CN101580344A - High strength glass fiber composition - Google Patents

High strength glass fiber composition Download PDF

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Publication number
CN101580344A
CN101580344A CNA2009100999787A CN200910099978A CN101580344A CN 101580344 A CN101580344 A CN 101580344A CN A2009100999787 A CNA2009100999787 A CN A2009100999787A CN 200910099978 A CN200910099978 A CN 200910099978A CN 101580344 A CN101580344 A CN 101580344A
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glass fiber
mgo
cao
glass
sio
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CN101580344B (en
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张毓强
曹国荣
张兵
章林
邢文忠
顾桂江
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Jushi Group Co Ltd
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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a high strength glass fiber composition which comprises the components with the weight percentage: 58-65% of SiO2, 14-20% of Al2O3, 15-25% of CaO+MgO, 0.05-1% of K2O+Na2O, 0.05-1% of Fe2O3 and 0.1-2% of CeO2; wherein, the proportional relation of the components is that CaO/MgO is more than 0.7 and less than 2.2. By preference and combination of the components, the high strength glass fiber composition not only can fully utilize rich raw mineral materials of China, but also can reduce mold temperature, liquidus temperature and clarification temperature and has lower total cost and easy large scale commercial process under the premise of ensuring the high strength of glass fiber.

Description

A kind of high strength glass fiber composition
(1) technical field
The present invention relates to a kind of glass fiber compound, relate in particular to a kind of high strength glass fiber composition.
(2) background technology
Glass fibre belongs to inorganic fibers, strengthens the matrix material that resin can make excellent property with it.High strength glass fiber is mainly used in defence and military fields such as Aeronautics and Astronautics, weapons at first as the enhancing base material of advanced composite material.Along with the progress and the expanding economy of science and technology, high strength glass fiber has obtained widespread use in civilian, industrial circle such as motor, wind blade, pressurized vessel, offshore oil pipeline, sports equipment, automobile industry.
After U.S. Ovens-Kening Co.,Ltd develops the S glass fibre, various countries are the high strength glass fiber of the various compositions of Development and Production competitively, as the R glass fibre of company of French Saint-Gobain exploitation, the BMII glass fibre that Byelorussia Polotsk company produces, the high-strength 2# glass fibre of Nanjing of China glass fibre studying and designing institute exploitation etc.Wherein, the main component of S glass fibre is SiO 2, Al 2O 3, MgO, its glass ware forming temperature is higher, wire-drawing temperature up to 1571 ℃ about, liquidus temperature reaches 1470 ℃, the difficulty that this causes in the glass preparation is difficult to realize large-scale industrial production.At SiO 2, Al 2O 3, the MgO ternary component the basis on, also introduced Li in the composition of high-strength 2# glass fibre 2O, B 2O 3, CeO 2, Fe 2O 3Its mold temperature has only about 1245 ℃, liquidus temperature is 1320 ℃, both temperature are all much lower than S glass fibre, but its mold temperature must improve wire-drawing temperature than the low good drawing that but is unfavorable for glass of liquidus temperature, adopt leting slip a remark of special shape, to prevent that glass devitrification phenomenon takes place in the drawing process, the difficulty that this causes in the temperature control also is difficult to realize large-scale industrial production.
(3) summary of the invention
The present invention is directed to the problem of above-mentioned existence, a kind of high strength glass fiber composition is proposed, guaranteeing under the high-intensity prerequisite of glass fibre, it can make full use of the raw mineral materials of China's abundant, can realize the reduction of mold temperature, liquidus temperature and clarifying temp again, and overall cost is lower, is easy to realize large-scale industrial production.
For solving the problems of the technologies described above, the agent technology scheme that the present invention adopts is: a kind of high strength glass fiber composition, contain following component, based on described SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 2, each components contents is expressed as follows with weight percent:
SiO 2 58～65％
Al 2O 3 14～20％
CaO+MgO 15～25％
K 2O+Na 2O 0.05～1％
Fe 2O 3 0.05～1％
CeO 2 0.1～2％
Wherein, component concentration is followed following proportionlity: 0.7＜CaO/MgO＜2.2.
