CN101700960B - Glass fiber formula - Google Patents
Glass fiber formula Download PDFInfo
- Publication number
- CN101700960B CN101700960B CN2009100168463A CN200910016846A CN101700960B CN 101700960 B CN101700960 B CN 101700960B CN 2009100168463 A CN2009100168463 A CN 2009100168463A CN 200910016846 A CN200910016846 A CN 200910016846A CN 101700960 B CN101700960 B CN 101700960B
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- CN
- China
- Prior art keywords
- glass
- parts
- formula
- zno
- glass fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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
- 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
- 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
- C03C3/11—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
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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 relates to production formulas of glass fibers, in particular to a glass fiber formula with excellent acid etching resistance. The formula is characterized in that the components include SiO2, Al2O3, B2O3, F, CaO, MgO, K2O, Na2O, ZnO and TiO2. Compared with the E glass formula widely applied at present, the formula of the invention has the advantage that as ZnO and TiO2 are introduced and the content of B2O3 is reduced, the acid resistance of the glass fiber is dramatically improved, and the electrical property, the mechanical property and the operating property are improved to some extent. The formula is suitable for mass production under the condition of E glass tank furnace production technology.
Description
Technical field
The present invention relates to a kind of production formula of continuous glass fibre, relate in particular to a kind of glass fiber formula with good acid attack resistance, this fiber is applicable in the sour environment.
Background technology
Be used to make the most frequently used glass composition of continuous glass fibre precursor and be " E glass ".The liquidus temperature of E glass is 1050 ℃ or lower, and E glass is alkali metal oxide content less than 1% aluminium, boron, silicate glass.Because of containing higher boron content, structural framework is loose, is not sufficiently complete, and acid attack resistance is relatively poor, is very peeled off with resin matrix by acid attack easily under sour environment by the glass reinforced plastic of its preparation, loses intensity rapidly.
To this shortcoming, scientific research institution of many enterprises has carried out big quantity research.Spun glass like the said glass ingredient production of the patent of number of patent application 200710069773.5 compares the acid attack resistance that has improved glass greatly with the E glassy phase.But because it does not contain boron and fluorine etc. fully and fluxes, reduces capillary composition; Viscosity is very big under its high temperature; Be difficult to clarify, be easy to during wire-drawing shape to occur the fiber quality that defectives such as calculus, striped cause being produced at present technology condition poor; And product cost is high, is difficult to large-scale promotion application.
The present invention is directed to these characteristics of traditional E glass and existing acidproof erosion glass; Seek the factor that influences the glass acid resistance in the glass ingredient through a large amount of experiments; The adjustment prescription is sought best composition blend proportion, improving the acidproof rodent while, has guaranteed its good working performance.
Summary of the invention
For solving the shortcoming of traditional E glass acid resistance difference, the invention provides the glass formula that a kind of acid resistance is extremely superior, operation is more stable.
The fibre property of glass composition of the present invention comprises: fiberization temperature, liquidus temperature and Δ T.Fiberization temperature is defined as the temperature that viscosity is 1000 pools; Reduce fiberization temperature, increase operation annex work-ing life, be easy to produce, reduce production costs greatly.Liquidus temperature is defined as glass liquid state equilibrated top temperature between the matrix cystal phase with it, is easy to form crystal when being lower than this temperature, and fiberizing is interrupted.Another fibrosis performance is Δ T, is defined as the poor of fiberization temperature and liquidus temperature, and bigger Δ T helps fiberizing, has reduced the control requirement to process facility, reduces production costs.
The present invention partly is a kind of glass composition, and this glass composition is fit to make acidproof erosive continuous glass fibre.This glass composition is adapted at large tank furnace used middle production of existing E glass; Agalmatolite, living lime stone, borocalcite, silica powder, fluorite, Natural manganese dioxide and the soda ash etc. that use present E glass generally to adopt are main raw material, adopt the direct fusion method to process spun glass at an easy rate.
Compsn of the present invention each composition by weight percentage comprises SiO
256.0%, Al
2O
314.5%, B
2O
30.6%, CaO 23.0%, and MgO 1.5%, and F 0.2%, R
2O (K
2O+Na
2O) 0.74%, with SiO
2Get about 56.0% Al
2O
3Get about 14.5%, for guaranteeing melting properties that glass is good and lower fiberization temperature B
2O
3Get 0.6%, F gets 0.2%, and introduces 0.2% TiO
2, TiO
2Can reduce the viscosity of glass when high temperature and play certain fluxing action, and also can improve the acid resistance of glass; For improving the acid resistance of glass, introduce 2.5% ZnO, ZnO is that glass forms midbody, in the glass forming process, with ZnO
4Form gets in the network structure, can improve the chemicalstability and the acidproof aggressiveness of glass; R
2O gets the electrical insulation capability of 0.74% assurance spun glass.
