CN103232165A - Glass fiber, preparation method thereof and glass fiber composite material - Google Patents
Glass fiber, preparation method thereof and glass fiber composite material Download PDFInfo
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- CN103232165A CN103232165A CN201310161555XA CN201310161555A CN103232165A CN 103232165 A CN103232165 A CN 103232165A CN 201310161555X A CN201310161555X A CN 201310161555XA CN 201310161555 A CN201310161555 A CN 201310161555A CN 103232165 A CN103232165 A CN 103232165A
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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
- C03C13/00—Fibre or filament compositions
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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
- C03C3/083—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
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Abstract
The invention discloses a glass fiber, a preparation method thereof and a glass fiber composite material. The nominal diameter of the glass fiber ranges from 3 micro to 15 micro and the deviation value of the diameter of the glass fiber is within +/-15% of the nominal diameter. According to the weight percent, in the glass fiber, the alumina content is 20-33%, the silicon oxide content is 4.11-5.48 times of calcium oxide and the calcium oxide content is 0.9-2.1 times of magnesium oxide. Under the condition of high alumina content (20-33% or 23-33% or 25-33%), the glass fiber can generate a new product property with the function of dispersion of aluminum, silicon, calcium and magnesium, so that the problem in the prior art that the dissolving and the quality of air bubbles cannot be controlled resulting from high glass viscosity as a result of high aluminum content is solved; energy and consumption are greatly reduced; the carbon emission is lowered; the devitrification temperature is low, so that mass production can be carried out; and besides, pollutant discharge of toxic boron gas is not generated in the production process.
Description
Technical field
The present invention relates to glass fibre, its preparation method, this glass fibre has low recrystallization temperature, high strength, low viscosity feature.This glass fibre can be used for making glass fiber compound material.
Background technology
Existing glass fibre and glass fiber compound material goods all have some defectives:
1, high, medium-alkali glass fibre: by weight percentage, silicon oxide-containing is about 67% in its composition, and magnesium oxide is about 1%, and calcium oxide is about 9.5%, the about 5-7% of aluminum oxide, and the about 2-10% of sodium oxide, fluorine oxide is about 0.5%, and boron oxide is about 3%, barium oxide about 2%.The defective of its goods is, the viscosity height in the production technique, and production energy consumption is big; When glass diameter≤9 micron, (N/tex) is poor for breaking tenacity, generally all below 0.4, so technique effect is poor, the necessity that overcomes is arranged.
2, alkali-free E glass fibre: by weight percentage, silicon oxide-containing is about 55% in its composition, and magnesium oxide is less than 2%, and calcium oxide is greater than 20%, and aluminum oxide is about 14%, and sodium oxide is less than 1%, boron oxide about 8%.Its defective processed is:
Viscosity height in A, its production technique, production energy consumption is big, and a large amount of boron poison gas dischargings is arranged in the production;
B, because the boron composition is fast to the erosion of refractory brick, will stop production in 2 years and to change many refractory brick that are etched, refractory brick cost height, 2 year life-span of production line is too short;
C, when glass diameter≤9 micron, breaking tenacity (N/tex) is generally all about 0.5, so the breaking tenacity weak effect; The necessity that overcomes is arranged.
3, fluorine glass/glass fiber: count as weight percents, the content of silicon oxide is about 44% in this glass, and calcium oxide content is about 22%, content of magnesia is about 7%, alumina content is 20%, and fluorine content is about 7%, and the content of calcium oxide is 3 times of magnesian content.Its defective is:
A large amount of fluorine poison gas dischargings is arranged in A, the production, and environmental issue is serious.So the necessity that overcomes is arranged.
B, because the production technique of this high temperature has been accelerated the erosion of fluorine composition to refractory brick, determine annual will the stopping production to change many refractory brick that are etched, carry out cold repair to production line; Refractory brick replace and cost very high, add that the life-span that production line will stop production every year is too short, more raised total cost.
4, Zhong Guo S level high-strength glass fibre: by weight percentage, silicon oxide-containing is about 63% in its composition, and calcium oxide is about 0.3%, and magnesium oxide is about 14%, and aluminum oxide is about 25%, boron oxide about 2%; Its defective is:
A, when glass diameter≤9 micron, breaking tenacity (N/tex) generally all about 0.7-0.8, has the necessity that overcomes;
The viscosity of this goods is too high in B, its production technique, and production energy consumption is too big, and yield efficiency is very low, and a line is only produced per year about hundred tons;
The production technique of C and its this high temperature is accelerated the boron composition to the erosion of refractory brick, has determined all will carry out cold repair to production line its every year; Refractory brick replace and cost very high, add that the life-span of production line is too short, more raised total cost, so the necessity that overcomes is arranged.
5. the inventor discloses the glass fibre that high strength and energy-saving, emission-reducing, environment friendly and low viscosity feature are arranged, and application number is 201110060932.1, and the defective of this technical scheme is:
Because the calcium oxide ratio is higher in the technical scheme, the crystallization viscosity of its many compositions is 10
2.5(handkerchief second)-10
2.9(handkerchief second), be much higher than 10
3.0The mold temperature of (handkerchief second) glass fibre.So this only improves wire-drawing temperature at process system, adopt the refrigerating unit of leting slip a remark especially to prevent from producing in the drawing process crystallization devitrification.But this is unfavorable for normally realizing the production of high efficiency extensive production capacity again.
6, prior art CN101580344A (Chinese megalith group): 1. its 0.7＜CaO/MgO＜2.2,2. preferred Al2O3 content range is 15-18% (5 pages in specification sheets); 3. and the aluminum oxide of its 6 examples all in 16%; (seeing its specification sheets 11,12 page tables 1, table 2) reflects a kind of technology prejudice.
7, external S level high-strength glass fibre: by weight percentage, silicon oxide-containing is about 65% in its composition, and magnesium oxide is about 10%, aluminum oxide about 25%; Its defective is:
A, when glass diameter≤9 micron, breaking tenacity (N/tex) generally all in 0.9, limited to, and the necessity that overcomes is arranged by intensity;
B, production energy consumption are too big, and yield efficiency is very low, and a line is only produced per year about hundred tons.
The production technique of C and this very high temperature has been accelerated the erosion to refractory brick, has determined all will carry out cold repair to production line its every year; Refractory brick replace and cost very high, add that the life-span of production line is too short, more raised total cost, so the necessity that overcomes is arranged.
8, documents: prior art TW201144249A relatively, embodiment 15 its aluminum oxide 18.7% wherein, the content of silicon oxide is 4.5 times of calcium oxide content, the content of calcium oxide is 1.33 times of magnesian content; And among its 19 embodiment, 2 silicon oxide are only arranged: the content of calcium oxide, calcium oxide: magnesian content within the scope of the present invention, and these 2 embodiment aluminum oxide all are lower than 20%.Because aluminum oxide all is lower than 20%, there is the low defective of breaking tenacity (N/tex) of glass fibre in prior art TW201144249A.
