CN107082569A - A kind of glass fiber compound and glass fibre - Google Patents
A kind of glass fiber compound and glass fibre Download PDFInfo
- Publication number
- CN107082569A CN107082569A CN201710413849.5A CN201710413849A CN107082569A CN 107082569 A CN107082569 A CN 107082569A CN 201710413849 A CN201710413849 A CN 201710413849A CN 107082569 A CN107082569 A CN 107082569A
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- Prior art keywords
- glass
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- mgo
- glass fibre
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Classifications
-
- 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
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
Abstract
The invention provides a kind of glass fiber compound, including following component：SiO250wt%~56wt%；Al2O318wt%~24wt%；SiO2With Al2O3Total content 72wt%~78wt%；Al2O3/SiO2Mass fraction ratio 0.32~0.42；TiO20.5wt%~2.5wt%；ZnO 0.5wt%~2.0wt%；ZrO23.0wt%~5.0wt%；Fe2O30.1wt%~0.6wt%；CaO 6wt%~10wt%；MgO 9wt%~12wt%；CaO and MgO total content 16wt%~20wt%；MgO/CaO mass fractions ratio 1.0~1.5；Na2O、K2O and Li2O total content 0.2wt%~1.0wt%；Said components amount to 100%.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, more particularly to a kind of glass fiber compound and glass fibers
Dimension.
Background technology
Glass fibre belongs to inorganic non-metallic material, and it has, and high mechanical strength, electrical insulating property are good, heat resistance is strong, physics
Many advantages, such as chemical property is stable, is widely used in Aero-Space, automobile, ship, petrochemical industry, the energy, electric power, building etc. many
Field, is the maximum inorfil reinforcing material of current application amount.In the application process of glass fibre, with composite system
Product sizes is continuously increased, and people propose higher and higher require to the mechanical property especially modulus of elasticity of glass fibre.
For lifting glass fiber strength and the method for modulus, at present existing many correlative studys.Most typical is exactly S
Glass and R glass.S glass basic composition is：65wt% SiO2, 25wt% Al2O3, 10wt% MgO.S glass fibres
Theoretical filament strength is up to 4500MPa, and modulus of elasticity is more than 85GPa, and mechanical property is very excellent.But its forming temperature exceedes
1470 DEG C, and easily crystallization, production difficulty is very big, it is impossible to realize large-scale promotion application.R glass is also that a kind of high intensity is done
Modulus glass fiber, it is usually by SiO2、Al2O3, CaO, MgO composition, be generally considered to be production difficulty and mechanical property
One kind is compromise, so that compared with S glass, with more producing feasibility.
Japan Patent JP8231240 discloses a kind of glass fiber compound, and it contains 62~67wt% SiO2, 22~
27wt% Al2O3, 7~15wt% MgO, 0.1~1.1wt% CaO, 0.1~1.1wt% B2O3.The glass fibre leads to
Cross and add a small amount of CaO and B2O3So that number of bubbles is obviously improved with respect to S glass fibres, but shaping is still extremely difficult, into
Type temperature is more than 1460 DEG C.
Japan Patent JP2003171143 also illustrates a kind of high-strength high-modulus glass fiber, and it contains 55~65wt%
SiO2, 17~23wt% Al2O3, 7~15wt% MgO, 2~6wt% CaO, 1~7wt% TiO2.Compared with S glass
Glass, although the glass fibre mechanical property has been sacrificed, processability, which has, to be obviously improved, forming temperature is about 1340~
1380℃.But TiO in the glass2Content is very high so that glass colour is partially deep, which has limited its some fields application.
A kind of high-performance glass fiber composition of Publication No. US2010/0160139 U.S. Patent Publication, including：
64~75wt% SiO2, 16~24wt% Al2O3, 8~12wt% MgO, 0.25~3wt% Li2O+Na2O.Relative to
S glasses, this glass fibre adds a certain amount of Li2O and Na2O, thus reduce the high temperature viscosity and shaping difficulty of glass.
