CN102557459A

CN102557459A - Glass fiber with high strength and energy-saving, emission-reducing, environment-friendly and low-viscosity characteristics, preparation method for glass fiber, and glass fiber composite material

Info

Publication number: CN102557459A
Application number: CN2011100609321A
Authority: CN
Inventors: 杨德宁
Original assignee: Individual
Current assignee: Individual
Priority date: 2010-03-18
Filing date: 2011-03-15
Publication date: 2012-07-11
Also published as: WO2011113303A1

Abstract

The invention relates to a glass fiber with high strength and energy-saving, emission-reducing, environment-friendly and low-viscosity characteristics. The nominal diameter of the glass fiber is 5 to 13mu m; and the deviation value of the diameter of the glass fiber is within +/-15 percent of the nominal diameter. The glass fiber is characterized by comprising the following components in percentage by weight: 8 to 39 percent of aluminum oxide, silicon oxide, calcium oxide, 0.01 to 3 percent of iron oxide, 0.01 to 8.8 percent of sodium oxide, 0 to 10 percent of boron oxide, 8.1 to 20 percent of magnesium oxide and 0 to 1 percent of fluorine oxide, wherein the content of the silicon oxide is 1.9 to 4.1 times that of the calcium oxide, and the content of the calcium oxide is 1.2 to 1.6 times that of the magnesium oxide.

Description

Spun glass and preparation method and glass fiber compound material that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged

Technical field

The present invention relates to spun glass of HS and energy-saving, emission-reducing, environment friendly and LV characteristic and preparation method thereof, reach the matrix material that uses this spun glass; Concrete; The nominal diameter that relates to this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Sodium oxide, red stone, aluminum oxide, silicon oxide, quicklime, Natural manganese dioxide in the predetermined requisite special scope is arranged or also have the new range of choice of titanium oxide, barytic composition to invent; And the technical scheme of factor proportion relationship change invention between the predetermined silicon oxide, quicklime, Natural manganese dioxide; It is the innovative technology scheme of the selection invention of the close limit between a kind of end value of silicon, calcium, magnesium factor proportion scope of relatively existing all glasses technology; Overcome various traditional must be the technological prejudice of hydrotropy composition by sodium or boron; Key also is; Adopted the technology essential factor of having taked to omit the technical scheme of invention to sodium or boron; And the selection invention of the scope of the big content of aluminum oxide formed new a kind of integration factor invention technical scheme with it, produced the product property of eutectic function of LV temperature property, the high alumina content of unforeseeable product, and the goods diameter that produces evenly, quality rises, intensity rising 1-3 doubly, the service life of equipment lengthening, production efficiency improves and a kind of spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of the technique effect of environmental protection, energy-saving and emission-reduction etc. and preparation method thereof and the matrix material that uses this spun glass.

Background technology

Existing glass fiber and glass fiber compound material goods:

1, high, medium-alkali glass fibre: by weight percentage, silicon oxide-containing is about 67% in its composition, and Natural manganese dioxide is about 1%, and quicklime 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 in its production technique is high, and production energy consumption is big, and when glass diameter≤9 micron, breaking tenacity (N/tex) value difference generally all below 0.4, has the necessity that overcomes.

2, alkali free glass fibre: by weight percentage, silicon oxide-containing is about 55% in its composition, and Natural manganese dioxide is about 3%, and quicklime is about 19%, and aluminum oxide is about 14%, and sodium oxide is about 1%, the about 8-14% of boron oxide; The defective of its goods is that the viscosity in its production technique is high, and production energy consumption is big, and a large amount of boron poison gas dischargings is arranged in the production; When glass diameter≤9 micron, breaking tenacity (N/tex) value difference generally all about 0.4, has the necessity that overcomes.

3, domestic S level high-strength glass fibre: by weight percentage, silicon oxide-containing is about 63% in its composition, and quicklime is about 0.3%, and Natural manganese dioxide is about 14%, and aluminum oxide is about 25%, boron oxide about 2%; The defective of its goods is, when glass diameter≤9 micron, breaking tenacity (N/tex) value difference 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 1000 tons.And its this high alumina pyritous production technique determined all will carry out cold repair to production line its every year, strengthened cost, so the necessity that overcomes is arranged.

4, external S level high-strength glass fibre: by weight percentage, silicon oxide-containing is about 65% in its composition, and Natural manganese dioxide is about 10%, aluminum oxide about 25%; When glass diameter≤9 micron, breaking tenacity (N/tex) value difference is generally all in 0.9.

