CN105461231A - Chemical corrosion-resistance, high-strength and high-modulus glass fiber composition - Google Patents
Chemical corrosion-resistance, high-strength and high-modulus glass fiber composition Download PDFInfo
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- CN105461231A CN105461231A CN201510545056.XA CN201510545056A CN105461231A CN 105461231 A CN105461231 A CN 105461231A CN 201510545056 A CN201510545056 A CN 201510545056A CN 105461231 A CN105461231 A CN 105461231A
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Abstract
The invention relates to a chemical corrosion-resistance, high-strength and high-modulus glass fiber composition. The above glass fiber has high strength, high modulus, high temperature resistance, corrosion resistance and other comprehensive performances. The composition can be widely applied in high-performance composite materials and in heat and corrosion resistant environment. The composition is characterized in that 0.5-1.5wt% of ZrO2 is added, and no Li2O, TiO2 or F2 is added, so the high strength and the high modulus of the composition are guaranteed, and the acid and alkali resistance of glass is improved. The glass fiber composition adopts a SiO2-Al2O3-CaO-MgO four-component system as a main component, and mainly comprises 59.0-62.0wt% of SiO2, 16.0-19.0wt% of Al2O3, 8.0-13.0wt% of CaO, 9.0-11.0wt% of MgO, 0.5-1.2wt% of R2O and 0.5-1.50wt% of ZrO2. The glass fiber composition can realizes tank furnace process direct production.
Description
Technical field
The present invention relates to a kind of resistance to chemical attack high-strength high-modulus glass fiber composition, particularly relate to the high performance composite field that E glass fibre can not meet the demands, can in the field of environmental engineering of wind electricity blade, gas cylinder, chemical pipeline, heat-and corrosion-resistant and the widespread use of power engineering field.
Background technology
Along with glass fibre is at the expanding day of traffic, industry, building, environmental area, have more high strength, modulus, the special dimension such as resistance to acids and bases, resistance to deterioration, common alkali free glass fibre can not be met the need of market due to the defect of its performance.The glass fibre of existing multiple high strength and modulus in the market.Such as S-2 and R glass fibre, its tensile strength of fiber is up to 4400MPa, and the performance such as Young's modulus and heatproof improves greatly.S-2 glass fibre glass melting temperature needs 1650 DEG C, and fiberizing temperature reaches about 1470 DEG C, and nozzle plate temperature is high, and full platinum need be used just to found as the kiln of liner.In addition, owing to needing higher temperature to cause bushing life to shorten dramatically, production cost is very high limits application market.R glass fibre mold temperature is greater than 1370 DEG C, but its liquidus temperature is also large about 1350 DEG C, and both closely.The difference of fiberizing temperature and liquidus temperature and △ T, determine the processability of glass fibre.△ T is larger, and the suppleness in fiberglass moulding process is larger; On the contrary, △ T is less, just easily produces crystallization, damages bushing, reduces wire-drawing operation stability.The production cost of visible S-2 and R glass is quite high, and drawing process is also very harsh and be not suitable for large-scale production, limits market application.
Definition: 1: liquidus temperature-be commonly considered as: glass is by the top temperature of vitreous state to crystalline state, and now primary phase and liquid phase coexist and reaching balances each other.During higher than liquidus temperature, crystallization can not be produced; But during lower than liquidus temperature, glass melt can produce crystallization.
2: △ T: the difference of fiberizing temperature and liquidus temperature, determines the processability of fiberglass.△ T is larger, and the possibility producing crystallization in fiberglass moulding process is less; On the contrary, △ T is less, and the possibility producing crystallization increases, and particularly bushing Renewal process more easily produces crystallization, affects normal operation.
3: in essence without lithium phase: refer in formula and do not add oxidate for lithium, this formula, not containing lithium, reduces raw materials cost.
4: directly wire drawing tank furnace: this kind of glass is adapted at founding in similar E glass fibre refractory materials tank furnace kiln.
5: strain point: glass carries out the lower limit temperature of anneal.
6: softening temperature: glass fibre starts the temperature of softening.Softening point value is higher, and the temperature resistance of material can be better.