9, the air blade material in glass fiber compound material especially, because the intensity of the glass fibre that uses is low, or the cost of S level glass is too high, yield poorly, so the wind sweeping area of air blade does not increase, seriously restricted the conversion of wind energy to electric energy, restricted the cost of electricity-generating of wind-powered electricity generation, its cost is much higher than thermoelectricity, water power.So, improve glass cost performance of product and intensity, could fundamentally solve the cost of wind-powered electricity generation.This is that people thirst for solving and never having a great difficult problem of succeeing.
Summary of the invention
Because defective and the deficiency of above-mentioned prior art, the present invention need provide a kind of glass fibre, its energy-conservation, fall under the prerequisite of cost, environmental protection, raising plant factor and production capacity: can reach nominal diameter within 3 microns to 15 microns, the deviate of this glass fiber diameter is in nominal diameter ± 15%, when its diameter was less than or equal to 9 microns, the breaking tenacity of glass fibre (N/tex) reached the high tensile breaking tenacity of 0.65-1.0.
Technical scheme of the present invention is achieved in that
A kind of glass fibre, its nominal diameter at 3 microns in 15 microns, the deviate of this glass fiber diameter is in nominal diameter ± 15%, it is characterized in that: count as weight percents, in this glass fibre, alumina content is 20-33%, and content of magnesia is 5.5-20%, the content of silicon oxide is 4.11--5.48 times of calcium oxide content, and the content of calcium oxide is 0.9--2.1 times of content of magnesia.
Described glass fibre is characterized in that, the breaking tenacity when diameter is less than or equal to 9 microns is 0.7-1.1.
Described glass fibre is characterized in that, the content of silicon oxide is 4.11 times of calcium oxide content--4.55 times, the content of calcium oxide is 0.9-1.9 times of content of magnesia.
Described glass fibre is characterized in that, counts as weight percents, and in this glass fibre, the content of silicon oxide is 4.55 times of calcium oxide content---5.48 times.
Described glass fibre is characterized in that, counts as weight percents, and in this glass fibre, alumina content is 23-33%.
Described glass fibre is characterized in that, counts as weight percents, and in this glass fibre, alumina content is 25-33%.
A kind of glass fiber compound material, this matrix material comprise the described glass fibre of claim 1--5 in plastic substrate and the embedding plastic substrate.
A kind of preparation method of glass fibre, the nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, it is characterized in that:
The melten glass body that forms in the step 2, step 1 stretches and the formation glass fibre through some holes of the refractory metal plate of porous high speed, through cooling, can make described fiberglass products.
The preparation method of described glass fibre is characterized in that, this glass fibre is 10 in viscosity
1.5The temperature of handkerchief during second is 1480 ℃-1690 ℃; Viscosity is 10
2The temperature of handkerchief during second is 1370 ℃-1490 ℃.
Implement the technology of glass fibre of the present invention and this glass fibre of preparation, have following beneficial effect:
A, glass fibre of the present invention, relatively existing glass technology: 1, be (20-33%) integration factor invention technical scheme that the selection invention of silicon, calcium, magnesium factor proportion close limit or different range adds a kind of high aluminium content; 2, adopted the technical scheme of the technology essential factor of fluorine, boron, barium being omitted invention again, overcome various traditional must be the technology prejudice of hydrotropy composition by fluorine, barium, boron especially;
B, glass fibre of the present invention have been found the new property of product: 1, found aluminium, silicon, the calcium of the high alumina content (20-33%) of product, the new product property of magnesium eutectic function; 2, found the lower character of viscosity temperature of product; That 3, has found product is conducive to the lower recrystallization temperature character of coupling of glass fibre moulding and mold temperature;
C, glass fiber product of the present invention have produced the relatively unforeseeable technique effect of prior art:
1, owing to found aluminium, silicon, the calcium of the high alumina content of glass fiber product of the present invention, the new product property of magnesium eutectic function, so alumina content is 20--33% or 23-33% or 25-33%, make the nominal diameter of glass fibre of the present invention within 3 microns to 15 microns, the deviate of this glass fiber diameter is in nominal diameter ± 15%, and the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) can reach the very high tension breaking tenacity technique effect of 0.65-1.0;
2, because the lower character of viscosity temperature of glass fiber product of the present invention has produced the significantly energy-saving and cost-reducing technique effect that reduces carbon emission again;
3, owing to found glass fiber product of the present invention, the existing patent that compares the inventor, have and be beneficial to the lower recrystallization temperature character of coupling of glass fibre moulding and mold temperature, so can avoid adopting a kind of refrigerating unit of particularly leting slip a remark of production efficiency difference to prevent from producing the crystallization devitrification in the drawing process, thereby be conducive to the production that glass fibre of the present invention can normally be realized high efficiency extensive production capacity;
4, because the character of glass fiber product of the present invention can all be carried out cold repair to production line every year, there is production efficiency to heighten, reduced the cost techniques effect again;
5, because glass fiber product of the present invention omits the technical scheme of invention to the technology essential factor of fluorine, boron, barium, there is not the poison gas of discharging boracic or fluorine in the production, reach and optimize the technique effect that environmental protection is produced.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, to do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below, apparently, accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the normal section synoptic diagram of the low viscous fiberglass products of low recrystallization temperature high strength of the present invention.
Fig. 2 is the preparation technology's of the low viscous glass fibre of low recrystallization temperature high strength of the present invention schematic flow sheet.
Embodiment
More than to according to the forming and characteristic of a kind of glass fibre by low recrystallization temperature high strength low viscosity feature of the embodiment of the invention, manufacturing is described below has the method for the glass fibre of low recrystallization temperature high strength low viscosity feature to be described in detail according to a kind of of the embodiment of the invention:
According to one embodiment of the present invention, the nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in.Count as weight percents, in this glass fibre, alumina content is 20-33%, and the content of silicon oxide is 4.11 times-5.48 times of calcium oxide content, and the content of calcium oxide is 0.9 times-2.1 times of content of magnesia.
Fig. 1 is according to glass fibre 1 normal section synoptic diagram of the present invention, and this glass fibre has low recrystallization temperature high strength low viscosity feature.
Fig. 2 is the preparation technology's of a kind of glass fibre that low recrystallization temperature high strength low viscosity feature arranged of the present invention schematic flow sheet.From scheming as seen, the flow process of its moulding process is: (1), the raw material that will be scheduled to prepare are put into feeding warehouse, (2), from feeding warehouse, raw material is transported in the kiln of molten bath then, (3) enter the molten bath and carried out fusion and clarification discharge bubble by preset temperature, (4), liquid molten mass is through platinum alloy wire drawing orifice plate, draw and stretch out glass fiber, drying obtains finished product again.
Now with the making its goods and be described further with the stretching technology of reeling off raw silk from cocoons of the preparation technology of glass fibre of the present invention, its manufacturing processed comprises following steps:
(1), at first, preparation raw material forms to calculate proportioning raw materials according to the glass fibre of above-mentioned first embodiment and various modified example thereof.
