CN108503227A - A kind of high-performance glass fiber composition and glass fibre - Google Patents
A kind of high-performance glass fiber composition and glass fibre Download PDFInfo
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- CN108503227A CN108503227A CN201810305970.0A CN201810305970A CN108503227A CN 108503227 A CN108503227 A CN 108503227A CN 201810305970 A CN201810305970 A CN 201810305970A CN 108503227 A CN108503227 A CN 108503227A
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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
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Abstract
The present invention relates to a kind of high-performance glass fiber composition and glass fibres.The present invention provides a kind of high-performance glass fiber compositions, including following component：SiO250wt%~55.9wt%；Al2O320.1wt%~24wt%；SiO2With Al2O3Total content 70.5wt%~79.5wt%；TiO20.2wt%~1.5wt%；0~2.0wt% of ZnO；ZrO20~2.0wt%；Fe2O30.1wt%~0.6wt%；CaO 4wt%~8wt%；MgO12.1wt%~17wt%；Total content 16.5wt%~24.5wt% of CaO and MgO；B2O33.5~6wt%；Li2O、Na2O and K2Total content 0.2wt%~1.0wt% of O；Said components amount to 100%.The particular percentile content that the present invention passes through the above-mentioned each component of control so that finally obtained high-performance glass fiber composition has high-modulus, low production difficulty and good comprehensive performance.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials more particularly to a kind of high-performance glass fiber composition and
Glass fibre.
Background technology
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, and with glass fiber compound material increasingly enlargement, light-weighted development trend, people are to glass
The mechanical property of glass fiber especially specific strength, specific modulus modulus propose increasingly higher demands.
For promoted glass fiber strength and modulus method, at present there are many correlative study.Most typical is exactly S
Glass and R glass.S glass basic composition is：The SiO of 65wt%2, the Al of 25wt%2O3, the MgO of 10wt%.S glass fibres
Theoretical filament strength is up to 4500MPa, and elasticity modulus is more than 85GPa, and mechanical property is very excellent.But its forming temperature is more than
1470 DEG C, and easily crystallization, production difficulty is very big, cannot achieve 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
A kind of compromise, to compared with S glass, have more producing feasibility.
Chinese patent CN200480015986.4 discloses a kind of glass fiber compound, it contains 50~65wt%'s
SiO2, the Al of 12~20wt%2O3, the B of the MgO of the CaO of 13~16wt%, 6~12wt%, 0~3wt%2O3,0~3wt%'s
TiO2,The K of 0~2wt%2O+Na2O.The glass fibre belongs to R grades of glass, by controlling Al2O3It is obtained preferably with CaO content
Mechanical property and meltdown property, but specific modulus only has 35-36MPa.kg-1.m3, it is difficult to meet the needs of higher performance.
Chinese patent CN200680041114.4 discloses a kind of high-performance glass fiber composition, and it contains 60.5~
The SiO of 70.5wt%2, the Al of 10~24.5wt%2O3, the R of the RO of 6~20wt%, 0~3wt%2O.The patent glass fibre
Composition also belongs to R grades of glass scopes in fact, but its interest field announced is excessively wide in range, and general row industry personnel is difficult to pass through
Its technical solution easily realizes its technical goal.
Japan Patent JP2003171143 also illustrates a kind of high-strength high-performance glass fibre, it contains 55~65wt%
SiO2, the Al of 17~23wt%2O3, the TiO of the CaO of the MgO of 7~15wt%, 2~6wt%, 1~7wt%2.Compared with S glass
Glass, although the glass fibre mechanical property is sacrificed, processability, which has, to be obviously improved, and forming temperature is about 1340~
1380℃.But TiO in the glass2Content is very high so that glass colour is partially deep, and which has limited its applications in certain fields.
A kind of high strength glass fiber composition of the U.S. Patent Publication of Publication No. US2010/0160139, including：
The SiO of 64~75wt%2, the Al of 16~24wt%2O3, the Li of the MgO of 8~12wt%, 0.25~3wt%2O+Na2O.Relative to
S glasses, this glass fibre add a certain amount of Li2O and Na2O reduces glass so as to improve the high temperature melting situation of glass
It is molded difficulty.
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 is less than the Li of 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, due to reducing Li2O dosages, in order to balance its production difficulty, it is again
Add be more than 1% Na2O, and this may bring more side effects.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of high-performance glass fiber composition and glass
Glass fiber has high-modulus, low production difficulty and good comprehensive performance.
The present invention provides a kind of high-performance glass fiber compositions, including following component：
Preferably, the SiO2Content is 50.6wt%~55.9wt%；The Al2O3Content be 20.4wt%~
23.6wt%；The SiO2With Al2O3Total content be 71.1wt%~79.2wt%.