In the glass fiber compound of the present invention, SiO 2Be the main oxides that forms the glass skeleton, and work to stablize each component.The present invention limits SiO 2Content range be 58～65%, if its content too low can influence glass intensity; If its content too Gao Zehui makes the too high clarification difficulty that causes of the viscosity of glass.Preferred SiO 2Content range is 59～62%.
In glass fiber compound of the present invention, Al 2O 3Also be the oxide compound that forms the glass skeleton, and playing an important role aspect prevention glass phase-splitting and the water resisting property.The present invention limits Al 2O 3Content range be 14～20%, if the too low meeting of its content raises liquidus temperature, make glass intensity and water resisting property variation simultaneously; If its content too Gao Zehui makes the too high clarification difficulty that causes of the viscosity of glass.Preferred Al 2O 3Content range is 15～18%.
In the glass fiber compound of the present invention, CaO and MgO mainly play the effect of regulating glass viscosity and feed glass crystallization.Glass fiber compound of the present invention is with SiO 2, Al 2O 3, CaO, MgO four-tuple be divided into main body, by the content ratio of appropriate design CaO, MgO, introduced lime feldspar (CaAl 2Si 2O 8) and diopside (CaMgSi 2O 6) competitive growth between the crystal, thereby delay this two kinds of crystalline growths, reach the purpose that reduces the danger of glass devitrification.The total content scope that the present invention limits CaO and MgO is 15～25%, and the proportional range of regulation CaO/MgO is 0.7～2.2, if the too low meeting of its ratio causes and can't normally introduce two kinds of crystalline competitive growths; If its ratio too Gao Zehui causes two kinds of crystalline competitive growths unbalance, increase the danger of glass devitrification on the contrary.The total content scope of preferred CaO of the present invention and MgO is 17～23%, and preferred proportional range is 1～1.8.
Because high-strength glass relatively is difficult to the fusing clarification, in order to guarantee the clear quality of glass metal, fully homogenizing glass has been introduced CeO in the glass fiber composition of the present invention 2, it not only can play good clarification and nontoxic, the part oxidation of divalent iron ion can also be become ferric ion, and the green of glass fibre is shoaled.The present invention limits CeO 2Content range be 0.1～2%, preferred CeO 2Content range is 0.1～1.5%.
In the glass fiber compound of the present invention, also introduce minor N a 2O and K 2O can reduce glass viscosity, improves the crystallization property of glass.But the introducing amount is unsuitable many, to avoid reducing glass intensity.The present invention limits Na 2O and K 2The total content scope of O is 0.05～1%.
In the glass fiber compound of the present invention, Fe 2O 3Introducing play fluxing action preferably, it can reduce glass viscosity, improves the moulding and the crystallization property of glass.The present invention limits Fe 2O 3Content range be 0.05～1%.
On the basis of major scheme, can introduce a spot of Li in the glass fiber compound of the present invention 2O can improve the processability of glass effectively under the situation of not damaging intensity.But Li 2The introducing amount of O is unsuitable excessive, because excessive Li 2Silicon structure in the broken easily ring glass structure of O, thus glass intensity is descended; In addition, contain Li 2The cost of material of O is higher, has improved production cost significantly.The present invention limits Li 2The content of O is SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 20.1～1% of gross weight.
On the basis of major scheme, also can introduce B in the glass fiber compound of the present invention 2O 3, B 2O 3Introducing play fluxing action preferably, it can reduce glass viscosity, improves the moulding and the crystallization property of glass.The present invention limits B 2O 3Content be SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 20.1～2% of gross weight.