(2), be ready to comprise former feed bin, molten bath kiln, the stretching of the platinum alloy bushing in the wire drawing hole required product line device of technology that reels off raw silk from cocoons is arranged.
(3), press the Production Flow Chart of technology shown in Figure 2, the predetermined raw material of (1) step preparation is put into feeding warehouse, from feeding warehouse, raw material is transported in the kiln of molten bath then, carries out fusion and discharge bubble by preset temperature after having entered the molten bath, form liquid molten mass.
Following technology has two kinds of selections:
A kind of is directly to make glass melt through the wire drawing hole of platinum alloy, stretched formation glass fibre finished product of the present invention, and this is direct pool kiln wiredrawing moulding process.
Another kind of is through ball making process, makes glass sphere, glass sphere is sent into the wire drawing hole of crucible and platinum alloy metal sheet again, and stretching forms glass fibre finished product of the present invention.
Because the above-mentioned glass fibre according to the embodiment of the invention except being applied to glasscloth, silk, felt, more is mainly used in glass fiber compound material.
Below, embodiments of the invention are described in detail (in addition, in this manual, unless specialize, the content of various compositions all is weight percentage in the glass).
Embodiment one
Count as weight percents, the content of silicon oxide is 54.8% in this glass, and calcium oxide content is 12.2%, content of magnesia is 8%, alumina content is 25%, and the content of its silicon oxide is 4.5 times of calcium oxide content, and the content of calcium oxide is 1.52 times of magnesian content.
Its actual viscosity temperature that dissolves is 10
1.5Temperature when (handkerchief second) is 1690 ℃ of viscosity temperatures, actual homogenizing exhaust bubble viscosity temperature 10
2It is 1495 ℃ when (handkerchief second); Moulding viscosity temperature 10
3(handkerchief second) is 1295 ℃; Rolling over that brilliant temperature reaches the standard grade is 1265 ℃.
The nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.88.
Embodiment two
Count as weight percents, the content of silicon oxide is 56.3% in this glass, and calcium oxide content is that 13% content of magnesia is 8.7%, and alumina content is 22%, the content of its silicon oxide is 4.3 times of calcium oxide content, and the content of calcium oxide is 1.5 times of magnesian content.
The actual viscosity temperature that dissolves is 10
1.5Temperature when (handkerchief second) is 1660 ℃ of viscosity temperatures, actual homogenizing exhaust bubble viscosity temperature 10
2It is 1465 ℃ when (handkerchief second); Moulding viscosity temperature 10
3(handkerchief second) is 1275 ℃; Rolling over that brilliant temperature reaches the standard grade is 1245 ℃.
The nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.75.
Embodiment three
Count as weight percents, the content of silicon oxide is 58.4% in this glass, and calcium oxide content is that 12% content of magnesia is 8.6%, and alumina content is 21%, the content of its silicon oxide is 4.9 times of calcium oxide content, and the content of calcium oxide is 1.4 times of magnesian content.
The actual viscosity temperature that dissolves is 10
1.5Temperature when (handkerchief second) is 1630 ℃ of viscosity temperatures, actual homogenizing exhaust bubble viscosity temperature 10
2It is 1460 ℃ when (handkerchief second); Moulding viscosity temperature 10
3(handkerchief second) is 1250 ℃; Rolling over that brilliant temperature reaches the standard grade is 1225 ℃.
The nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.2.
Embodiment four
Count as weight percents, the content of silicon oxide is 51.5% in this glass, and calcium oxide content is that 12.3% content of magnesia is 8.2%, and alumina content is 28%, the content of its silicon oxide is 4.2 times of calcium oxide content, and the content of calcium oxide is 1.5 times of magnesian content.
The actual viscosity temperature that dissolves is 10
1.5Temperature when (handkerchief second) is 1690 ℃ of viscosity temperatures, actual homogenizing exhaust bubble viscosity temperature 10
2It is 14850 ℃ when (handkerchief second); Moulding viscosity temperature 10
3(handkerchief second) is 1290 ℃; Rolling over that brilliant temperature reaches the standard grade is 1275 ℃.
The nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.98.
Embodiment five
Count as weight percents, the content of silicon oxide is 59% in this glass, and calcium oxide content is that 11.1% content of magnesia is 7.9%, and alumina content is 22%, the content of its silicon oxide is 5.3 times of calcium oxide content, and the content of calcium oxide is 1.4 times of magnesian content.
The actual viscosity temperature that dissolves is 10
1.5Temperature when (handkerchief second) is 1660 ℃ of viscosity temperatures, the actual homogenizing exhaust bubble viscosity temperature 10 of annealing
2It is 1480 ℃ when (handkerchief second); Moulding viscosity temperature 10
3(handkerchief second) is 1260 ℃; Rolling over that brilliant temperature reaches the standard grade is 1230 ℃
The nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.75.
Embodiment six
Count as weight percents, the content of silicon oxide is 53.7% in this glass, and calcium oxide content is that 12.5% content of magnesia is 8.8%, and alumina content is 25%, the content of its silicon oxide is 4.3 times of calcium oxide content, and the content of calcium oxide is 1.4 times of magnesian content.
The actual viscosity temperature that dissolves is 10
1.5Temperature when (handkerchief second) is 1630 ℃ of viscosity temperatures, the actual homogenizing exhaust bubble viscosity temperature 10 of annealing
2It is 1480 ℃ when (handkerchief second); Moulding viscosity temperature 10
3(handkerchief second) is 1270 ℃; Rolling over that brilliant temperature reaches the standard grade is 1230 ℃
The nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.88.
Comparative Examples 1, S level glass embodiment
Count as weight percents, the content of silicon oxide is 58% in this glass, calcium oxide content is that 1% content of magnesia is 15%, alumina content is 25%, boron oxide content is 14%, barium oxide content is 10%, and the content of its silicon oxide is 58 times (outside technical solution of the present invention 4.11-5.48 times scopes) of calcium oxide content, and the content of calcium oxide is 0.06 times of magnesian content.
The actual viscosity temperature that dissolves is 10
1.5Temperature when (handkerchief second) is 1740 ℃ of viscosity temperatures; Actual homogenizing exhaust bubble viscosity temperature 10
2It is 1620 ℃ when (handkerchief second); Moulding viscosity temperature 10
3(handkerchief second) is 1410 ℃;
The nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.8.
Comparative Examples 2, fluorine glass embodiment
Count as weight percents, the content of silicon oxide is 44% in this glass, calcium oxide content is 22%, content of magnesia is 7%, and alumina content is 20%, and fluorine content is that 7% (technical solution of the present invention is not fluorine-containing, and viscosity temperature and breaking tenacity (N/tex) are also better than it, can be considered the invention of key element elliptical), the content of its silicon oxide is 3.1 times (outside technical solution of the present invention 4.11-5.48 times scopes) of calcium oxide content, the content of calcium oxide is 3 times of magnesian content.