Preferably, the TiO2Content is 0.2wt%~0.9wt%.
Preferably, the CaO content is 4.5wt%~7.9wt%；The content of MgO is 12.1wt%~16wt%；Institute
The total content for stating CaO and MgO is 17wt%~23.5wt%.
Preferably, the ZrO2Content is 0.2wt%~1.2wt%.
Preferably, the ZnO content is 0.5wt%~1.6wt%.
Preferably, the Fe2O3Content is 0.2wt%~0.5wt%.
Preferably, the B2O3Content is 3.5~5wt%.
Preferably, the Li2O、Na2O、K2Total content 0.3wt%~0.8wt% of O.
The present invention provides a kind of high-performance glass fibers, are prepared by the composition described in above-mentioned technical proposal.
Compared with prior art, the present invention provides a kind of high-performance glass fiber compositions, including following component：SiO2
50wt%~55.9wt%；Al2O320.1wt%~24wt%；SiO2With Al2O3Total content 70.5wt%~79.5wt%；
TiO20.2wt%~1.5wt%；0~2.0wt% of ZnO；ZrO20~2.0wt%；Fe2O30.1wt%~0.6wt%；
CaO 4wt%~8wt%；MgO12.1wt%~17wt%；Total content 16.5wt%~24.5wt% of CaO and MgO；B2O3
3.5~6wt%；Li2O、Na2O and K2Total content 0.2wt%~1.0wt% of O；Said components amount to 100%.The present invention passes through
Control the particular percentile content of above-mentioned each component so that finally obtained high-performance glass fiber composition have high-modulus,
Low production difficulty and good comprehensive performance.
Specific implementation mode
The present invention provides high-performance glass fiber composition and glass fibre, those skilled in the art can use for reference this
Literary content is suitably modified technological parameter realization.In particular, it should be pointed out that all similar substitutions and modifications are to art technology
It is it will be apparent that they shall fall within the protection scope of the present invention for personnel.The present invention method and application by compared with
Good embodiment is described, related personnel obviously can not depart from the content of present invention, in spirit and scope to methods herein
It is modified or suitably changes and combine with application, to realize and apply the technology of the present invention.
The present invention provides a kind of high-performance glass fiber compositions, including following component：
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 can increase the viscosity and fusion temperature of glass,
Cause glass fibre molding difficulty and production cost higher.SiO in the present composition2Content is 50wt%~55.9wt%,
Preferably 50.6wt%~55.9wt%, more preferably 50.8wt%~55.8wt%；Most preferably 50.8wt%~
55.4wt%.
Aluminium oxide (Al2O3) be also to form one of main oxides of glass network, it have improve glass mechanical property,
Improve the effect of chemical durability of glass, but since there are two types of ligand forms in glass network for aluminium oxide, the mode of action is more
It is complicated.If Al2O3Content range is improper, just will appear the problems such as glass viscosity is excessive, glass is difficult at fibre, easy crystallization.This hair
Al in bright composition2O3Content is 20.1wt%~24wt%, preferably 20.4wt%~23.6wt%；More preferably
20.4wt%~23.5wt%.
In addition, the present invention further defines SiO2With Al2O3Total content be 70.5wt%~79.5wt%, preferably
71.1wt%~79.2wt%.
Calcium oxide (CaO) and magnesia (MgO) generally belong to glass network modifier oxides in alkali-free glass system,
Have the function of reducing glass high temperature viscosity, improve devitrification of glass tendency.Wherein MgO ionic radius are less than CaO, thus higher
MgO ratios contribute to form finer and close glass network structure, promote glass modulus.It is raw but if content of MgO is excessively high
Production difficulty can become difficult to receive.CaO content described in the present composition is 4wt%~8wt%, it is preferred that CaO content is
4.5wt%~7.9wt%, more preferably 5.2wt%~7.8wt%；Most preferably 5.2wt%~7.6wt%；Content of MgO is
12.1wt%~17wt%, it is preferred that content of MgO is 12.1wt%~16wt% in the present composition, more preferably
12.1wt%~14.8wt%；Most preferably 12.2wt%~14.6wt%；The total content of CaO and MgO be 16.5wt%~
24.5wt%, preferably 17wt%~23.5wt%, more preferably 17.3wt%~21.8wt%.
Titanium dioxide (TiO2) addition help to improve glass temperature flowing and tendency towards devitrification, improve fiberglass woven
Tool performance and corrosion resistance.But otherwise the content of titanium dioxide can influence glass colour no more than 1.5wt%.The present invention
TiO in composition2Content be 0.2wt%~1.5wt%, preferably 0.2wt%~0.9wt%；More preferably 0.2wt%~
0.8wt%；Most preferably 0.2wt%~0.7wt%.