But, if Li in the system glass2O and Na2O additions are relatively low, then act on unobvious；Addition is too high, then has a strong impact on glass
The insulating properties and decay resistance of glass fiber, therefore the fibre-forming performance of glass fibre is still difficult to control to.
Application No. CN201080070857.0 patent discloses a kind of high strength glass fiber, and its composition is included：
56~61wt% SiO2, 16~23wt% Al2O3, 8~12wt% MgO, 6~10wt% CaO, 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 practical embodiments, in order to balance its production difficulty, it adds the Na more than 1%2O, and
Too high Na2O can have an impact to the chemical stability of glass fibre.
Application No. CN201180028428.1 patent also discloses that a kind of high strength glass fiber, its composition bag
Contain：57~63wt% SiO2, 19~23wt% Al2O3, 10~15wt% MgO, 4~11wt% CaO, and SiO2、
Al2O3, CaO, MgO total total content be more than 99.5wt%.Glass fibre modulus of elasticity is up to more than 96GPa in the patent,
But simultaneously because it requires to control very low Fe2O3And alkali metal oxide content, not only cost of material is high, devitrification problem and molten
All there is certain solution difficulty in change problem.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of glass fiber compound and glass fibers
Dimension, while having excellent mechanical property and the processability compared with low viscosity.
The invention provides a kind of glass fiber compound, including following component：
Said components amount to 100%.
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 of glass, chemical stability and heat endurance, but too high levels can increase the viscosity and fusion temperature of glass,
Cause glass fibre shaping difficulty and production cost higher.SiO of the present invention2Content is 50wt%~56wt%, is preferably
52wt%~55.8wt%.
Aluminum oxide (Al2O3) be also to form one of main oxides of glass network, it have reduction devitrification of glass tendency,
Chemical durability of glass, the effect of mechanical strength are improved, if but Al2O3Too high levels, can cause glass viscosity excessive, glass again
Into fine difficult, it is also easy to devitrification problem occur.Al of the present invention2O3Content be 18wt%~24wt%, preferably 19wt%~
22.5wt%.
The Al2O3And SiO2Total content and mass fraction ratio are significant to alumina silicate glass modulus of elasticity,
Al2O3Relative scale is higher, and glass modulus is big, but production difficulty and tendency towards devitrification can also be dramatically increased simultaneously, present invention limit
Determine SiO2With Al2O3Total content be 72wt%~78wt%, preferably 73.5wt%~77.6wt%.Al2O3/SiO2Quality point
Number ratio is 0.32~0.42, it is preferred that the Al2O3/SiO2Mass fraction ratio is 0.36~0.42.The proportion energy
Enough ensure that glass fibre has optimal modulus of elasticity and melt drawing performance, recrystallization temperature.
Calcium oxide (CaO) and magnesia (MgO) belong to glass structure network modifying oxide, with reduction glass high temperature
Viscosity, the effect for improving devitrification of glass tendency.Wherein MgO ionic radius are less than CaO, thus higher MgO ratios, contribute to shape
Into finer and close glass network structure, glass modulus is lifted.But if content of MgO is too high, production difficulty can become to be difficult to
Receive.CaO content of the present invention is 6wt%~10wt%, it is preferred that CaO content is 6.4wt%~9.6wt%, and MgO contains
Measure as 9wt%~12wt%, more preferably 9.4wt%~11.4wt%.CaO and MgO total content is 16wt%~20%, excellent
Elect 17.2wt%~19.8% as.MgO/CaO mass fractions ratio is 1.0~1.5, it is preferred that the MgO/CaO mass fractions
Ratio is 1.1~1.44.
A small amount of Fe contained therein2O3Be conducive to tank furnace heat transfer, but if too high levels, to the face of glass fibre
Color and heat transfer property are all adversely affected.Iron oxide content of the present invention is defined to 0.1wt%~0.6wt%, preferably 0.2wt%
~0.5wt%.