The actual viscosity temperature that dissolves is 10
1.5Temperature when (handkerchief second) is 1750 ℃ of viscosity temperatures; Actual homogenizing exhaust bubble viscosity temperature 10
2It is 1630 ℃ when (handkerchief second); Moulding viscosity temperature 10
3(handkerchief second) is 1420 ℃;
The nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, it is characterized in that: the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.68.
Comparative Examples 3, E level glass embodiment
Count as weight percents, the content of silicon oxide is 55% in this glass, calcium oxide content is that 16% content of magnesia is 5%, alumina content is 15%, boron oxide content is 9% (technical solution of the present invention oxygen-free boron, and viscosity temperature and breaking tenacity (N/tex) are also better than it, are to omit invention), the content of its silicon oxide is 3.4 times of calcium oxide content, and the content of calcium oxide is 3 times (outside technical solution of the present invention 0.8-2.2 times scopes) of magnesian content.
The actual viscosity temperature that dissolves is 10
1.5Temperature when (handkerchief second) is 1680 ℃; Actual homogenizing exhaust bubble viscosity temperature 10
2It is 1490 ℃ when (handkerchief second); Moulding viscosity temperature 10
3(handkerchief second) is 1310 ℃; Rolling over that brilliant temperature reaches the standard grade is 1230 ℃.
The nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, it is characterized in that: the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.56.
Comparative Examples 4, the inventor's prior art: application number is: 201110060932.1, denomination of invention is: " glass fibre and preparation method and glass fiber compound material that high strength and energy-saving, emission-reducing, environment friendly and low viscosity feature are arranged ".
Count as weight percents, the content of silicon oxide is 48.7% in this glass, calcium oxide content is that 16.8% content of magnesia is 12%, alumina content is 22.4%, sodium oxide content is 0.1%, the content of its silicon oxide is 2.9 times (outside technical solution of the present invention 4.11-5.48 times scopes) of calcium oxide content, and the content of calcium oxide is 1.4 times of magnesian content.
The actual viscosity temperature that dissolves is 10
1.5Temperature when (handkerchief second) is 1530 ℃; Actual homogenizing exhaust bubble viscosity temperature 10
2It is 1380 ℃ when (handkerchief second); Moulding viscosity temperature 10
3(handkerchief second) is 1170 ℃; Rolling over brilliant temperature reaches the standard grade and is 1220 ℃ and (rolls over brilliant temperature and be higher than 50 ℃ of mold temperatures, can only adopt the refrigerating unit of leting slip a remark especially to prevent from the drawing process producing the crystallization devitrification.But this is unfavorable for normally realizing the production of high efficiency extensive production capacity again).
The nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.72.
How technical solution of the present invention overcomes a plurality of prior art difficult points, has produced unforeseeable technique effect:
1, technical solution of the present invention is the more selection invention of close limit or different range of silicon, calcium, magnesium factor proportion; It is again the technical scheme of the solubility promoter key element of fluorine, boron being omitted invention; So overcome various traditional must be the technology prejudice of hydrotropy composition by fluorine, boron especially; Find and produced aluminium, silicon, the calcium of the high alumina content (content is 20-33% or 23-33% or 25-33%) of product, the new product property of magnesium eutectic function, so produced significantly energy-saving and cost-reducingly, reduce the technique effect of carbon emission again.
2, technical solution of the present invention overcome various traditional must be the technology prejudice of hydrotropy composition by fluorine, boron especially; It is again the technical scheme of the solubility promoter performance technologies key element of fluorine, boron being omitted invention; So do not have the poison gas of discharging boracic or fluorine in producing, reached and optimized the technique effect that environmental protection is produced.
3, technical solution of the present invention overcome various traditional must be the technology prejudice of hydrotropy composition by fluorine, boron especially; It is again the technical scheme of the solubility promoter performance technologies key element of fluorine, boron being omitted invention; So can all carry out cold repair to production line every year, there is production efficiency to heighten, reduced the cost techniques effect again.
4, technical solution of the present invention is owing to the new product property of the aluminium of having found the high alumina content of glass fiber product of the present invention, silicon, calcium, magnesium eutectic function; Because the lower character of viscosity temperature of glass fiber product of the present invention heightens so produced in production efficiency; Reduced cost again; The poison gas that does not have discharging boracic or fluorine in the production; Significantly save energy and reduce the cost and reduce again under the prerequisite of carbon emission: breaking tenacity (N/tex) can reach the very high tension breaking tenacity technique effect of 0.7-1.1.
So technique effect of the generation of the product innovation character of technical solution of the present invention and discovery; Can overcome the defective of the complete different technologies scheme generation of following multiple prior art products:
1, high, medium-alkali glass fibre: by weight percentage, silicon oxide-containing is about 67% in its composition, and magnesium oxide is about 1%, and calcium oxide is about 9.5%, the about 5-7% of aluminum oxide, and the about 2-10% of sodium oxide, fluorine oxide is about 0.5%, and boron oxide is about 3%, barium oxide about 2%; The defective of its goods is, the viscosity height in its production technique, and production energy consumption is big; When glass diameter≤9 micron, (N/tex) is poor for breaking tenacity, generally all below 0.4, so technique effect is poor.
And the obvious different technical scheme (see claim 1) of the present invention, glass fibre of the present invention omits the technical scheme of invention to the solubility promoter key element of fluorine, boron; The new product property of the aluminium of high alumina content, silicon, calcium, magnesium eutectic function; Because the lower character of viscosity temperature of glass fiber product of the present invention; Produce production efficiency and heightened, reduced cost again; The poison gas that does not have discharging boracic or fluorine in the production; Significantly save energy and reduce the cost and reduce again under the prerequisite of carbon emission: breaking tenacity (N/tex) can reach the very high tension breaking tenacity technique effect of 0.7-1.1, can overcome the defective of height, medium-alkali glass fibre.
2, alkali-free E glass fibre: by weight percentage, silicon oxide-containing is about 55% in its composition, and magnesium oxide is less than 2%, and calcium oxide is greater than 20%, and aluminum oxide is about 14%, and sodium oxide is less than 1%, boron oxide about 8%.Its defective processed is: production energy consumption is big, and a large amount of boron poison gas dischargings is arranged in the production; Because the boron composition is fast to the erosion of refractory brick, 2 years many refractory brick that are etched of replacing that will stop production, refractory brick cost height, 2 year life-span of production line is too short; The breaking tenacity weak effect; Boron oxide discharges a large amount of boracic poison gas aborning, and environmental issue is serious.