5, the air blade material in glass fiber compound material especially; Because the intensity of the spun glass that uses is low, or the cost of S level glass is too high, yields 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 HS glass cost performance of product and HS more, could fundamentally solve the cost of wind-powered electricity generation, be that people thirst for solving and the great difficult problem of achieving success never.

6, show all alkali-free boron fiberglass both at home and abroad, all contain the boron of 6-10%, a large amount of boracic poison gas of discharging in the production, environmental issue is serious.

7, show alkali-free fluorine glass, all contain the fluorine oxide of 6-10%, alumina content is within 8-18%, and environmental protection is poor, and work efficiency is low, and product strength is poor.

8, be used for refinforced cement, the alkaline-resisting zirconium glass fiber that contains of prior art yield poorly, and its viscosity temperature character is very high, and breaking tenacity is very poor again, is merely about 0.4 (N/tex), makes the effect of refinforced cement that very big defective arranged.

Summary of the invention

Because the defective and the deficiency of above-mentioned prior art; The inventor is based on being engaged in this type of product design manufacturing pragmatic experience and expertise for many years; Actively study innovation; In the hope of the deficiency and the defective that can overcome prior art, after having solved complicated production technique problem, propose to adopt the special nominal diameter that relates to this spun glass within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.45-1.3, and the technical scheme of the invention of factor proportion relationship change between predetermined silicon oxide, quicklime, the Natural manganese dioxide is arranged, and is the innovative technology scheme of the selection invention of the close limit between a kind of end value of silicon, calcium, magnesium factor proportion scope of relatively more existing all glasses technology.Overcome various traditional must be the technological prejudice of hydrotropy composition by sodium or boron.Key also is; Adopted the technology essential factor of having taked to omit the technical scheme of invention to sodium or boron; And the selection invention of the scope of the big content of aluminum oxide formed new a kind of integration factor invention technical scheme with it again; Produced the product property of eutectic function of LV temperature property, the high alumina content of unforeseeable product, and the goods diameter that produces evenly, quality rises, intensity rising 1-3 doubly, the service life of equipment lengthening, production efficiency improves and a kind of spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of the technique effect of environmental protection, energy-saving and emission-reduction etc. and preparation method thereof and the matrix material that uses this spun glass.

First embodiment of the invention provides a kind of spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Wherein, this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 8-39% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-8.8%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 1.9 times-4.1 times of calcium oxide content, and the content of quicklime is 1.2 times-1.6 times of content of magnesia.

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Breaking tenacity when wherein, its diameter is less than or equal to 9 microns (N/tex) is 0.45-1.3.

According to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of first embodiment of the invention, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Wherein, this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 19-39% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-2%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1550 ℃-1700 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1620 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1480 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1160 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.6-1.3.

According to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of first embodiment of the invention, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Wherein, this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 8-30% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-2%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1500 ℃-1640 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1230 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.45-1.1.

According to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of first embodiment of the invention, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Wherein, this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 8-19% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-2%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1500 ℃-1580 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1520 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1310 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1160 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.45-0.7.

According to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of first embodiment of the invention, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Wherein, this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 8-39% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-2%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1550 ℃-1700 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1620 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1480 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1330 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.45-1.3.

According to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of first embodiment of the invention, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Wherein, this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 26-39% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-2%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1610 ℃-1710 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1500 ℃-1640 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1310 ℃-1490 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1200 ℃-1340 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.75-1.3.

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Wherein, by weight percentage, zirconic content is 1-25% in this spun glass.

According to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of first embodiment of the invention, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Wherein, (1), as weight percents the meter, in its goods content: 1. Natural manganese dioxide accounts for 7-20%; 2. quicklime is in magnesian 1.0 times-1.8 times scope; 3. silicon oxide is that 4. silicon oxide is that 5. aluminum oxide is 0.1-30% in 2.2 times-3.8 times the scope of quicklime in magnesian 2.6 times-5.6 times scope; 6. sodium oxide is 0-18%, and 7. barium oxide is 0-5%; (2), the strain point temperature of its goods is in 560 ℃-720 ℃ scope; (3), the water-intake rate of its goods is in the scope of 0-0.001%; (4), as weight percents the meter, the content summation of Natural manganese dioxide, quicklime, three kinds of compositions of silicon oxide reaches 51%-100% in its goods.