In the present invention, the addition of zinc oxide (ZnO) helps to improve glass temperature flowing and tendency towards devitrification, improves glass
Fibre machinery performance and decay resistance.ZnO of the present invention content is 0.5wt%~2.0wt%, it is preferred that the ZnO's contains
Measure as 0.5wt%~1.5wt%.
The present invention with the addition of titanium dioxide (TiO in glass fibre2) and zirconium oxide (ZrO2), this kind of ionic radius is small, electricity
The big oxide of field intensity, with the effect for improving devitrification of glass performance, improving modulus of elasticity and chemical durability of glass.This hair
In bright, TiO2Content is 0.5wt%~2.5wt%, preferably 1.0wt%~2.0wt%；ZrO2Content be 3.0wt%~
5.0wt%, preferably 3.2wt%~4.5wt%.
It is currently preferred, the TiO2, ZnO and ZrO2Total content be 5.0wt%~7.0wt%.
It is currently preferred, also it with the addition of Li in the glass fiber compound2O、Na2O and K2One kind or many in O
Kind, they help to reduce glass viscosity, improve devitrification of glass tendency.But alkali metal content also can not be too high, otherwise it can damage
The chemical stability of glass.It is currently preferred, in the glass fiber compound, Na2O、K2O and Li2O total contents are
0.2wt%~1.0wt%, preferably 0.5wt%~0.8wt%.
According to the present invention, preferably, on the premise of glass fibre mechanical property is not influenceed, in order to improve glass
Fiberizing performance, glass fiber compound of the present invention can also contain the F no more than 3wt%2、B2O3、Y2O3、BaO、La2O3、
CeO2In one or more.
The present invention is by accurately controlling Al2O3/SiO2With MgO/CaO ratio and respective content range so that glass fibre
Not only there is high modulus of elasticity, while melt drawing performance and recrystallization temperature are in tolerance interval；And add suitably
The TiO that ratio ionic radius is small, electric-field intensity is big2, ZnO and ZrO2, the modulus of elasticity of glass fibre can be further lifted again,
And produce certain effect for suppressing devitrification of glass.Therefore, because containing said components in glass fibre of the present invention, and accurately control
The content and ratio of each component, so that glass fibre obtains excellent mechanical property and the processability compared with low viscosity.
Present invention also offers a kind of glass fibre, prepared by above-mentioned composition.
The present invention has no particular limits to the preparation method of the glass fibre, can know for those skilled in the art
Method, preferably tank furnace method produce, can specifically prepare by the following method：
Tank furnace is put into after various raw materials are well mixed, after fusing, clarification, homogenizing, glass metal is obtained；
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 being well mixed, is transported to tank furnace feed bin；Then
Compound is put into tank furnace by tank furnace feed bin, is melted under conditions of 1400~1800 DEG C, clarification and homogenization, obtains glass
Liquid；
The glass metal is cooled to 1250~1350 DEG C, flowed out through platinum bushing plate, under the traction of wire drawing machine, wire drawing into
A diameter of 3~25 μm of glass fiber；
The glass fiber is obtained into glass fibre by misting cooling, size coating.
After glass fibre is obtained, performance test is carried out to the glass fibre.
Test result indicates that, the forming temperature of glass fibre of the present invention is no more than 1350 DEG C, and crystallization ceiling temperature is less than
1300 DEG C, the modulus of elasticity of glass fibre is more than 95GPa.
Embodiment
In order to further illustrate the present invention, the glass fiber compound and glass provided with reference to embodiment the present invention
Glass fiber is described in detail.