Zinc oxide (ZnO) and zirconium oxide (ZrO can also be added in glass fibre of the present invention2), this kind of ionic radius is small, electric
The big oxide of field intensity has the function of improving devitrification of glass performance, improves elasticity modulus and chemical durability of glass.This hair
In bright composition, ZnO content is 0~2.0wt%, it is preferred that ZnO content is 0.5wt%~1.6wt%；The present composition
Middle ZrO2Content is 0~2.0wt%, it is preferred that ZrO2Content is 0.2wt%~1.2wt%；More preferably 0.5wt%~
1.0wt%.
A small amount of iron oxide (Fe contained therein2O3) be conducive to tank furnace heat transfer, but if too high levels, to glass
The color and heat transfer property of fiber all adversely affect.Iron oxide content of the present invention is limited to 0.1wt%~0.6wt%, preferably
For 0.2wt%~0.5wt%；More preferably 0.3wt%~0.4wt%.
The present invention is special, and a certain amount of boron oxide (B is also added in the glass fiber compound2O3).A small amount of
B2O3Strengthens network intensity in glass network can be entered, to improve glass mechanical property, while it additionally aids reduction glass
High temperature viscosity accelerates clarification, improves the effect of devitrification of glass tendency.Glass composition B of the present invention2O3Content is 0~6wt%, preferably
For 3.5wt%~6.0wt%, more preferably 3.5wt%~5.0wt%.
Contain a small amount of Na in glass fiber compound of the present invention2O and K2O, and it is substantially free of Li2O.They are usually to introduce
Other components adjust the impurity component brought into when glass melting atmosphere, do not add individually generally.A small amount of Na2O and K2O contributes to
Reduce glass viscosity, improve devitrification of glass tendency, if but content it is higher, the chemical stability of glass can be damaged.Glass of the present invention
Glass composition Li2O、Na2O、K2O total contents are 0.2wt%~1.0wt%, more preferably 0.3wt%~0.8wt%.
According to the present invention, preferably, under the premise of not influencing glass fibre mechanical property, in order to improve glass
Fiberizing performance, glass fiber compound of the present invention can also contain the F no more than 3wt%2、Y2O3、BaO、La2O3、CeO2
In it is one or more.
For alkali-free glass fibre, composition design is very challenging property in fact.On the one hand, alkali-free glass fibre master
Form usually nothing but SiO2、Al2O3、B2O3, MgO, CaO, then be equipped with a small amount of assisted oxidation object, the space that can design adjustment has
Limit；On the other hand, a kind of outstanding glass fibre require again mechanical property, meltdown property, chemical stability, production difficulty,
It is optimal as possible in terms of manufacturing cost and certain properties, and usually the two is conflicting.Therefore, glass fibre
The key points and difficulties of design are that how to find most appropriate makes its performance and production difficulty reach optimum balance at subassembly
Point.The present invention has found the optimal proportion of each key component by theoretical modeling and a large amount of contrast experiment, obtained glass fibers
Dimension not only has excellent mechanical property, while its melt drawing performance and production difficulty significantly reduce.
The present invention also provides a kind of high-performance glass fibers, are prepared by above-mentioned composition.
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 according to formula, after fusing, clarification, homogenizing, obtain glass metal；
The glass metal obtains glass fibre after temperature adjustment, outflow and wire drawing process.
The present invention first mixes various raw materials according to recipe calculation in mixing tank, after mixing, is transported to
Tank furnace feed bin；Then batch automatic ration is put into tank furnace by tank furnace feed bin, melted under conditions of 1400~1800 DEG C,
Clarification and homogenization obtain grade glass liquid；
The glass metal is cooled to 1250~1350 DEG C, is flowed out through platinum bushing plate, under the traction of wire drawing machine, wire drawing at
A diameter of 3~25 μm of glass fiber；
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.
The experimental results showed that the forming temperature of glass fibre of the present invention is no more than 1300 DEG C, crystallization ceiling temperature is less than
1250 DEG C, the elasticity modulus of glass fibre is more than 95GPa.
In order to further illustrate the present invention, with reference to embodiment to high-performance glass fiber composition provided by the invention
And glass fibre is described in detail.