According to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of first embodiment of the invention, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Wherein, (1), meter as weight percents, in its goods content: 1. the content of quicklime is 0.6 times-2.4 times of magnesian content, 2. the content of silicon oxide is 1.3 times-5.8 times of magnesian content; 3. the content of silicon oxide is 1.3 times-5.8 times of content of quicklime; 4. aluminum oxide is 0.1-30%, and 5. sodium oxide is 0-18%, and 6. barium oxide is 0-20%; (2), wherein the content summation of Natural manganese dioxide, quicklime, three kinds of compositions of silicon oxide reaches 51%-99.9%; (3), the water-intake rate of its goods is in the scope of 0-0.001%.

According to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of first embodiment of the invention, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Wherein, (1), as weight percents the meter, in its goods content: 1. Natural manganese dioxide accounts for 7-20%; 2. the content of quicklime is 1.0 times-1.8 times of magnesian content; 3. the content of silicon oxide is 2.6 times-5.6 times of magnesian content, and 4. the content of silicon oxide is 2.2 times-3.8 times of content of quicklime, and 5. aluminum oxide is 0.1-30%; 6. sodium oxide is 0-18%, and 7. barium oxide is 0-5%; (2), the strain point temperature of its goods is in 560 ℃-720 ℃ scope; (3), the water-intake rate of its goods is in the scope of 0-0.001%; (4), as weight percents the meter, the content summation of Natural manganese dioxide, quicklime, three kinds of compositions of silicon oxide reaches 51%-99.9% in its goods.

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Wherein, count as weight percents, in its goods content: quicklime is magnesian 1.15 times-1.8 times.

According to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of first embodiment of the invention, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Wherein, (1), as weight percents the meter, in its goods content: 1. Natural manganese dioxide accounts for 9.1-22%; 2. the content of quicklime is 0.6 times-2.0 times of magnesian content; 3. the content of silicon oxide is 2.8 times-5.6 times of magnesian content, and 4. the content of silicon oxide is that 5. aluminum oxide is 0.1-30% in 2.3 times-3.8 times the scope of content of quicklime; 6. sodium oxide is 0-18%, and 7. barium oxide is 0-5%; (2), the strain point temperature of its goods is in 560 ℃-720 ℃ scope; (3), the water-intake rate of its goods is in the scope of 0-0.001%; (4), as weight percents the meter, the content summation of Natural manganese dioxide, quicklime, three kinds of compositions of silicon oxide reaches 51%-99.9% in its goods.

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Wherein, count as weight percents, when alumina content reached 0-3.8% in the goods: viscosity was 10 ¹The melting process temperature of (handkerchief second) is 1300 ℃-1400 ℃; Viscosity is 10 ²The clarification of (handkerchief second), exhaust bubble technological temperature are 1120 ℃-1260 ℃; Viscosity is 10 ³The moulding process temperature of (handkerchief second) is 1010 ℃-1060 ℃; The folding strength of its goods reaches 60-100MPa.

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Wherein, count as weight percents, when alumina content reached 3.8-15% in the goods: viscosity was 10 ¹The melting process temperature of (handkerchief second) is 1320 ℃-1430 ℃; Viscosity is 10 ²The clarification of (handkerchief second), exhaust bubble technological temperature are 1140 ℃-1290 ℃; Viscosity is 10 ³The moulding process temperature of (handkerchief second) is 1040 ℃-1130 ℃; The folding strength of its goods reaches 80-130MPa.

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Wherein, count as weight percents, when alumina content reached 15-23% in the goods: viscosity was 10 ¹The melting process temperature of (handkerchief second) is 1360 ℃-1550 ℃; Viscosity is 10 ²The clarification of (handkerchief second), exhaust bubble technological temperature are 1250 ℃-1430 ℃; Viscosity is 10 ³The moulding process temperature of (handkerchief second) is 1060 ℃-1200 ℃; The folding strength of its goods reaches 100-180MPa.

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention; The nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, wherein; Count as weight percents; In this glass, the content of silicon oxide is 2.6 times-5 times of magnesian content, and the content of silicon oxide is 2.4 times-3.4 times of content of quicklime.

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Wherein, a kind of spun glass increases cement material, and this material comprises cement matrix and embeds each the glass fiber reinforced cement material that especially contains 1-25% zirconium white composition that utilizes the foregoing description in the cement matrix.

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Wherein, a kind of glass fiber compound material, this matrix material comprise plastic substrate and embed the glass fiber compound material that the utilization in the plastic substrate is made according to the spun glass of the foregoing description.