Embodiment 1
By each feedstock transportation to mixing tank, after being well mixed, compound is delivered to tank furnace feed bin, each raw material contains
Amount is according to shown in table 1；
Compound in tank furnace feed bin is put into tank furnace, in tank furnace, compound gradually melts through more than 1400 DEG C of high temperature
It is melted into after glass metal, clarified, homogenizing, it is stable and the glass metal of high-quality enters wire-drawing operation passage；
Glass metal in wire-drawing operation passage is cooled to after suitable temperature, flowed out through platinum bushing plate, it is quick by wire drawing machine
The glass fiber of 3~25 μm of diameter is distracted into, glass fiber is wound in after misting cooling, size coating, boundling on wire drawing machine
Spinning cake；
All spinning cakes obtain glass fibre after the process such as twist thread, weave cotton cloth, be surface-treated.
Performance test is carried out to the glass fibre, as a result referring to table 1, table 1 is that the embodiment of the present invention and comparative example are provided
Glass fibre formula and performance.
Embodiment 2~6
Preparation method is same as Example 1, and simply the content of each raw material is changed, specific as shown in table 1.
Performance test is carried out to the glass fibre, as a result referring to table 1, table 1 is that the embodiment of the present invention and comparative example are provided
Glass fibre formula and performance data table.
Comparative example 1~2
According to the formula shown in table 1, by various feedstock transportations to mixing tank, after being well mixed, compound is delivered to pond
Kiln feed bin, the content of each raw material is according to shown in table 1；
Compound in tank furnace feed bin is put into tank furnace, in tank furnace, compound gradually melts through more than 1400 DEG C of high temperature
It is melted into after glass metal, clarified, homogenizing, it is stable and the glass metal of high-quality enters wire-drawing operation passage；
Glass metal in wire-drawing operation passage is cooled to after suitable temperature, flowed out through platinum bushing plate, it is quick by wire drawing machine
The glass fiber of 3~25 μm of diameter is distracted into, glass fiber is wound in after misting cooling, size coating, boundling on wire drawing machine
Spinning cake；
All spinning cakes obtain glass fibre after the process such as twist thread, weave cotton cloth, be surface-treated.
Performance test is carried out to the glass fibre, as a result referring to table 1, table 1 is that the embodiment of the present invention and comparative example are provided
Glass fibre formula and performance data table.
The formula and performance data table for the glass fibre that the embodiment of table 1 and comparative example are provided
From above-described embodiment and comparative example, the present invention is improved by accurate adjustment various ingredients and its concrete content
The combination property of glass fibre.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
1. a kind of glass fiber compound, it is characterised in that including following component：
2. composition according to claim 1, it is characterised in that the SiO2Content is 52wt%~55.8wt%；It is described
Al2O3Content is 19wt%~22.5wt%；The SiO2With Al2O3Total content be 73.5wt%~77.6wt%；It is described
Al2O3/SiO2Mass fraction ratio is 0.36~0.42.
3. composition according to claim 1, it is characterised in that the TiO2Content is 1.0wt%~2.0wt%.
4. composition according to claim 1, it is characterised in that the CaO content is 6.4wt%~9.6wt%；It is described
Content of MgO is 9.4wt%~11.4wt%；The total content of the CaO and MgO are 17.2wt%~19.8wt%；The MgO/
CaO mass fractions ratio is 1.1~1.44.
5. composition according to claim 1, it is characterised in that the ZrO2Content is 3.2wt%~4.5wt%.
6. composition according to claim 1, it is characterised in that the ZnO content is 0.5wt%~1.5wt%.
7. composition according to claim 1, it is characterised in that the Na2O、K2O and Li2O total content is 0.5wt%
~0.8wt%.
8. composition according to claim 1, it is characterised in that the TiO2, ZnO and ZrO2Total content be 5.0wt%
~7.0wt%.
9. composition according to claim 1, it is characterised in that the composition also includes：F no more than 3wt%2、
B2O3、Y2O3、BaO、La2O3And CeO2In one or more.