And the obvious different technical scheme (see claim 1) of the present invention, glass fibre of the present invention omits the technical scheme of invention to the solubility promoter key element of fluorine, boron; The new product property of the aluminium of high alumina content, silicon, calcium, magnesium eutectic function; Because the lower character of viscosity temperature of glass fiber product of the present invention; Produce production efficiency and heightened, reduced cost again; The poison gas that does not have discharging boracic or fluorine in the production; Significantly save energy and reduce the cost and reduce again under the prerequisite of carbon emission: breaking tenacity (N/tex) can reach the very high tension breaking tenacity technique effect of 0.65-1.0, can overcome the defective of alkali-free E glass fibre.
3, fluorine glass fibre: count as weight percents, the content of silicon oxide is about 44% in this glass, and calcium oxide content is about 22%, content of magnesia is about 7%, alumina content is 20%, and fluorine content is about 7%, and the content of calcium oxide is 3 times of magnesian content.Its defective is: a large amount of fluorine poison gas dischargings is arranged in the production, because the production technique of this high temperature has been accelerated the erosion of fluorine composition to refractory brick, determine annual will the stopping production to change many refractory brick that are etched, carry out cold repair to production line; The boron composition is fast to the erosion of refractory brick, refractory brick replace and cost very high, add that the life-span of production line is short, more raised total cost; The fluorine composition discharges a large amount of boracic poison gas aborning, and environmental issue is serious.
And the obvious different technical scheme (see claim 1) of the present invention, glass fibre of the present invention omits the technical scheme of invention to the solubility promoter key element of fluorine, boron; The new product property of the aluminium of high alumina content, silicon, calcium, magnesium eutectic function; Because the lower character of viscosity temperature of glass fiber product of the present invention; Produce production efficiency and heightened, reduced cost again; The poison gas that does not have discharging boracic or fluorine in the production; Significantly save energy and reduce the cost and reduce again under the prerequisite of carbon emission: breaking tenacity (N/tex) can reach the very high tension breaking tenacity technique effect of 0.65-1.0, can overcome the defective of fluorine glass fibre.
4, Zhong Guo S level high-strength glass fibre: by weight hundred the proportion by subtraction meter, silicon oxide-containing is about 61% in its composition, calcium oxide is about 0.3%, magnesium oxide is about 14%, aluminum oxide is about 25%, boron oxide about 4%; Its defective is:
When glass diameter≤9 micron, breaking tenacity (N/tex) generally all about 0.7-0.8, has the necessity that overcomes; The viscosity of this goods is too high in its production technique, and production energy consumption is too big, and yield efficiency is very low, and a line is only produced per year about hundred tons; And the production technique of its this high temperature, accelerate the boron composition to the erosion of refractory brick, determined all will carry out cold repair to production line its every year; Refractory brick replace and cost very high, add that the life-span of production line is too short, more raised total cost; Boron oxide discharges a large amount of boracic poison gas aborning, and environmental issue is serious.So the necessity that overcomes is arranged.
And obviously different technical scheme (see claim 1) of the present invention, glass fibre of the present invention omits the technical scheme of invention to the solubility promoter performance technologies key element of fluorine, boron; The new product property of the aluminium of high alumina content, silicon, calcium, magnesium eutectic function; Because the lower character of viscosity temperature of glass fiber product of the present invention; Produce production efficiency and heightened, reduced cost again; The poison gas that does not have discharging boracic or fluorine in the production; Significantly save energy and reduce the cost and reduce again under the prerequisite of carbon emission: especially because the new product property of the aluminium of high alumina content, silicon, calcium, magnesium eutectic function, can when technical solution of the present invention aluminum oxide Da Gaoda 25%--32%, be suitable for the viscosity temperature of ordinary production in addition, but so ordinary production, breaking tenacity (N/tex) can reach the S level high-strength glass fibre that surpasses existing top China, the glass fiber product of the very high tension breaking tenacity of 0.8-1.0; Can overcome the defective of the S level high-strength glass fibre of China.
5. overcome the inventor's prior art, the technical scheme of (application number is that 201110060932.1 patented invention name is called: glass fibre and preparation method and glass fiber compound material that high strength and energy-saving, emission-reducing, environment friendly and low viscosity feature are arranged) is without any moulding viscosity temperature 10
3The announcement of the relation of (handkerchief second) and the brilliant temperature of folding.
Actual defective is: recrystallization temperature is higher, is owing to be easy to be directed at the calcium oxide ratio higher (content of its silicon oxide is that calcium oxide content is 1.9 times-4.1 times) of crystallization in the technical scheme, the crystallization viscometric properties of its many technical schemes be 10
2.5(handkerchief second)-10
2.9(handkerchief second), be much higher than 10
3.0The mold temperature of (handkerchief second) glass fibre (Comparative Examples 4 referring to reality in the specification sheets is exactly like this); So this can only improve wire-drawing temperature at process system, adopt the refrigerating unit of leting slip a remark especially to prevent from producing in the drawing process crystallization devitrification; But this technology is unfavorable for normally realizing the production of high efficiency extensive production capacity again.
Solution of the present invention is to improve in the technical scheme of existing new technology, the calcium oxide ratio reduction that is easy to be directed at crystallization, (referring to Comparative Examples 4; With the present invention first to six embodiment): in the technical scheme of the inventor's existing new technology, the content of silicon oxide is 2 kinds of selections of 4.11 times-4.56 times or 4.57 times-5.48 times (rather than prior art 1.9 times-4.1 times) of calcium oxide content, this selection has reduced the calcium oxide content ratio that is directed at the folding crystalline substance, also is its extraneous selection invention; From the present invention first to six embodiment as seen: crystallization viscosity all is lower than 10
3.0The mold temperature of (handkerchief second) glass fibre.
And the present invention obviously different technical scheme (see claim 1) relatively the inventor's application number be that 201110060932.1 patented invention name is called: glass fibre and preparation method and glass fiber compound material that high strength and energy-saving, emission-reducing, environment friendly and low viscosity feature are arranged), found the new property of product: (have and be beneficial to the lower recrystallization temperature character of coupling of glass fibre moulding and mold temperature), so can avoid adopting a kind of refrigerating unit of leting slip a remark especially of production efficiency difference to prevent from producing the crystallization devitrification in the drawing process, thereby be conducive to the production that glass fibre of the present invention (also having very high tension breaking tenacity technical characterictic) can normally be realized high efficiency extensive production capacity;
6, prior art CN101580344A (Chinese megalith group): 1. its 0.7＜CaO/MgO＜2.2,2. preferred Al2O3 content range is 15-18% (5 pages in specification sheets); 3. and the aluminum oxide of its 6 examples all in 16%; (seeing its specification sheets 11,12 page tables 1, table 2) reflects a kind of technology prejudice.