Summary of the invention
The shortcoming such as the mold temperature that the present invention is directed to existing high-performance reinforcing glass fiber is high, task difficulty is large, a kind of fire-resistant corrosion high strength, high-modulus glass fiber composition is newly devised by optimization of C/C composites, said composition can be founded in E glass fibre refractory materials tank furnace, and the premium properties such as glass fibre has that tensile strength is high, Young's modulus is high, thermotolerance is high and chemical resistance is high, suitably reduce the mold temperature of glass fibre, at high-performance glass fiber production field, there is fine economic worth and use value.
Technical scheme of the present invention is: a kind of resistance to chemical attack high-strength high-modulus glass fiber composition, is characterized in that: its composition is with SiO
2-Al
2o
3-CaO-MgO quaternary system is main, and four kinds of primaries components shared massfraction in glass fibre is 95.2-98.5%, in described quaternary system, add 0.5-1.2%R
2the ZrO of O, 0.5-2.0% component
2, all the other are Fe
2o
3.
The present invention is not containing Li
2o.
The present invention is not containing TiO
2.
The each composition of the present invention comprises by weight:
59.0-62.0%SiO
2
16.0-19.0%Al
2O
3
8.0-13.0%CaO
9.0-11.0%MgO
0.5-1.2%R
2O
0.5-2.0％ZrO
2
Fe
2O
3≤0.25%
Further claimed scope is as follows again:
59.0-61.0%SiO
2
16.0-18.5%Al
2O
3
8.0-13.0%CaO
9.0-11.0%MgO
0.5-0.8%R
2O
0.5-1.5％ZrO
2。
CaO content of the present invention is 8.0-13.0%.
SiO of the present invention
2content is 59.0-62.0%.
SiO of the present invention
2+ Al
2o
3>=76.0%, 3.1≤SiO
2/ Al
2o
3≤ 3.9.
Content of MgO of the present invention is between 9-11%.
The present invention also comprises total amount by weight and is no more than the Fe of 0.25%
2o
3.
The present invention founds in similar E glass fibre refractory materials tank furnace kiln, adopts the direct wire-drawing operation of platinum rhodium bushing to produce.
The tensile strength of glass fibre of the present invention is 2700-2800MPa, Young's modulus 84-86Gpa
The invention provides a kind of resistance to chemical attack high-strength high-modulus glass fiber formula, belong to SiO
2-Al
2o
3-CaO-MgO quaternary system.Its maximum feature is the ZrO containing 0.5-1.5%
2, not containing Li
2o and TiO
2without F
2.Li is added in glass formula
2o, suitably can reduce glass melting temperature; But in glass formula, suitably adjust CaO, MgO, SiO
2, Al
2o
3, R
2o(N
a2o+K
2o) content and ratio also can give the higher Young's modulus of fiber and intensity.This composition, exactly by optimizing and revising each component, is selected, near phase boundary line or eutectic point, to reduce fiberizing temperature, reduces task difficulty.Li is drawn through many experiments
2the corrosion-resistant property of O on glass does not affect substantially.Introduce Li
2the cost of material of O is high, adds raw materials cost.So can not Li be added completely in high-strength and high-modulus amount glass fiber formula
2o.TiO
2can chemical durability of glass be improved to a certain extent, but TiO
2belong to coloring oxide, one of color quality index also becoming client of glass fibre.TiO is not added in this formula
2, ensure that the whiteness of glass fibre, improve the diathermancy in glass smelting simultaneously, widened the application in field color being had to requirement; F
2be the composition of fluxing in glass industry, significantly can accelerate the speed of response of glass batch, due to F
2be easy to volatilization and to environmental hazard greatly, to equipment corrosion seriously, limit it completely and use in patent of the present invention, object is acquisition a kind of excellent property, eco-friendly glass fiber compound.