On the basis of major scheme, can also introduce a spot of fluorine in the glass fiber compound of the present invention and improve glass melting.The present invention limits F in the described glass fiber compound 2Content be SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 20～0.5% of gross weight, its lower limit 0% expression is substantially equal to zero but non-vanishing; Be preferably 0.05～0.5%.
In addition, on the basis of major scheme, also can introduce a spot of TiO in the glass fiber compound of the present invention 2, to bring into the impurity form by raw mineral materials basically, the glass viscosity when it not only can reduce high temperature also has certain fluxing action.The present invention limits TiO in the described glass fiber compound 2Content be SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 20～1% of gross weight, its lower limit 0% expression is substantially equal to zero but non-vanishing; Be preferably 0.05～1%.
Preferred version 1 of the present invention:
Described glass fiber composition is made up of following component, based on described SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 2, each component is expressed as follows with weight percent:
SiO 2 58-65％
Al 2O 3 14～20％
CaO+MgO 15～25％
K 2O+Na 2O 0.05～1％
Fe 2O 3 0.05～1％
CeO 2 0.1～2％
TiO 2 0～1％
F 2 0～0.5％
Wherein, component concentration is followed following proportionlity: 1＜CaO/MgO＜1.8.
Preferred version 2:
Described glass fiber composition is made up of following component, based on described SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 2, each component is expressed as follows with weight percent:
SiO 2 58～65％
Al 2O 3 14～20％
CaO+MgO 15～25％
K 2O+Na 2O 0.05～1％
Fe 2O 3 0.05～1％
CeO 2 0.1～2％
Li 2O 0.1～1％
TiO 2 0～1％
Wherein, component concentration is followed following proportionlity: 1＜CaO/MgO＜1.8.
Preferred version 3:
Described glass fiber composition is made up of following component, based on described SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 2, each component is expressed as follows with weight percent:
SiO 2 59～62％
Al 2O 3 15～18％
CaO+MgO 17～23％
K 2O+Na 2O 0.05～1％
Fe 2O 3 0.05～1％
CeO 2 0.1～1.5％
B 2O 3 0.1～2％
Li 2O 0.1～1％
TiO 2 0～1％
Wherein, component concentration is followed following proportionlity: 1＜CaO/MgO＜1.8.
Compared with prior art, beneficial effect of the present invention is: the present invention is by the preferred and combination to component, guaranteeing under the high-intensity prerequisite of glass fibre, it can make full use of the raw mineral materials of China's abundant, can realize the reduction of mold temperature, liquidus temperature and clarifying temp again, and overall cost is lower, is easy to realize large-scale industrial production.
(4) embodiment
By the following examples technical scheme of the present invention is specifically described, content of the present invention is not subjected to any restriction of following examples.Wherein embodiment component total content is slightly less than 100%, and can be understood as residual volume is a small amount of component that trace impurity maybe can not analyze.
The detailed process of the embodiment of the invention is as follows: each component can be obtained from suitable raw material, in proportion various raw materials are mixed, make each component reach final expection weight percent, mixed admixtion melts and clarifies, thereby glass metal is drawn out by leting slip a remark on the bushing and forms glass fibre then, glass fibre is pulled around form former spinning cake or yarn group to the drawing wire machine rotating head, and these glass fibre can carry out deep processing to meet the expected requirements with ordinary method.
Listed six embodiment of the present invention in table 1 and the table 2, it is numbered C1-C6, and two comparative examples are arranged in addition, is respectively traditional E glass and high-strength S glass.Each components contents of glass fiber compound is represented with weight percent in the table.
For the advantage of glass fiber compound of the present invention is described, provided four basic parameters in the table:
The 1-mold temperature is 10 corresponding to glass melt in viscosity 3Temperature during pool.
The 2-liquidus temperature, the temperature that nucleus begins to form when cooling off corresponding to glass melt, the i.e. ceiling temperature of devitrification of glass.
3-Δ T value, mold temperature and liquidus temperature poor, the temperature range of the wire-drawing shape that expresses possibility.