Second embodiment of the invention provides a kind of preparation method that the spun glass of HS and energy-saving, emission-reducing, environment friendly and LV characteristic is arranged; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Wherein, step 1, according to each described glass fiber formula of claim 1-8 dispose required various sodium oxide in the predetermined requisite special scope, red stone, aluminum oxide, silicon oxide, quicklime, Natural manganese dioxide are arranged or also have titanium oxide, barytic composition and predetermined silicon oxide, quicklime, Natural manganese dioxide between the raw material of innovative technology scheme of composition of specific proportions relation; Stir afterwards in temperature of fusion fusing through mixing corresponding to each glass fiber formula; Form the spun glass liquid of predetermined viscosity, homogenizing is clarified again; Discharge bubble, form flowable molten mass; Step 2, high speed stretches and forms spun glass through some holes of a porous refractory metal plate to the melten glass corpus fibrosum that forms in the step 1, through cooling, can make described fiberglass products.

According to the method for second embodiment of the invention, wherein, this spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1530 ℃-1700 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1430 ℃-1620 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1180 ℃-1480 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1320 ℃.

Here be noted that content of the present invention and some right of priority parts, its breaking tenacity to spun glass was not measured at that time, can only measure material to its folding strength, so right of priority partly has the statement of material folding strength.

Description of drawings

Fig. 1 is a kind of normal section synoptic diagram that the fiberglass products of HS and energy-saving, emission-reducing, environment friendly and LV characteristic is arranged of the present invention.

Fig. 2 is the preparation technology's of a kind of spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic arranged of the present invention a schematic flow sheet.

The explanation of Reference numeral

1: represent a kind of fiberglass products that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged

Embodiment

Therefore the spun glass of prior art generally can, cause the restriction of aspects such as various viscosity temperatures with silicon oxide as main matrix or skeleton.Technical scheme of the present invention innovation ground utilizes having of aluminum oxide, silicon oxide, Natural manganese dioxide and quicklime, sodium oxide, red stone, titanium oxide composition to flux or the composition of congruent melting character is used as the major ingredient of spun glass, and according to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of the embodiment of the invention on the composition with performance on all different with the spun glass of prior art.Below, embodiments of the invention are carried out detailed explanation.

First embodiment

According to one embodiment of the invention, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, it is characterized in that:

This glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, titanium oxide, red stone, sodium oxide, wherein, and meter as weight percents; Alumina content is 10-39% in this spun glass; Iron oxide content is 0.01-3%, and sodium oxide content is 0.01-8.8%, and boron oxide content is 0-10%; Content of magnesia is 8.1-20%; Fluorine oxide content is 0-1%, and the content of silicon oxide is 1.9 times-4.1 times of calcium oxide content, and the content of quicklime is 1.2 times-1.6 times of content of magnesia.

Its preparation method is characterised in that: step 1; According to each described glass fiber formula of claim 1-8 dispose required various sodium oxide in the predetermined requisite special scope, red stone, aluminum oxide, silicon oxide, quicklime, Natural manganese dioxide are arranged or also have titanium oxide, barytic composition and predetermined silicon oxide, quicklime, Natural manganese dioxide between the raw material of innovative technology scheme of composition of specific proportions relation; Stir afterwards in temperature of fusion fusing through mixing corresponding to each glass fiber formula; Form the spun glass liquid of predetermined viscosity, homogenizing is clarified again; Discharge bubble, form flowable molten mass;

Step 2, high speed stretches and forms spun glass through some holes of a porous refractory metal plate to the melten glass corpus fibrosum that forms in the step 1, through cooling, can make described fiberglass products.

The present invention reels off raw silk from cocoons under the prerequisite of technology adopt stretching; Adopted the specified proportion composition of relations prescription of above-mentioned brand-new technology scheme again; Changed the multiple technologies prejudice of prior art, solved people and thirsted for solving and never having the technical barrier of succeeing, promptly in a glass fiber product; Under the prerequisite that solves nominal diameter deviate above-mentioned high breaking tenacity performance and certain, mainly solved the multiple technologies effect that reduces viscosity temperature problem and environmental protection and elaborated.In addition, a large amount of adding of existing technology aluminum oxide can make the intensity of spun glass improve but can increase the temperature of fusion of spun glass and the temperature under other various viscosity.One of which can make being limited to below 25% of adding aluminum oxide; Its two, be exactly when the aluminum oxide that adds 25%, adopts general has the alkali boron-free glass to equip can not to produce at all.Can add the aluminum oxide of proper content according to requirement according to the spun glass of present embodiment to the demand and the temperature under the various viscosity of intensity.(in addition, in this manual, only if specialize, the content of various compositions all is weight percentage in the spun glass.)