SiO in the present invention's formula
2it is 59.0-61.0%, SiO that content is optimized more up to 59.0-62.0%
2be main glass framework ingredient, its content increase can significantly improve intensity, temperature tolerance, the chemical resistance of glass; Al
2o
3content is 16.0-19.0%, Al
2o
3intensity and the modulus of glass can be improved, Al
2o
3the increase of content, glass structure is finer and close, and intensity, modulus also improve thereupon.SiO
2, Al
2o
3while raising glass viscosity, modulus and other performances, glass melting temperature also can be caused to raise, the refractory materials material temperature tolerance use kiln and glass melting temperature propose requirements at the higher level, require higher to the high temperature suitability of the bushing that wire-drawing shape uses and the cooling power of cooling fin, very big increase facility investment, is unfavorable for wire-drawing shape.Except specific SiO in patent of the present invention
2, Al
2o
3outside the respective content of component, also specific SiO
2/ Al
2o
3between 3.1-3.9, this specific component makes glass fibre have higher intensity, modulus, and is beneficial to fiberizing; Content of MgO is that 9.0-11.0%, MgO make glass have good toughness, significantly improves the modulus of glass, MgO belongs to the high temperature viscosity that the outer component of network effectively can reduce glass simultaneously, certain benefit has been founded to glass, but the too high crystallization that can promote glass of MgO, improve the recrystallization temperature of glass.CaO can reduce the high temperature viscosity of glass, but its content too much can increase the tendency towards devitrification of glass, increases the fragility of glass.Limit CaO content in the present invention's formula and be not more than 13.0%, improve the softening temperature to 930 DEG C of glass, improve the heat resistance of glass, CaO can accelerate the shaping speed of glass simultaneously, makes glass have shorter material property, is beneficial to wire-drawing shape.
So these four kinds of principal constituents can not unconfined increase or minimizing, this glass formula is by the blend proportion of these four kinds of components of adjustment, make it be in high-temperature stable compositing area, ensure that the mechanics mechanical property that fiber is final, be unlikely to the difficulty increasing wire-drawing shape technique simultaneously.
ZrO
2effectively can improve the resistance to acids and bases of glass, ZrO in silicate glass
2only has cubes [ZrO8] a kind of coordination.Due to Zr
4+ionic radius is comparatively large, and in glass structure, belong to network outer body can effectively be filled in glass network space, and containing ZrO
2silicate glass in acid-base solution after aquation hydrated product be difficult to be dissociated into ion, therefore ZrO
2very stable under acid-base solution corrodes, ZrO
2solubleness in silicate glass is little, and the temperature of fusion that introduction volume too much can significantly improve glass increases glass metal high temperature viscosity, increases increased devitrification resistance, adds fiber task difficulty aborning.And introduce ZrO
2raw material be zirconium English powder, price is higher, adds the ZrO of 0.5-2.0% in the present invention's formula
2more optimal is 0.5-1.5%, not only can ensure to have higher chemical resistance, but also ensure that temperature of fusion, glass cost are not high.
Fe
2o
3it is a kind of coloring element, larger on the heat transmitting impact of glass colour and glass, too high levels can affect the diathermancy of glass, for making glass, there is good outward appearance, reduce product operational difficulty aborning simultaneously, reduce iron level in glass as much as possible, use the raw material that iron level is low, use Calcined polishing aluminum oxide to introduce Al
2o
3, in the present invention, limit Fe
2o
3≤ 0.25%.
R
2o(N
a2o+K
2o) it is necessary for introducing, and content optimizes content range at 0.5-0.8% more at 0.5-1.2%.R
2o is very large to reducing glass viscosity and improving tendency towards devitrification effect.And the Sodium sulfate anhydrous.min(99) added can regulate the oxidation-reduction quality in batch melting process, ensure the founding of glass, clarify, homo-effect, obtain high-quality glass.R simultaneously
2the existence of O has to there being the kiln of electricity fusing-aid effect of well fluxing, and at utmost can play the effect of electricity fusing-aid, reduce the difficulty of founding, clarifying to a certain extent.
Specific embodiment:
At the following formulated admixtion of use for laboratory, be melting into glass block, carry out Performance Detection, for verifying the present invention further, the glass ingredient having carried out this invention composition at our company's tank furnace production equipment carries out experimental production.