10. a kind of glass fibre, it is characterised in that prepared as the composition described in any one of claim 1~9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710413849.5A CN107082569A (en) | 2017-06-05 | 2017-06-05 | A kind of glass fiber compound and glass fibre |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710413849.5A CN107082569A (en) | 2017-06-05 | 2017-06-05 | A kind of glass fiber compound and glass fibre |
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| Publication Number | Publication Date |
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| CN107082569A true CN107082569A (en) | 2017-08-22 |
Family
ID=59608714
Family Applications (1)
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| CN201710413849.5A Pending CN107082569A (en) | 2017-06-05 | 2017-06-05 | A kind of glass fiber compound and glass fibre |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373268A (en) * | 2018-04-08 | 2018-08-07 | 重庆国际复合材料股份有限公司 | A kind of high-modulus glass fiber composition and glass fibre |
| CN108395109A (en) * | 2018-04-08 | 2018-08-14 | 重庆国际复合材料股份有限公司 | A kind of high-modulus glass fiber composition and glass fibre |
| CN108545949A (en) * | 2018-06-04 | 2018-09-18 | 泰安顺茂新材料技术有限公司 | Can fibrosis glass composition and preparation method |
| CN108609859A (en) * | 2018-06-07 | 2018-10-02 | 重庆国际复合材料股份有限公司 | A kind of novel high-modulus glass fiber composition and glass fibre |
| US11214512B2 (en) | 2017-12-19 | 2022-01-04 | Owens Coming Intellectual Capital, LLC | High performance fiberglass composition |
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| CN105084768A (en) * | 2015-08-11 | 2015-11-25 | 重庆国际复合材料有限公司 | Composite for glass fiber preparation, high-modulus glass fiber and method for preparing high-modulus glass fiber |
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2017
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| JP2003005318A (en) * | 2001-06-26 | 2003-01-08 | Nix Co Ltd | Automatic developing machine |
| CN102849958A (en) * | 2012-10-12 | 2013-01-02 | 重庆国际复合材料有限公司 | Glass fiber |
| CN103449728A (en) * | 2013-08-23 | 2013-12-18 | 中材科技股份有限公司 | Corrosion-resistant high-strength high-modulus fiber and fabric prepared from fiber |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11214512B2 (en) | 2017-12-19 | 2022-01-04 | Owens Coming Intellectual Capital, LLC | High performance fiberglass composition |
| CN108373268A (en) * | 2018-04-08 | 2018-08-07 | 重庆国际复合材料股份有限公司 | A kind of high-modulus glass fiber composition and glass fibre |
| CN108395109A (en) * | 2018-04-08 | 2018-08-14 | 重庆国际复合材料股份有限公司 | A kind of high-modulus glass fiber composition and glass fibre |
| WO2019196590A1 (en) * | 2018-04-08 | 2019-10-17 | 重庆国际复合材料股份有限公司 | High modulus glass fiber composition and glass fiber |
| CN108545949A (en) * | 2018-06-04 | 2018-09-18 | 泰安顺茂新材料技术有限公司 | Can fibrosis glass composition and preparation method |
| CN108545949B (en) * | 2018-06-04 | 2019-08-13 | 泰安顺茂新材料技术有限公司 | Can fibrosis glass composition and preparation method |
| CN108609859A (en) * | 2018-06-07 | 2018-10-02 | 重庆国际复合材料股份有限公司 | A kind of novel high-modulus glass fiber composition and glass fibre |
| CN108609859B (en) * | 2018-06-07 | 2021-09-24 | 重庆国际复合材料股份有限公司 | Novel high-modulus glass fiber composition and glass fiber |
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Address after: 400082 Dadukou District of Chongqing Bridge Industrial Park B District Applicant after: Chongqing international composite Limited by Share Ltd Address before: 400082 Chongqing Polycomp International Corporation Dadukou District of Chongqing Bridge Industrial Park B District Applicant before: Chongqing Polycomp International Corp. |
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Application publication date: 20170822 |