Viscosity performance

The mensuration of embodiment of the invention medium viscosity adopts U.S. THETA rotation high temperature viscosimeter.

From the viscosity data of several keys comparatively speaking (when alumina content reaches 30% left and right sides):

(1), temperature of fusion: the spun glass viscosity that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to the embodiment of the invention is 10 ^0.5Temperature when (handkerchief second) is 1480 ℃-1680 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1420 ℃-1600 ℃.

And above-mentioned prior art medium-alkali glass fibre, C level fiberglass, E level alkali-free boron fiberglass and S grade high-strength fiberglass products, because viscosity 10 ^0.5(handkerchief second) and 10 ¹The temperature of fusion of (handkerchief second) is higher than 1600 ℃, so adopt the basic survey of U.S. THETA rotation high temperature viscosimeter not go out.

And the melt viscosity of the present invention when the meeting that has added 20% or 30% causes the aluminum oxide that viscosity rises greatly (get higher limit) be also than low 100 ℃-300 ℃ of above-mentioned prior art E level or medium-alkali glass fibre, C level fiberglass, S level fiberglass viscous preparations temperature, and the spun glass viscosity that adds about aluminum oxide 5-8% than medium-alkali glass fibre, C level fiberglass is also low more than 200 ℃.The insider knows that this will extremely help:

One of which has energy-saving and cost-reducing very big technological comparative advantages, because the energy consumption maximum is the high-temperature zone, as falls 200 ℃ of temperature of fusion, minimum energy-conservation 30-40%;

Its two, high-quality fusing is arranged, the technical superiority of extremely low defective;

Its three because temperature of fusion reduces greatly, will lower greatly the erosion of refractory materials, furnace life is prolonged greatly, significantly reduce the cold repair time and the expense that have a strong impact on production capacity.Like the S level fiberglass, every 1-2 will the minimum stopping production 2-3 of cold repair month; E level boron glass and for example, because boron content is at 6-10%, also 3-4 must cold repair; Stopping production 2-3 month; And the refractory materials that uses is high zirconia material, and not only material cost exceeds 3-4 doubly, but also takes 1-2 or 3-4 does a large amount of replacings.And make according to life-span in the molten bath of the spun glass of the embodiment of the invention can medium-alkali glass fibre longer, can be lower because of the existing various spun glass of viscosity ratio according to the spun glass of the embodiment of the invention, minimum can the use reaches just cold repair of 5-8.

(2), exhaust bubble and clarification viscosity temperature: the present invention includes salicly at the preferred version more than 20%, viscosity is 10 ²Temperature is 1180 ℃-1280 ℃ when (handkerchief second), and alumina content existing all medium-alkali glass fibres of 5% only, its viscosity 10 ²The mold temperature of (handkerchief second) reaches more than 1380 ℃.

Various E class alkali free glass fibres and aluminum content are about 15% E level boron glass, and S level fiberglass especially because fusing and row's bubble, homogenizing difficulty, has all proposed to add oxygen blast, adds Pai Pao, added process means such as shallow pond equipment, and its cost is high, efficient is low.

When the aluminum oxide that has added about 20%, they 10 according to the spun glass of the embodiment of the invention ²Temperature when (handkerchief second) is 1180 ℃-1280 ℃ a viscosity temperature advantage; The present invention not only work efficiency is high; Cost is low; And the Fibre diameter deviate that can form high level with significantly reduce bubble, to product strength the effect of lifting can be arranged also, so the technique effect of the raising product with stable quality property of present technique scheme and intensity is fairly obvious.

Breaking tenacity performance (pressing the CB/T7690.2 specified standards measures)

(annotate in addition: following all breaking tenacitys refer to more all that nominal diameter at this spun glass is at≤9 microns the time breaking tenacity [N/tex] value)

The insider knows; The breaking tenacity value of glass depends primarily on the content of aluminum oxide; Aluminum oxide also plays topmost effect to intensity in the composition reticulated structure of product, be directly proportional with the content of aluminum oxide, also is inversely proportional to boron content; Cause the goods composition uneven because boron can volatilize, the composition reticulated structure is destroyed loose.