Performance is as following table:
Can be found by above Data Comparison, SiO
2content improves strain point and the softening point temperature that effectively can improve glass, namely improves the temperature tolerance of glass, widens the application of product in fields such as high temperature acid-fast alkali-proof field of environmental engineering, vehicle mufflers.Glass fibre softening temperature in the present invention is more than 920 DEG C, and relatively common E glass fibre improves 70-80 DEG C, and strain point improves 80 DEG C, and temperature tolerance is corresponding raising also.Use the glass fibre that this heat resistance is high, the weather resistance that sound damper uses can be improved, also can reduce the impact on environment; Al2O
3but the modulus fiberizing temperature that raising effectively can increase glass increases too many; CaO, MgO can reduce the fiberization temperature of glass, and the ratio both suitably regulating can adjust the scope of △ T, is beneficial to wire-drawing operation.Can be found out by data, this composition series fiberizing temperature, 140-180 DEG C lower than S-2 glass fibre, about 40-81 DEG C lower than R glass fibre, so this composition compares S-2, R glass fibre be more conducive to the production of mass-producing tank furnace.
The tensile strength that the resistance to chemical attack high-strength high-modulus glass fiber composition that the present invention produces records glass fibre according to ASTMD2343 standard is 2700-2800MPa, Young's modulus 84-86Gpa.
Carried out the simultaneous test of erosion resistance to glass fiber compound involved in common E glass fibre, domestic high strength glass fiber and the present invention, concrete outcome is as follows simultaneously:
1: glass particle chemical resistance is tested: will grind respectively without boron fluoride-free glass, S glass and glass composition of the present invention, sieve the glass particle got between 70 ~ 80 orders.Carry out chemical resistant properties detection respectively:
Alkali resistance detects: constant temperature is immersed in 96h in the 5%NaOH solution of 80 DEG C.
Acid resistance detects: constant temperature is immersed in the 10%H of 96 DEG C
2sO
496h in solution.
Water tolerance detects: constant temperature is immersed in 96h in the seawater of 96 DEG C.
Take out sample filtering, dry in 100 DEG C of baking ovens, respectively calculation sample quality retention rate.
2: the chemical resistance experiment product produced and other fibers having been carried out to above condition, contrast by experiment, the glass fiber compound chemical resistance that the present invention relates to is with suitable without boron floride-free glass fibre, compare with S glass fibre: alkali resistance improves about 17%, acid resistance improves about 12%, is conducive to applying in heat-and corrosion-resistant high strength and modulus environment.
Claims (12)
1. a resistance to chemical attack high-strength high-modulus glass fiber composition, is characterized in that: its composition is with SiO
2-Al
2o
3-CaO-MgO quaternary system is main, and four kinds of primaries components shared massfraction in glass fibre is 95.2-98.5%, in described quaternary system, add 0.5-1.2%R
2o, 0.5-2.0%ZrO
2, all the other are Fe
2o
3.
2. resistance to chemical attack high-strength high-modulus glass fiber composition as claimed in claim 1, is characterized in that not containing Li
2o.
3. high resistance to chemicals corrosion high-strength high-modulus glass fiber composition as claimed in claim 1, is characterized in that not containing TiO
2.
4. resistance to chemical attack high-strength high-modulus glass fiber composition as claimed in claim 1, is characterized in that each composition comprises by weight:
59.0-62.0%SiO
2
16.0-19.0%Al
2O
3
8.0-13.0%CaO
9.0-11.0%MgO
0.5-1.2%R
2O
0.5-2.0％ZrO
2
Fe
2O
3≤0.25%。
5. resistance to chemical attack high-strength high-modulus glass fiber composition as claimed in claim 1, it is characterized in that each composition comprises by weight, further claimed scope is as follows:
59.0-61.0%SiO
2
16.0-18.5%Al
2O
3
8.0-13.0%CaO
9.0-11.0%MgO
0.5-0.8%R
2O
0.5-1.5％ZrO
2。
6. resistance to chemical attack high-strength high-modulus glass fiber composition as claimed in claim 1, its feature is that CaO content is 8.0-13.0%.
7. resistance to chemical attack high-strength high-modulus glass fiber composition as claimed in claim 1, is characterized in that SiO
2content is 59.0-62.0%.