The present invention obviously different technical scheme alumina contents of the present invention is 18.1%-33% or 21.1-33%, and the content of silicon oxide is 4.11 times-5.48 times of calcium oxide content, and the content of calcium oxide is 0.9 times-2.1 times of content of magnesia.Broken this technology prejudice:
Aforementioned it, glass fiber product of the present invention the solubility promoter performance technologies key element of fluorine, boron is omitted the technical scheme of invention because the lower character of viscosity temperature of glass fiber product of the present invention, production efficiency heightens, and has reduced cost again; The poison gas that does not have discharging boracic or fluorine in the production, significantly save energy and reduce the cost and reduce again under the prerequisite of carbon emission, especially because the new product property of the aluminium of high alumina content, silicon, calcium, magnesium eutectic function, not only broken high alumina in this traditional processing technology (surpassing 18%) can viscosity too high technology prejudice: (it is too high that a. dissolves viscosity, dissolve and badly can produce aluminum oxide and the silica crystal raw material can not form glassy phase by molten Hong, and a quarrel point quarrel piece occurs; B. row's bubble viscosity is too high can produce a large amount of bubbles; And these 2 all can have a strong impact on glass through superfine platinum hole the time, the fracture of wire phenomenon constantly occurs, and can not the big production of continuity); Also can when technical solution of the present invention aluminum oxide Da Gaoda 25%--32%, be suitable for the viscosity temperature of ordinary production in addition, but so ordinary production, breaking tenacity (N/tex) can reach the S level high-strength glass fibre that surpasses existing top China, the glass fiber product of the very high tension breaking tenacity of 0.8-1.0.
7, external S level high-strength glass fibre: by weight percentage, silicon oxide-containing is about 65% in its composition, and magnesium oxide is about 10%, aluminum oxide about 25%; Its defective is: its viscosity is too high, and production energy consumption is too big, and yield efficiency is very low, and yield efficiency is very low, and a line is only produced per year about hundred tons, and when glass diameter≤9 micron, breaking tenacity (N/tex) value difference is generally all in 0.9; Production energy consumption is too big, and yield efficiency is very low, and a line is only produced per year about hundred tons; And the production technique of this high temperature, accelerated the erosion of boron composition to refractory brick, determined all will carry out cold repair to production line its every year; Refractory brick replace and cost very high, add that the life-span of production line is too short, more raised total cost.
Because the lower character of viscosity temperature of glass fiber product of the present invention; Produce production efficiency and heightened, reduced cost again; The poison gas that does not have discharging boracic or fluorine in the production; Significantly save energy and reduce the cost and reduce again under the prerequisite of carbon emission; Especially, the new product property of the aluminium of high alumina content, silicon, calcium, magnesium eutectic function, can when technical solution of the present invention aluminum oxide Da Gaoda 25%--32%, be suitable for the viscosity temperature of ordinary production in addition, so but ordinary production breaking tenacity (N/tex) can reach the S level high-strength glass fibre that surpasses existing top China 0.8, the glass fiber product of the tension breaking tenacity of 5-1.0; Can overcome the defective of external S level high-strength glass fibre.
8, documents: prior art TW201144249A relatively, embodiment 15 its aluminum oxide 18.7% wherein, the content of silicon oxide is 4.5 times of calcium oxide content, the content of calcium oxide is 1.33 times of magnesian content; And among its 19 embodiment, 2 silicon oxide are only arranged: the content of calcium oxide, calcium oxide: magnesian content within the scope of the present invention, and these 2 embodiment aluminum oxide all are lower than 20%, because aluminum oxide all is lower than 20%; The low defective of breaking tenacity (N/tex) that has glass fibre;
Its only 2 embodiment aluminum oxide be higher than 20%, but not at silicon oxide of the present invention: the content of calcium oxide, calcium oxide: in the magnesian content range, so it does not only have aluminium, silicon, the calcium of high alumina content in the technical solution of the present invention, the new low viscosity temperature property of magnesium eutectic function, do not disclose aluminium, silicon, the calcium of high alumina content in the technical solution of the present invention, the new low viscosity temperature property of magnesium eutectic function yet.
Especially, the new product property of the aluminium of high alumina content, silicon, calcium, magnesium eutectic function in the technical solution of the present invention, not only oxidable aluminium is when 20-25%, the low viscosity temperature that is suitable for ordinary production is arranged and high tensile breaking tenacity [seeing 6 embodiment and Comparative Examples] is arranged, also can be suitable for the low viscosity temperature of ordinary production in addition and high tensile breaking tenacity [seeing 6 embodiment and Comparative Examples] is arranged during up to 25%--33% at aluminum oxide;
So technical solution of the present invention not only can be produced the glass fiber product of the breaking tenacity (N/tex) 0.85 that has top S level high-strength glass fibre now under the low viscosity temperature condition; Also can be under the low viscosity temperature condition, produce the breaking tenacity (N/tex) that surpasses existing top S level high-strength glass fibre, reach the glass fiber product of the more high tensile breaking tenacity of 0.85-1.1;
Technical solution of the present invention not only can overcome the low defective of breaking tenacity (N/tex) of prior art TW201144249A glass fibre; Can also be because of the new low viscosity temperature property of the aluminium of high alumina content, silicon, calcium, magnesium eutectic function, produced: A, production efficiency heighten, and have reduced cost again; B, the energy-saving and cost-reducing carbon emission that reduces again significantly; C, be 10 because new low viscosity temperature property has formed an actual viscosity temperature that dissolves
1.5When (handkerchief second), be conducive to fully dissolving of aluminium in the raw material of high-alumina and silicon, significantly reduce the new platform of technology controlling and process of quarrel point and calculus, be conducive to the lifting of glass fibre quality and yield; D, formed an actual homogenizing exhaust bubble viscosity temperature 10 because of new low viscosity temperature property
2Fully discharge the new platform of technology controlling and process of especially trickle bubble when (handkerchief second), be conducive to the lifting of glass fibre quality and yield;
9, compare prior art CN101119939A: 1. its aluminum oxide is 12-20%, calcium: two end values of magnesium are 12/12: 17/6=1: 2.8 times, obvious proportionlity of the present invention is the close limit selection invention; 2. and its 7 example alumina contents of this documents in 15%, it is not found and discloses 21.1-29.9%'s of the present invention, silicon oxide: the ratio of calcium oxide when 4.11 times one 5,48 times scope technical scheme, the eutectic of the silicon of high aluminium content, calcium, magnesium, aluminium and low viscosity high strength characteristics and unforeseeable technique effect.Be significantly smaller than the scope of aluminum oxide 21.1-33% of the present invention.As seen this documents is not a technical scheme consistent with objects of the present invention.And this prior art does not disclose silicon, calcium, the magnesium of high aluminium content of the present invention, eutectic and low viscosity high strength characteristics and the unforeseeable technique effect of aluminium.
10, compare prior art US455072 (31.03.1975): 1. the aluminum oxide 10-12% of its claim is significantly less than content of the present invention, 2. have only one to be Al2O3 content 10.07 in the example, also be significantly less than content of the present invention, 3. and the silicon oxide of other example this invention is not the character (being doubly above big difference of 1-2) of 21.1-29.9% high-alumina component content of the present invention, and: calcium oxide and calcium oxide: magnesium oxide is not within the scope of the present invention.And this prior art does not disclose high aluminium content of the present invention, silicon oxide: the ratio of calcium oxide when 4.11 times-5,48 times the scope technical scheme, the eutectic of silicon, calcium, magnesium, aluminium and low viscosity high strength characteristics and unforeseeable technique effect.
