na in glass composition of the present invention2O、K2O and Li2O total content is limited to 0.2~1.0wt%, it is preferred that for 0.2~
0.8%.
In addition to the components described above, the present invention is substantially free of other components, such as F, ZnO, ZrO2, BaO, SrO and rare earth element
Deng.Here " being substantially free of ", which refers to, does not add specially, and every kind of constituent content is lower than 0.1%.Because of usual glass fibre group
It point is introduced by natural minerals, might have as impurity and be not belonging to the microelement of major constituent of the present invention and be brought into.Such as
It must be entirely 0 that fruit, which strictly limits these impurity components in the present invention, both unrealistic, also uneconomical.Therefore, from cost of material and
Glass fiber quality angle comprehensively considers, and content of impurities defines no more than 1wt% in the present invention, it is preferred that content of impurities
No more than 0.5wt%.
The present invention by definitely define glass composition at be grouped as and constituent part between particular association relationship, obtain
To a kind of high-performance glass fiber for being easy to large-scale production, it has excellent mechanical property and lower production difficulty,
It lower cost can accomplish scale production under prior art conditions.A large number of experiments show that the present invention is glass fiber dipped
Yarn tensile strength is up to 3000MPa or so, and stretch modulus is up to 94GPa or so, and the forming temperature of glass fibre is no more than
1280 DEG C, crystallization ceiling temperature is lower than 1230 DEG C, can meet modern tank furnace method large-scale production completely and require.
Specific embodiment
The present invention provides a kind of high-performance glass fiber composition and glass fibre for being easy to large-scale production, abilities
Field technique personnel can use for reference present disclosure, be suitably modified realization of process parameters.In particular, it should be pointed out that all similar replaces
Change and change apparent to those skilled in the art, they shall fall within the protection scope of the present invention.Of the invention
Method and application are described by preferred embodiment, and related personnel can obviously not depart from the content of present invention, spirit
Methods herein and application are modified or appropriate changes and combinations in range, carry out implementation and application the technology of the present invention.
The present invention is not particularly limited the preparation method of the glass fibre, can be for known to those skilled in the art
Method, preferably tank furnace method produce, can specifically prepare by the following method:
Various raw materials are put into tank furnace after mixing, after fusing, clarification, homogenizing, obtain glass metal；
The glass metal is obtained into glass fibre after cooling, outflow and wire drawing process.
The present invention first mixes various raw materials in mixing tank, after mixing, is transported to tank furnace feed bin；Then
Mixture is put into tank furnace by tank furnace feed bin, is melted, clarification and homogenization under conditions of 1400~1800 DEG C, obtains glass
Liquid；
The glass metal is cooled to 1200~1300 DEG C, is flowed out through platinum bushing plate, under the traction of wire drawing machine, wire drawing at
The glass fiber that diameter is 3~25 μm；
The glass fiber is coated to obtain glass fibre by misting cooling, size.
After obtaining glass fibre, the glass fibre is tested for the property.
In order to further illustrate the present invention, below with reference to embodiment to high-performance glass fiber composition provided by the invention
And glass fibre is described in detail.
Embodiment 1
By each feedstock transportation to mixing tank, after mixing, mixture is delivered to tank furnace feed bin, each raw material contains
Amount is according to shown in table 1；
Mixture in tank furnace feed bin is put into tank furnace, in tank furnace, mixture is gradually melted through 1400 DEG C or more of high temperature
Be melted into glass metal, it is clarified, homogenizing after, stablize and the glass metal of high-quality enters wire-drawing operation channel；
After glass metal in wire-drawing operation channel is cooled to suitable temperature, flowed out through platinum bushing plate, it is quick by wire drawing machine
It is distracted into 3~25 μm of diameter of glass fiber, glass fiber is wound on wire drawing machine after misting cooling, size coating, boundling
Spinning cake；
All spinning cake dryings, doff are chopped etc. after processes, obtain various types of glass fiber products.
The glass fibre is tested for the property, as a result referring to table 1, table 1 provides for the embodiment of the present invention and comparative example
Glass fibre formula and performance data table.
Embodiment 2~15
Preparation method is same as Example 1, and only the content of various raw materials is changed, specific as shown in table 1.
The glass fibre is tested for the property, as a result referring to table 1.