According to the embodiment of the invention, of preceding viscosity part, in the time of can knowing aluminum oxide adding 20-25% or 25-30%, viscosity also is lower than prior art, and the platform of a good technological span of control is arranged.The advantage of breaking tenacity degree value of the present invention is; In the fiberglass product of any equal type; Because 150 ℃-250 ℃ much better viscosity performance is arranged; Under equal viscosity temperature and equipment condition, can add 10%-15% or more aluminum oxide composition than prior art, so the rising space of very big breaking tenacity is arranged.

(1), high, medium-alkali glass fibre goods, aluminum oxide is merely about 5%, and its technical scheme is difficult for adding aluminum oxide, otherwise can not implement because of viscosity is too high to produce, its nominal diameter is in the time of≤9 microns, breaking tenacity (N/tex) is about 0.4.Can reach 25% and the present invention can add more aluminum oxide in equivisous temperature and processing unit, make the breaking tenacity 50-100% that can rise.

(2), E class alkali free glass fibre, when adding 15% left and right sides aluminum oxide,, can not add more aluminum oxide because its viscosity is too high, its nominal diameter is in the time of≤9 microns, breaking tenacity (N/tex) is about 0.45.And the present invention is low because of viscosity, can with equivisous temperature the time, can add the aluminum oxide of 25%-30%, and again because boracic composition not, it is cancellated loose can not form goods, intensity rising 80-130%.

(3), surpass 26% aluminum oxide because the viscosity performance of existing S level glass has determined it not add, thus its glass nominal diameter in the time of≤9 microns, breaking tenacity (N/tex) can only reach about 0.7-0.8.And the present invention can just can add the aluminum oxide of 30%-39% because the LV advantage can be arranged under equal processing unit and viscosity temperature, make intensity rising 50-80% or more than.

Environmental-protecting performance

In the production technique; Existing E level boron glass (account for existing global glass total amount 90%); Boracic reaches 8-12%, and (boron of 10% content for example will add the boron composition raw material of 25-30% because a large amount of volatilizations is arranged; The boron composition of volatilization 15-20% when in fusing, producing fluxing action), produce the boron poisonous gas.And the present invention can not add boron, can also be with lower viscosity temperature fusing, so can fundamentally solve the environmental issue in the E level boron glass production more than 90% that accounts for global glass output now.

Water ratio (according to standard GB/T9914.1 standard test)

According to the spun glass of the embodiment of the invention, the water ratio of its goods is in the scope of 0-0.5%.

Fibre diameter (pressing the GB/T7690.5 regulation measures)

According to the spun glass of the embodiment of the invention because the controllability of viscosity, the deviate of the nominal diameter of this spun glass not only can reach ± 15% in, also can reach high-levelly ± 10% in.

In order to describe technical scheme in more detail according to the embodiment of the invention, enumerated out detailed prescription in the table below and respective performances following:

Table 1

* do not go out with high temperature rotary viscosity instrumentation, obtain through calculating.

Table 2

Visible from table 1, the technical scheme among the scope of the present invention's 1-4 sample, its glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, titanium oxide, red stone, sodium oxide; Wherein, count as weight percents, alumina content is 19-25% in this spun glass; Titanium oxide content is 0.0003-4.9%, and iron oxide content is 0.01-3%, and sodium oxide content is 0.01-8.8%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia.

Visible from table 2, the technical scheme among the scope of the present invention's 5-11 sample, its glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, titanium oxide, red stone, sodium oxide; Wherein, count as weight percents, alumina content is 26-39% in this spun glass; Titanium oxide content is 0.0003-4.9%, and iron oxide content is 0.01-3%, and sodium oxide content is 0.01-8.8%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia.

Visible from above table, its viscosity temperature all various product viscosity temperature than prior art is low, and especially temperature of fusion 10 ^0.5(handkerchief second), 10 ¹Viscosity temperature when (handkerchief second) is than all existing technology, the sample 2,4,5 of comparison sheet 3; The sample viscosity temperature that adds the 15-25% aluminum oxide hangs down 150 ℃-250 ℃, and this explanation the present invention can be on the equipment that technology originally arranged, under the same temperature; The aluminum oxide of adding 15-20% is also producing under same viscosity, thus the intensity of the 50-100% that rises greatly, the sample 1,3 of comparison sheet 3; The sample that has only added the 3-7% aluminum oxide; The sample that the present invention has added the 20-31% aluminum oxide is also low 100 ℃-230 ℃ in above-mentioned viscosity temperature, and this explanation can energy efficient, improves the quality of products.