12, CN1162950A (22.10.1997) relatively: its principal right requires and example, and 1. especially the technology essential factor proportionlity of silicon, calcium, magnesium is not within the scope of the present invention; 2. and the fluorine composition of the example of its specification sheets almost all reach 5-10%; And all the elements of the present invention not fluorine-containing composition, the present invention is that a kind of fluorine composition omits invention; So 3. they are not only different with the present invention, and extremely serious to the corrosion of producing equipment, maintenance and depreciable cost are high, and environmental protection destruction is extremely serious, and the present invention is the solution to this technical barrier.And this prior art do not disclose the high aluminium content of 20-33% of the present invention, and the ratio of calcium oxide is at 4.11 times-5.48 times scope technical scheme, the eutectic of silicon, calcium, magnesium, aluminium and low viscosity high strength characteristics and unforeseeable technique effect.
13, the air blade material in glass fiber compound material especially, because the intensity of the glass fibre that uses is low, or the cost of S level glass is too high, yield poorly, so the wind sweeping area of air blade does not increase, seriously restricted the conversion of wind energy to electric energy, restricted the cost of electricity-generating of wind-powered electricity generation, its cost is much higher than thermoelectricity, water power.
When being applied to matrix material, an advantage is that the present invention can be at lower cost on the big production line of porcelain kiln of E, A glass fibre, article one, line year is produced hundreds of thousands of ton S level or super S level high-strength fiber glass, change line of global expensive S level glass and only produce S level glass 200-300 ton per year, not only cost is too high and the production capacity bottleneck that can't supply in a large number, the production capacity of long-standing S level glass just, the bottleneck difficult problem that production efficiency and cost are too high.And the above-mentioned technique effect of technical solution of the present invention can provide sufficient core material material guarantee to wind electricity blade on production capacity and on the lower cost.The core of wind energy transformation efficient is that the high strength fibre product can make the air blade lightweight, thus the lightweight of the seizure wind energy that produces, the expansion of high strength blade exhibition wind area and the ratio difficult problem of solution wind-powered electricity generation efficient and cost.
When being applied to matrix material, because glass breaking tenacity of the present invention can significantly rise, so can enlarge the intensity effect of matrix material, promote lightweights such as its car, ship, chemical petroleum tank body, pipeline; Especially in wind power industry, because cost is low, more be significantly less than the expensive glass of S level, and intensity can meet and exceed the expensive glass of S level.So with its glass fibre of making and resin composite materials, the high strength of 1 times of rising can be arranged or the composite product of lightweight more than 1 times under equality strength.
In this application to the air blade material of wind-power electricity generation, what further specify is: since usually in glass fiber composite material resin only account for below 30%, glass fibre accounts for more than 70%, and matrix material is played skeleton and intensity most important functions.As described above, perhaps glass intensity rises one times, and then available 50% reaches same intensity.And resin also can descend 50% in proportion, and matrix material weight also falls 50%, and intensity also can be constant; Perhaps weight rises one times, and then the intensity of matrix material can rise one times.Owing to can make E level, the A level glass of the original usefulness of employing of present wind power blade, change into and use intensity of the present invention to rise more to be significantly less than S level glass cost more than one times, and can meet and exceed the glass of the present invention of S level glass intensity the time, can make matrix material under the situation of equivalent weight, intensity rising 60%-100% or more, just can an exhibition wind area is strengthened 60%-100% or more than.This will make, and (the glass cost only is percentum of wind energy turbine set construction cost) wind power transformation is the efficient rising 60%-100% of electric power under same or slightly high any condition of total cost.(existing design can accomplish to adopt the design that strengthens exhibition wind area 15%, and wind-powered electricity generation efficient just rises 15%, has also got on but fan blade has weighed other costs, and frictional force has also got on, and also can not reach the purpose of wind power transformation electric energy well; And characteristics of the present invention are can not increase air blade weight and frictional force when increasing air blade wind sweeping area 60-100%, and wind power transformation is the efficient of the electric power 60%-100% that can rise).
And if realized that cost does not rise substantially, wind energy efficiency rising 60-100%, just can form the cost of wind energy and energy transformation or wind energy capturing efficiency and be better than the thermoelectricity cost greatly, this will provide the support of a kind of industry meaning of core material glass technological invention for the reproducible energy-wind power generation of cleaning (because wind-powered electricity generation wind energy conversion cost is generally than about the high 40-50% of thermoelectricity now).Thereby make the efficient of wind-powered electricity generation and the economy of cost, surpass the efficient of thermoelectricity and the economy of cost.It also is the great technical contribution to the difficult problem solution of new renewable energy source industry.
The present invention is 4.11 times-5.48 times and different technical schemes existing all glass technology compositions because adopted especially silicon, ca proportion, especially adopted up to the alumina content of 20%-33% or 23-33% or 25-33% the time, selection invention technical scheme to the proportionlity between silicon, magnesium, the calcium has produced: (1) is to the omission inventive features of the fluorine of prior art, boron, composition key element; (2) new high aluminium content, the eutectic of silicon, calcium, magnesium, aluminium and low viscosity feature.(3) and simultaneously can produce the feature controlled that more is conducive to extensive high-quality production between mold temperature and the recrystallization temperature.(4) the high breaking tenacity feature of Chan Shenging; The product innovation character of never crossing that combines together that aforementioned these four kinds of row are levied can't be inferred prior, and is unpredictable; And many technology prejudice have been overcome, just in new purposes, produced unforeseeable above-mentioned technique effect, produced the variation of " matter " and " amount " of above-mentioned technique effect, illustrated that technical scheme is non-obvious, have outstanding substantive distinguishing features and significant technical progress, creative.
Produced unforeseeable above-mentioned technique effect, here wanting ben is that if do not have suitable mold temperature and the coupling of recrystallization temperature, the product of high breaking tenacity is scale operation effectively just, quality and yield all will descend greatly, and cost also can rise.This also is invention core point of the present invention.The present invention is based on this point and has 4 described material characters concurrently.So can produce a large amount of energy-conservation of practicality, environmental protection improves production capacity, reduces cost, and reduces unforeseeable above-mentioned technique effects such as Carbon emission.
The above, only be for preferable preferred embodiment of the present invention is described, yet it is not to be limitation of the present invention, any personnel that are familiar with this technology may utilize the technology contents of above-mentioned announcement to be changed or be modified to the equivalent embodiment of equivalent variations, can implement glass fibre and preparation method and glass fiber compound material by difference requirement and performance.As seen, hold within the every content that does not break away from technical solution of the present invention, the especially claim, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (9)
1. glass fibre, its nominal diameter at 3 microns in 15 microns, the deviate of this glass fiber diameter is in nominal diameter ± 15%, it is characterized in that: count as weight percents, in this glass fibre, alumina content is 20-33%, and content of magnesia is 5.5-20%, the content of silicon oxide is 4.11--5.48 times of calcium oxide content, and the content of calcium oxide is 0.9--2.1 times of content of magnesia.