Comparative example
It is formulated according to shown in table 1, by various feedstock transportations to mixing tank, after mixing, mixture is delivered to pond
Kiln feed bin, the content of each raw material is according to shown in table 1；
Mixture in tank furnace feed bin is put into tank furnace, in tank furnace, mixture is gradually melted through 1400 DEG C or more of high temperature
Be melted into glass metal, it is clarified, homogenizing after, stablize and the glass metal of high-quality enters wire-drawing operation channel；
After glass metal in wire-drawing operation channel is cooled to suitable temperature, flowed out through platinum bushing plate, it is quick by wire drawing machine
It is distracted into 3~25 μm of diameter of glass fiber, glass fiber is wound on wire drawing machine after misting cooling, size coating, boundling
Spinning cake；
All spinning cake dryings, doff are chopped etc. after processes, obtain glass fibre.
The glass fibre is tested for the property, as a result referring to table 1.
The formula and performance data table for the glass fibre that 1 embodiment of table and comparative example provide
Table 1 is continuous
Table 1 is the glass combination chemical constituent of each embodiment and comparative example, and unit is mass percent.For convenient for meter
It calculates, when designing 1 glass ingredient of table, each component content ignores impurity component in table, to introduce ingredient total content as 100%, and
When actual test, since instrument error and trace impurity influence, may slightly have difference.
Glass fiber high-temperature viscosity is detected using the BROOKFIELD high temperature viscosity instrument of ORTON company production；Glass liquid phase
Line temperature is detected using Orton Model gradient furnace；Glass softening point softens point tester using Orton Model SP-1100
Measurement；
Tη=3 logIndicate that glass viscosity is 103Temperature when pool, the temperature of glass metal when being equivalent to glass fibre molding,
Referred to as glass fibre forming temperature.
TLiquidIt indicates glass liquidus temperature, is equivalent to temperature when glass crystallization speed is 0, also corresponds to devitrification of glass temperature
Spend the upper limit.
Δ T is Tη=3 logAnd TLiquidDifference, the molding difficulty of glass fibre, usual Δ T >=50 DEG C are generally characterized with it
When, the more stable wire-drawing shape of glass fibre energy.
Tensile strength and stretch modulus are the impregnation yarn strengths detected according to test method as defined in national standard GB/T20310
And modulus.
The experimental results showed that the glass fiber dipped yarn tensile strength of the present invention is up to 3000MPa or so, stretch modulus
94GPa or so, and the forming temperature of glass fibre is no more than 1280 DEG C, crystallization ceiling temperature is lower than 1230 DEG C.By above-mentioned implementation
Example and comparative example are it is found that the present invention improves the comprehensive of glass fibre by accurately adjusting various ingredients and its concrete content
Can, while also reducing production difficulty.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (7)
1. a kind of high-performance glass fiber composition for being easy to large-scale production, it is characterised in that including following component:
Remaining impurity composition total content is no more than 1wt%.
2. composition according to claim 1, it is characterised in that the SiO2Content is 59wt%~59.9wt%；It is described
Al2O3Content is 16.8wt%~18.9wt%；The SiO2With Al2O3Total content be 76.8wt%~78.8wt%.
3. composition according to claim 1, it is characterised in that the CaO content is 9wt%~9.9wt%；The MgO
Content is 10.2wt%~11.4wt%；The total content of the CaO and MgO is 20.1wt%~21.3wt%；The MgO/CaO
Mass fraction ratio is 1.01~1.23.
4. composition according to claim 1, it is characterised in that the B2O3Content is 0.3wt%~2.0wt%.
5. composition according to claim 4, it is characterised in that the B2O3Content is 0.3wt%~1.0wt%.
6. composition according to claim 4, it is characterised in that the Na2O、K2O and Li2The total content 0.2wt% of O~
0.8wt%.
7. a kind of high-performance glass fiber for being easy to large-scale production, it is characterised in that by any combination of claim 1-6
Object is prepared.
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| CN201811055775.3A CN109052971A (en) | 2018-09-11 | 2018-09-11 | A kind of high-performance glass fiber composition and glass fibre being easy to large-scale production |
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| CN201811055775.3A CN109052971A (en) | 2018-09-11 | 2018-09-11 | A kind of high-performance glass fiber composition and glass fibre being easy to large-scale production |
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| CN111039571A (en) * | 2019-12-19 | 2020-04-21 | 重庆国际复合材料股份有限公司 | High-refractive-index and high-transparency glass fiber |
| CN112759270A (en) * | 2020-12-31 | 2021-05-07 | 徐州关高研磨科技有限公司 | Glass fiber |
| CN115093123A (en) * | 2022-06-21 | 2022-09-23 | 重庆国际复合材料股份有限公司 | Low-expansion high-modulus glass fiber composition and glass fiber |
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| CN115093123B (en) * | 2022-06-21 | 2024-03-15 | 重庆国际复合材料股份有限公司 | Low-expansion high-modulus glass fiber composition and glass fiber |
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