Embodiment 1
According to the formula calculated by each feedstock transportation to mixing tank, after mixing, tank furnace is delivered to through feed proportioning system
Feed bin, the formula is according to shown in table 1；
Batch automatic ration in tank furnace feed bin puts into tank furnace, and in tank furnace, batch is through 1400 DEG C or more of high temperature
It is gradually fused into glass metal, after clarified, homogenizing, stablizes and the glass metal of high-quality enters wire-drawing operation channel；
It after glass metal is cooled to suitable temperature in wire-drawing operation channel, flows out through platinum bushing plate, is quickly led by wire drawing machine
Draw into the glass fiber of 3~25 μm of diameter, glass fiber is wound in silk after misting cooling, size coating, boundling on wire drawing machine
Cake；
All spinning cakes can be produced into various fiberglass products through the different processes such as chopped, drying, doff, braiding.
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.
Embodiment 2~6
Preparation method is same as Example 1, and only glass formula content is changed, specific as shown in table 1.
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.
Comparative example 1~2
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；
Batch automatic ration in tank furnace feed bin puts into tank furnace, and in tank furnace, batch is through 1400 DEG C or more of high temperature
It is gradually fused into glass metal, after clarified, homogenizing, stablizes and the glass metal of high-quality enters wire-drawing operation channel；
It after glass metal is cooled to suitable temperature in wire-drawing operation channel, flows out through platinum bushing plate, is quickly led by wire drawing machine
Draw into the glass fiber of 3~25 μm of diameter, glass fiber is wound in silk after misting cooling, size coating, boundling on wire drawing machine
Cake；
All spinning cakes can be produced into various fiberglass products through the different processes such as chopped, drying, doff, braiding.
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.
The formula and performance data table for the glass fibre that 1 embodiment of table and comparative example provide
By above-described embodiment and comparative example it is found that the present invention is improved by accurately adjusting various ingredients and its concrete content
The comprehensive performance of glass fibre.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.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 improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (10)
1. a kind of high-performance glass fiber composition, which is characterized in that including following component：
Said components amount to 100%.
2. composition according to claim 1, which is characterized in that the SiO2Content is 50.6wt%~55.9wt%；Institute
State Al2O3Content is 20.4wt%~23.6wt%；The SiO2With Al2O3Total content be 71.1wt%~79.2wt%.
3. composition according to claim 1, which is characterized in that the TiO2Content is 0.2wt%~0.9wt%.
4. composition according to claim 1, which is characterized in that the CaO content is 4.5wt%~7.9wt%；It is described
Content of MgO is 12.1wt%~16wt%；The total content of the CaO and MgO is 17wt%~23.5wt%.
5. composition according to claim 1, which is characterized in that the ZrO2Content is 0.2wt%~1.2wt%.
6. composition according to claim 1, which is characterized in that the ZnO content is 0.5wt%~1.6wt%.
7. composition according to claim 1, which is characterized in that the Fe2O3Content is 0.2wt%~0.5wt%.
8. composition according to claim 1, which is characterized in that the B2O3Content is 3.5~5wt%.
9. composition according to claim 1, which is characterized in that the Li2O、Na2O、K2The total content 0.3wt% of O~
0.8wt%.
10. a kind of high-performance glass fiber, which is characterized in that be prepared by claim 1~9 any one of them composition
It arrives.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810305970.0A CN108503227A (en) | 2018-04-08 | 2018-04-08 | A kind of high-performance glass fiber composition and glass fibre |
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| CN201810305970.0A CN108503227A (en) | 2018-04-08 | 2018-04-08 | A kind of high-performance glass fiber composition and glass fibre |
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ID=63380990
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279520A (en) * | 2020-11-06 | 2021-01-29 | 山东鑫恒新型材料有限公司 | High-performance glass fiber |
| US11214512B2 (en) | 2017-12-19 | 2022-01-04 | Owens Coming Intellectual Capital, LLC | High performance fiberglass composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003171143A (en) * | 2001-09-28 | 2003-06-17 | Nitto Boseki Co Ltd | Glass composition for glass fiber |
| CN1615280A (en) * | 2001-12-12 | 2005-05-11 | 罗克伍尔国际公司 | Fibres and their production |
| CN104781202A (en) * | 2012-10-18 | 2015-07-15 | Ocv智识资本有限责任公司 | Glass composition for the manufacture of fibers and process |
-
2018
- 2018-04-08 CN CN201810305970.0A patent/CN108503227A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003171143A (en) * | 2001-09-28 | 2003-06-17 | Nitto Boseki Co Ltd | Glass composition for glass fiber |
| CN1615280A (en) * | 2001-12-12 | 2005-05-11 | 罗克伍尔国际公司 | Fibres and their production |
| CN104781202A (en) * | 2012-10-18 | 2015-07-15 | Ocv智识资本有限责任公司 | Glass composition for the manufacture of fibers and process |
Cited By (2)
| 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 |
| CN112279520A (en) * | 2020-11-06 | 2021-01-29 | 山东鑫恒新型材料有限公司 | High-performance glass fiber |
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