2. glass fibre as claimed in claim 1 is characterized in that, the breaking tenacity when diameter is less than or equal to 9 microns is 0.7-1.1.
3. glass fibre as claimed in claim 1 is characterized in that, the content of silicon oxide is 4.11 times of calcium oxide content--4.55 times, the content of calcium oxide is 0.9-1.9 times of content of magnesia.
4. the described glass fibre of claim 1 is characterized in that, counts as weight percents, and in this glass fibre, the content of silicon oxide is 4.55 times of calcium oxide content---5.48 times.
5. the described glass fibre of claim 1 is characterized in that, counts as weight percents, and in this glass fibre, alumina content is 23-33%.
6. the described glass fibre of claim 1 is characterized in that, counts as weight percents, and in this glass fibre, alumina content is 25-33%.
7. glass fiber compound material, this matrix material comprise plastic substrate and embed the described glass fibre of claim 1--5 in the plastic substrate.
8. the preparation method of a glass fibre, the nominal diameter of this glass fibre within 3 microns to 15 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, it is characterized in that:
Step 1, prescription according to the described glass fibre of claim 1-6, dispose required various have predetermined requisite aluminum oxide, silicon oxide, calcium oxide, magnesium oxide composition and predetermined silicon oxide, calcium oxide, magnesium oxide, after mixing stirring, melt in the temperature of fusion corresponding to each glass fiber formula, form the glass metal of predetermined viscosity, homogenizing is clarified again, discharge bubble, form flowable molten mass;
The melten glass body that forms in the step 2, step 1 stretches and the formation glass fibre through some holes of the refractory metal plate of porous high speed, through cooling, can make described fiberglass products.
9. the preparation method of glass fibre as claimed in claim 8 is characterized in that, this glass fibre is 10 in viscosity
1.5The temperature of handkerchief during second is 1480 ℃-1690 ℃; Viscosity is 10
2The temperature of handkerchief during second is 1370 ℃-1490 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556711A (en) * | 2015-02-03 | 2015-04-29 | 重庆国际复合材料有限公司 | Special-shaped glass fiber and preparation method thereof |
| WO2016086500A1 (en) * | 2014-12-01 | 2016-06-09 | 杨德宁 | Application and preparation method of glass fiber having low devitrification temperature, low devitrification speed, high-temperature resistance and extra-high content of aluminum, and composite material |
| CN109952277A (en) * | 2016-11-14 | 2019-06-28 | Ａｇｃ株式会社 | The manufacturing method of melten glass and the manufacturing method of glass article |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104692652A (en) * | 2013-12-06 | 2015-06-10 | 杨德宁 | Glassware produced by cooling portion crystallization prevention method |
| CN104386914A (en) * | 2014-10-30 | 2015-03-04 | 泸州观宇玻璃制品有限公司 | Method for preparing glass cup |
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| CN114031292A (en) * | 2021-12-07 | 2022-02-11 | 中氢国储(杭州)精密制造有限公司 | Formula of high-alumina-silica glass tube and manufacturing method of high-alumina-silica glass tube |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101300199A (en) * | 2005-11-04 | 2008-11-05 | Ocv智识资本有限责任公司 | Composition for high performance glass, high performance glass fibers and articles therefrom |
| CN101580344A (en) * | 2009-06-29 | 2009-11-18 | 巨石集团有限公司 | High strength glass fiber composition |
| CN101815685A (en) * | 2007-08-03 | 2010-08-25 | S.D.R.生物科技程序技术有限责任公司 | Thermally resistant fiber glass |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1209244A (en) * | 1967-04-05 | 1970-10-21 | Owens Corning Fiberglass Corp | Glass composition |
| GB1462035A (en) * | 1973-02-02 | 1977-01-19 | Nat Res Dev | Microcrystalline material |
| JP4086210B2 (en) * | 1998-04-17 | 2008-05-14 | Ｈｏｙａ株式会社 | Substrate for information recording medium |
| JP2001348246A (en) * | 2000-06-01 | 2001-12-18 | Asahi Glass Co Ltd | Glass for substrate and glass substrate |
| JP2002220256A (en) * | 2001-01-22 | 2002-08-09 | Asahi Glass Co Ltd | Lead-free glass, electronic circuit board composition, and the electronic circuit board |
| FR2870842B1 (en) * | 2004-05-27 | 2007-11-02 | Saint Gobain | METHOD AND DEVICE FOR MANUFACTURING GLASS AND PRODUCTS OBTAINED USING THE SAME |
| CN100337954C (en) * | 2005-02-06 | 2007-09-19 | 河南安彩高科股份有限公司 | Non-alkali glass composition of high specific modulus value and its use |
| CN103482875B (en) * | 2010-03-18 | 2015-11-25 | 杨德宁 | Glass fibre and preparation method thereof, matrix material |
-
2013
- 2013-04-01 CN CN 201310108590 patent/CN103145333A/en not_active Withdrawn
- 2013-05-06 CN CN201310161555XA patent/CN103232165A/en active Pending
- 2013-05-06 WO PCT/CN2013/000510 patent/WO2013181925A1/en active Application Filing
- 2013-05-06 CN CN2013101615564A patent/CN103224327A/en active Pending
- 2013-05-06 WO PCT/CN2013/000507 patent/WO2013181922A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101300199A (en) * | 2005-11-04 | 2008-11-05 | Ocv智识资本有限责任公司 | Composition for high performance glass, high performance glass fibers and articles therefrom |
| CN101815685A (en) * | 2007-08-03 | 2010-08-25 | S.D.R.生物科技程序技术有限责任公司 | Thermally resistant fiber glass |
| CN101580344A (en) * | 2009-06-29 | 2009-11-18 | 巨石集团有限公司 | High strength glass fiber composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016086500A1 (en) * | 2014-12-01 | 2016-06-09 | 杨德宁 | Application and preparation method of glass fiber having low devitrification temperature, low devitrification speed, high-temperature resistance and extra-high content of aluminum, and composite material |
| CN104556711A (en) * | 2015-02-03 | 2015-04-29 | 重庆国际复合材料有限公司 | Special-shaped glass fiber and preparation method thereof |
| CN109952277A (en) * | 2016-11-14 | 2019-06-28 | Ａｇｃ株式会社 | The manufacturing method of melten glass and the manufacturing method of glass article |
| CN109952277B (en) * | 2016-11-14 | 2021-12-31 | Ａｇｃ株式会社 | Method for producing molten glass and method for producing glass article |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103145333A (en) | 2013-06-12 |
| WO2013181925A1 (en) | 2013-12-12 |
| WO2013181922A1 (en) | 2013-12-12 |
| CN103224327A (en) | 2013-07-31 |
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