Visible from table 1; Do not add the boron oxide composition more than the sample of the present invention and have only the sodium oxide composition below 1%; Can produce than the salic more intensity of the E level boron glass (boron oxide content is 8-15%) that the accounts for global glass ultimate production 95% E level glass of new capability more up to 1 times; Thereby do not have the volatilization of a large amount of boron poison gases aborning fully, the technique effect of good environmental protection effect is arranged.

Aluminum oxide is merely about 3% from the Comparative Examples of sample 12; And the aluminum oxide that contrasts other the present invention is to 25% or the sample of 26-31% content more than 19%; Especially the difference of melt viscosity temperature is merely 10 ℃-30 ℃ or 30 ℃-80 ℃; It is thus clear that in the technical scheme of the aluminium of the high aluminium content of newly discovered of the present invention, silicon, calcium, magnesium eutectic product property; The technological prejudice that can not add a large amount of aluminum oxide compositions that has prior art prejudice when breaking no boron, alkali-free; And during this high aluminium content, viscosity also is better than the high sodium of having of prior art or high boron content is arranged, and aluminium is merely the technical scheme about 1% or 8%; Prove newfound high aluminium content of the present invention aluminium, magnesium, silicon, calcium have a kind of eutectic character; And breaking tenacity character relatively, viscosity change little (than prior art also under low 15 ℃-20 ℃ the processing condition) but operating restraint, the breaking tenacity that can rise to 26% or 31% aluminium content from 0.4 (N/tex) of 3% aluminium content is 0.65 (N/tex) or 0.8 (N/tex) or 1.05 (N/tex).

And in the sample of the present invention; The iron level that has is 1 to 1.3; And barium oxide, titanium oxide content are arranged and can become opaque brown Huang or pale brown look; All well a lot of to adapt to than prior art spun glass in characteristics such as intensity, viscosity temperature and strain points; At the red stone that adds 1-1.5% or add an amount of barium oxide, titanium oxide, manganese oxide, powder blue isochrome again and produce the senior raw material of saving with practical value that high breaking tenacity performance is arranged of colors such as opaque blue or green blue, blue green, yellowish-brown, brown, black, the main raw material cost is descended reach the spun glass novel material goods about 10 times.

Visible from the various prior arts or the comparative example of table 3; Its technical scheme and the present invention reach 8.1-20% at magnesian composition; Necessarily having on aluminium, silicon, sodium, iron, titanium, magnesium, the calcium composition, also having on the component, and on the ratio between the silicon, magnesium, calcium; On this total technical scheme content, all there are 3-5 item or 4-5 item not to exist together.Just because the discovery and the innovation of the new property of technical scheme of the present invention, thus all reflected prior art relatively can produce environmental protection, energy-conservation, reduce discharging and production capacity efficient, reduce cost and the technique effect advantage of technical qualities control that intensity, viscosity temperature are favourable etc.

Here also to explain; The viscosimetric analysis of table 1, table 2 and table 3 is to adopt U.S. THETA rotation high temperature viscosimeter to survey, and breaking tenacity is measured in the GB/T7690.2 specified standards or according to measuring the numerical value that numerical value perhaps gets in the ratio reckoning of the alumina content of correspondence more.Water ratio is to measure by standard GB/T9914.1.

Example 1

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention is characterized in that: the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.45-1.3.

Example 2

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention is characterized in that: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 19-39% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-2%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1550 ℃-1700 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1620 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1480 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1160 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.6-1.3.

Example 3

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention is characterized in that: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 8-30% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-2%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1500 ℃-1640 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1230 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.45-1.1.

Example 4

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention is characterized in that: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 8-19% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-2%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1500 ℃-1580 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1520 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1310 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1160 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.45-0.7.

Example 5

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention is characterized in that: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 8-39% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-2%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1550 ℃-1700 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1620 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1480 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1160 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.45-1.3.

Example 6

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to first embodiment of the invention is characterized in that: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein; Count as weight percents, alumina content is 26-39% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-2%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1610 ℃-1710 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1500 ℃-1640 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1310 ℃-1490 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1200 ℃-1340 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.75-1.3

Example 7

On the basis of above-mentioned first embodiment, limit by weight percentage, barytic content is 0.01-14% in this spun glass.

Example 8

On the basis of above-mentioned first embodiment, limit by weight percentage, the content of aluminum oxide is 20-39% in this spun glass.

Example 9

On the basis of above-mentioned first embodiment, limit meter as weight percents, the content of silicon oxide is 2.0 times-3.6 times of calcium oxide content in this spun glass, and the content of quicklime is 1.3 times-1.6 times of content of magnesia, and magnesian content is 8.1-20%.