8. resistance to chemical attack high-strength high-modulus glass fiber composition as claimed in claim 1, is characterized in that SiO
2+ Al
2o
3>=76.0%, 3.1≤SiO
2/ Al
2o
3≤ 3.9.
9. resistance to chemical attack high-strength high-modulus glass fiber composition as claimed in claim 1, is characterized in that content of MgO is between 9-11%.
10. resistance to chemical attack high-strength high-modulus glass fiber composition as claimed in claim 1, is characterized in that also comprising the Fe that total amount is by weight no more than 0.25%
2o
3.
11. resistance to chemical attack high-strength high-modulus glass fiber compositions as claimed in claim 1, is characterized in that founding in similar E glass fibre refractory materials tank furnace kiln, adopt the direct wire-drawing operation of platinum rhodium bushing to produce.
12. resistance to chemical attack high-strength high-modulus glass fiber compositions as claimed in claim 1, is characterized in that the tensile strength of glass fibre is 2700-2800MPa, Young's modulus 84-86Gpa.
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|---|---|---|---|
| CN201510545056.XA CN105461231A (en) | 2015-08-31 | 2015-08-31 | Chemical corrosion-resistance, high-strength and high-modulus glass fiber composition |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046608A (en) * | 2017-12-25 | 2018-05-18 | 安徽同力新材料有限公司 | A kind of high-strength high temperature-resistant glass fibre |
| CN108585523A (en) * | 2018-07-13 | 2018-09-28 | 合肥连森裕腾新材料科技开发有限公司 | A kind of fibrous material of high-strength high temperature-resistant |
| CN112374763A (en) * | 2020-12-01 | 2021-02-19 | 宏和电子材料科技股份有限公司 | High-performance glass fiber component and manufacturing method thereof |
| CN113003941A (en) * | 2021-03-15 | 2021-06-22 | 南京玻璃纤维研究设计院有限公司 | Glass composition, glass fiber cotton, fiber blended yarn and preparation method |
| CN113372007A (en) * | 2021-05-07 | 2021-09-10 | 临沂天炬节能材料科技有限公司 | Corrosion-resistant glass fiber composition |
| 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 |
|---|---|---|---|---|
| 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 |
| CN101734862A (en) * | 2009-12-18 | 2010-06-16 | 泰山玻璃纤维有限公司 | Method for preparing environment-friendly high-modulus glass fiber |
| CN103596897A (en) * | 2010-12-22 | 2014-02-19 | Agy控股公司 | High strength glass composition and fibers |
-
2015
- 2015-08-31 CN CN201510545056.XA patent/CN105461231A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101734862A (en) * | 2009-12-18 | 2010-06-16 | 泰山玻璃纤维有限公司 | Method for preparing environment-friendly high-modulus glass fiber |
| CN103596897A (en) * | 2010-12-22 | 2014-02-19 | Agy控股公司 | High strength glass composition and fibers |
Cited By (7)
| 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 |
| CN108046608A (en) * | 2017-12-25 | 2018-05-18 | 安徽同力新材料有限公司 | A kind of high-strength high temperature-resistant glass fibre |
| CN108585523A (en) * | 2018-07-13 | 2018-09-28 | 合肥连森裕腾新材料科技开发有限公司 | A kind of fibrous material of high-strength high temperature-resistant |
| CN112374763A (en) * | 2020-12-01 | 2021-02-19 | 宏和电子材料科技股份有限公司 | High-performance glass fiber component and manufacturing method thereof |
| CN113003941A (en) * | 2021-03-15 | 2021-06-22 | 南京玻璃纤维研究设计院有限公司 | Glass composition, glass fiber cotton, fiber blended yarn and preparation method |
| CN113003941B (en) * | 2021-03-15 | 2022-12-06 | 南京玻璃纤维研究设计院有限公司 | Glass composition, glass fiber cotton, fiber blended yarn and preparation method |
| CN113372007A (en) * | 2021-05-07 | 2021-09-10 | 临沂天炬节能材料科技有限公司 | Corrosion-resistant glass fiber composition |
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Application publication date: 20160406 |