Prescription of the present invention has kept 0.6% B
2O
3, therefore 0.2% F has guaranteed temperature of fusion and the viscosity that glass is lower.In addition, with E glassy phase ratio, because B
2O
3, F reduces greatly, so its volatilization in kiln significantly reduces, alleviated environmental pollution.
Acid-resistant glass prescription of the present invention is characterized in that: this glass formula in 10% sulphuric acid soln, to set acid liquor temperature be digestion 4h, 24h, 48h, 96h respectively under 99 ℃ the condition, the weight residual rate is used K value representation, K
(96h)>=90%, and the weight residual rate of traditional E glass under similarity condition, K
(96h)Value is about 60%.
Among the present invention, glass is formed the reasons are as follows of being defined as above:
SiO
2, Al
2O
3And B
2O
3Be both the composition that forms the glass skeleton, so SiO
2Be defined as at 56.0% o'clock, can provide enough skeleton structures to be unlikely to improve greatly the fusing difficulty again.
Al
2O
3Can effectively stop the glass phase-splitting at 14.5% o'clock, the stabilized glass skeleton structure is unlikely to improve greatly glass viscosity again well, guarantees transaction capabilities.
B
2O
3Not only guarantee glass excellent acid aggressiveness at 0.6% o'clock, also effectively reduced the temperature of fusion and the glass viscosity of glass.
CaO, MgO can reduce the viscosity of glass metal, are beneficial to glass melting, make the fibrosis difficulty but CaO, MgO and amount the crystallization noted phase separation phenomena can occur greater than 25% o'clock glass, and particularly MgO content was greater than 5% o'clock, and the crystallization noted phase separation phenomena can increase the weight of.Therefore CaO is defined as 23%, and MgO is defined as 1.5%.
Na
2O, K
2O has the fusing assistant effect, and these compositions total at 1.0% o'clock, acidproof, the water resistance variation of glass, and influence the insulating property of product.Therefore with Na
2O+K
2O is defined as 0.74%.
Among the present invention, except that mentioned component, introduce by ore inevitably, at the most 1.5% TiO
2, SrO, Fe
2O
3, P
2O
5, ZrO
2, Cr
2O
3Deng composition.
Followingly according to case study on implementation the present invention is elaborated, glass is formed the composition that is based on claim 2 of the present invention in the table 1.Be mixed with batch of material by the composition of the glass shown in the table 1, in the platinum crucible of packing into, place in the electric furnace, under 1420～1480 ℃ condition, found into glass, be incubated 2 hours, take out the cooling back.
The acid resistance of tested glass:
1, the glass in the platinum crucible is taken out, grind.Use sample sifter to choose 65 orders～70 purpose samples, and take by weighing about 2.0g, be designated as M with electronic balance
0
2, the compound method of 10% sulphuric acid soln:
For the collimation of guaranteeing to test as far as possible, the disposable required acid solution of all experiments of foot of joining.Be example with preparation 10000ml acid solution below.
Take the 10000ml wide-necked bottle, the deionized water of packing into is placed in the pond, opens water pipe, guarantees that wide-necked bottle can both obtain cooling constantly.
Through calculating the requirement that can get 98% vitriol oil is 580ml.Measure the vitriol oil with graduated cylinder and slowly inject wide-necked bottle, injection speed is as the criterion with bottle wall non-scald on hand.
Treat solution cold fully but after, re-use stirrer and continue to stir 16 hours.
3, heating in water bath
Set 99 ℃ of water bath with thermostatic control temperature.The sample that takes by weighing is poured in the plastic beaker, in beaker, injected 150～200ml acid solution again, with rubber hose and plastics film sealing, beaker is put into water-bath again, behind 4h, 24h, 48h, 96h, take a sample respectively.To note in the experimentation letting water level be lower than 2/3rds of beaker.
4, sample washing
Beaker is taken out, while hot acid solution is poured out, it is slow that action is wanted, and prevents that glass sample runs off.Wash plastic beaker with wash bottle.Glass is transferred in the specified glass beaker, used a large amount of deionized water rinsings more than three times again.