The 4-filament strength, the drawing force that glass fiber precursor unit's fineness can be born.
Above-mentioned four basic parameters and measuring method thereof are that those skilled in the art are known.
By table 1 and table 2 as can be known, with high-strength S glassy phase ratio, glass fiber composition of the present invention has much lower mold temperature and liquidus temperature, and this helps cutting down the consumption of energy, and slows down the high temperature ageing of kiln and bushing.With traditional E glassy phase ratio, glass fiber composition of the present invention has much higher filament strength.This shows that it is well compromise that glass fiber composition of the present invention has reached, and than S glass more economically, be easy to realize the suitability for industrialized production of high strength glass fiber between the intensity of fusing, wire-drawing performance and the glass fibre of glass.
Table 1
Figure A20091009997800111
Table 2
Figure A20091009997800121

Claims (10)

1. a high strength glass fiber composition contains following component, based on described SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 2, each components contents is expressed as follows with weight percent:
SiO 2 58～65％
Al 2O 3 14～20％
CaO+MgO 15～25％
K 2O+Na 2O 0.05～1％
Fe 2O 3 0.05～1％
CeO 2 0.1～2％
Wherein, component concentration is followed following proportionlity: 0.7＜CaO/MgO＜2.2.
2, glass fiber compound according to claim 1 is characterized in that also containing in the described glass fiber composition Li 2O, its content are SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 20.1～1% of gross weight.
3, glass fiber compound according to claim 1 is characterized in that also containing in the described glass fiber composition B 2O 3, its content is SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 20.1～2% of gross weight.
4, glass fiber compound according to claim 1 is characterized in that also containing in the described glass fiber composition F 2, its content is SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 20～0.5% of gross weight.
5, glass fiber compound according to claim 1 is characterized in that also containing in the described glass fiber composition TiO 2, its content is SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 20～1% of gross weight.
6, according to the described glass fiber compound of one of claim 1～5, the content that it is characterized in that CaO+MgO in the described glass fiber composition is 17～23%.
7,, it is characterized in that the ratio of the content of CaO and MgO in the described glass fiber composition is 1～1.8 according to the described glass fiber compound of one of claim 1～5.
8, glass fiber compound according to claim 1 is characterized in that described glass fiber composition is made up of following component, based on described SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 2, be expressed as follows with weight percent:
SiO 2 58～65％
Al 2O 3 14～20％
CaO+MgO 15～25％
K 2O+Na 2O 0.05～1％
Fe 2O 3 0.05～1％
CeO 2 0.1～2％
TiO 2 0～1％
F 2 0～0.5％
Wherein, component concentration is followed following proportionlity: 1＜CaO/MgO＜1.8.
9, glass fiber compound according to claim 1 is characterized in that described glass fiber composition is made up of following component, based on described SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 2, be expressed as follows with weight percent:
SiO 2 58～65％
Al 2O 3 14～20％
CaO+MgO 15～25％
K 2O+Na 2O 0.05～1％
Fe 2O 3 0.05～1％
CeO 2 0.1～2％
Li 2O 0.1～1％
TiO 2 0～1％
Wherein, component concentration is followed following proportionlity: 1＜CaO/MgO＜1.8.
10, glass fiber compound according to claim 1 is characterized in that described glass fiber composition is made up of following component, based on described SiO 2, Al 2O 3, CaO, MgO, K 2O, Na 2O, Fe 2O 3And CeO 2, be expressed as follows with weight percent:
SiO 2 59～62％
Al 2O 3 15～18％
CaO+MgO 17～23％
K 2O+Na 2O 0.05～1％
Fe 2O 3 0.05～1％
CeO 2 0.1～1.5％
B 2O 3 0.1～2％
Li 2O 0.1～1％
TiO 2 0～1％
Wherein, component concentration is followed following proportionlity: 1＜CaO/MgO＜1.8.
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