5, suction filtration sample
This step need use vacuum pump, filter flask and sand hopper to accomplish jointly.The sand hopper quality is designated as M
1
Connect filter flask and vacuum pump, the sand hopper that will clean oven dry again is installed on the filter flask, opens switch, washes beaker bottom with wash bottle, and glass powder is transferred to funnel.Use deionized water rinsing hopper walls and bottom again after shifting fully, guarantee that glass is tiled in funnel bottom.
6, oven dry weighing
Baking oven is transferred to 100 ℃, put into the sand hopper drying more than three hours, take out after the constant weight, be cooled to room temperature.Weigh and be designated as M
2
7. calculate:
K＝(M
2-M
1)/M
0×100％
Table 1
| Comparative example | Comparative example | Glass ingredient of the present invention | |
| Composition | E glass | Patent 200710069773.5 | 1 |
| SiO 2 | 54 | 60.2 | 56.0 |
| Al 2O 3 | 14 | 13.0 | 14.5 |
| CaO | 22.8 | 22.0 | 23.0 |
| MgO | 0.46 | 3.0 | 1.5 |
| B 2O 3 | 7.3 | 0 | 0.6 |
| Li 2O | 0 | 0 | 0.20 |
| Na 2O | 0.50 | 0.5 | 0.45 |
| K 2O | 0.25 | 0.3 | 0.29 |
| ZnO | 0 | 0 | 2.5 |
| F | 0.7 | 0 | 0.2 |
| TiO 2 | 0.23 | 0.36 | 0.2 |
| K％(96h) | 60％ | 87％ | 94％ |
| Filament strength/MPa | 3058 | 3080 | 3050 |
| Volume specific resistance/(Ω cm) | 1.2×10 15 | 1.17×10 15 | 1.22×10 15 |
| Liquidus temperature/℃ | 1050 | 1170 | 1110 |
| Fiberization temperature/℃ | 1150 | 1258 | 1202 |
| ΔT/℃ | 100 | ?88 | ?92 |
In weight part mix according to 26 parts silica powder, 739 parts agalmatolite, 244 parts of unslaked lime, 22 parts of borocalcites, 2 parts of fluorites, 16 parts Natural manganese dioxide, 25 parts of zinc oxide, 8 parts soda ash and the glass ingredient of case study on implementation as shown in table 1.This glass acid resistance is superior, and K (96h) value is more than 90%, than E glass remarkable advantages is arranged.
Spun glass of the present invention has very superior acid resistance, is made into matrix material, can in certain sour environment, keep its intensity muchly.And it can stablize operation in the manufacturing condition of present E spun glass well clarification, homogenizing down, has than less cost suitable scale operation.
Claims (2)
1. acidproof erosive spun glass, it is characterized in that: described spun glass each composition by weight percentage comprises SiO
256.0%, Al
2O
314.5%, B
2O
30.6%, CaO 23.0%, and MgO 1.5%, and ZnO 2.5%, and F 0.2%, K
2O+Na
2O 0.74%, TiO
20.2%; It is to use silica powder, agalmatolite, unslaked lime, borocalcite, fluorite, zinc oxide, Natural manganese dioxide, soda ash, mixes the back fusion draw in weight part according to 26 parts silica powder, 739 parts agalmatolite, 244 parts of unslaked lime, 22 parts of borocalcites, 2 parts of fluorites, 16 parts Natural manganese dioxide, 25 parts of zinc oxide, 8 parts soda ash and forms.
2. the prepared fiber reinforced articles of acidproof according to claim 1 erosive spun glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100168463A CN101700960B (en) | 2009-07-17 | 2009-07-17 | Glass fiber formula |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100168463A CN101700960B (en) | 2009-07-17 | 2009-07-17 | Glass fiber formula |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101700960A CN101700960A (en) | 2010-05-05 |
| CN101700960B true CN101700960B (en) | 2012-02-01 |
Family
ID=42155893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100168463A Expired - Fee Related CN101700960B (en) | 2009-07-17 | 2009-07-17 | Glass fiber formula |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101700960B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261684A (en) * | 2014-09-17 | 2015-01-07 | 安徽吉曜玻璃微纤有限公司 | Vacuum insulation board core material and manufacturing method thereof |
| CN110611067A (en) * | 2018-06-15 | 2019-12-24 | 科建高分子材料（上海）股份有限公司 | Manufacturing process of AGM battery separator reinforced by acrylic emulsion |
| CN111534033A (en) * | 2020-06-15 | 2020-08-14 | 扬州爱非科鞋业有限公司 | Preparation method of anti-slip sole |
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2009
- 2009-07-17 CN CN2009100168463A patent/CN101700960B/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN101700960A (en) | 2010-05-05 |
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| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120201 Termination date: 20130717 |