Example 10

On the basis of above-mentioned first embodiment, limit (1), count as weight percents, in its goods content: 1. Natural manganese dioxide accounts for 7-20%; 2. quicklime is in magnesian 1.0 times-1.8 times scope; 3. silicon oxide is that 4. silicon oxide is that 5. aluminum oxide is 0.1-30% in 2.2 times-3.8 times the scope of quicklime in magnesian 2.6 times-5.6 times scope; 6. sodium oxide is 0-18%, and 7. barium oxide is 0-5%; (2), as weight percents the meter, the content summation of Natural manganese dioxide, quicklime, three kinds of compositions of silicon oxide reaches 51%-100% in its goods.The performance of its goods is that the strain point temperature of its goods is in 560 ℃-720 ℃ scope; The water-intake rate of its goods is in the scope of 0-0.001%.

Example 11

On the basis of above-mentioned first embodiment; Limit (1), meter as weight percents, in its goods content: 1. the content of quicklime is 0.6 times-2.4 times of magnesian content, and 2. the content of silicon oxide is 1.3 times-5.8 times of magnesian content; 3. the content of silicon oxide is 1.3 times-5.8 times of content of quicklime; 4. aluminum oxide is 0.1-30%, and 5. sodium oxide is 0-18%, and 6. barium oxide is 0-20%; (2), wherein the content summation of Natural manganese dioxide, quicklime, three kinds of compositions of silicon oxide reaches 51%-99.9%.The water-intake rate of its goods is in the scope of 0-0.001%.

Example 12

On the basis of above-mentioned first embodiment; Limit this glass fiber package silicon oxide-containing, Natural manganese dioxide and quicklime, wherein, count as weight percents; The content of silicon oxide is 2.1 times-6.5 times of magnesian content in this glass, and the content of silicon oxide is 1.8 times-4.6 times of content of quicklime.The performance of its goods is following:

Its visible transmission is than in the scope of 65%-95%; Its water-intake rate is in the scope of 0-0.3%; Its folding strength reaches 50-180MPa.

Example 13

According to the matrix material of the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of first embodiment of the invention, this matrix material comprises plastic substrate and embeds the glass fiber compound material that the utilization in the plastic substrate is made according to the spun glass of the foregoing description.

Second embodiment

The described preparation method that the spun glass of HS and energy-saving, emission-reducing, environment friendly and LV characteristic is arranged according to first embodiment of the invention; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is that its preparation method is characterised in that in nominal diameter ± 15%:

Step 1; According to the described glass fiber formula of first embodiment dispose required various sodium oxide in the predetermined requisite special scope, red stone, aluminum oxide, silicon oxide, quicklime, Natural manganese dioxide are arranged or also have titanium oxide, barytic composition and predetermined silicon oxide, quicklime, Natural manganese dioxide between the raw material of innovative technology scheme of composition of specific proportions relation; Stir afterwards in temperature of fusion fusing through mixing corresponding to each glass fiber formula; Form the spun glass liquid of predetermined viscosity, homogenizing is clarified again; Discharge bubble, form flowable molten mass;

Performance in its technology is following:

This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1480 ℃-1680 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1410 ℃-1600 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1180 ℃-1340 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1040 ℃-1220 ℃.In order to describe technical scheme in more detail, enumerate out the prescription and the corresponding performance of the glass fiber sample that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to an embodiment of the invention below in the table 1 according to the embodiment of the invention.

The 3rd embodiment

The spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to the above embodiment of the present invention; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%; Wherein, a kind of glass fiber compound material, this matrix material comprise plastic substrate and embed the glass fiber compound material that the utilization in the plastic substrate is made according to the spun glass of the foregoing description.

More than to according to the embodiment of the invention by the forming and characteristic of the spun glass of HS and energy-saving, emission-reducing, environment friendly and LV characteristic, the method for manufacturing according to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of the embodiment of the invention is described below.

The 4th embodiment

Fig. 1 is a kind of according to an embodiment of the invention the have spun glass of HS and energy-saving, emission-reducing, environment friendly and LV characteristic and goods normal section synoptic diagram of preparation technology.Visible from scheming, a kind of fiberglass products that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of Reference numeral 1 expression.

Fig. 2 is the preparation technology's of a kind of spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic arranged of the present invention a schematic flow sheet.Visible from scheming, 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) got into the molten bath and carried out fusion and clarification discharge bubble by preset temperature; (4), then be liquid molten mass,, draw and stretch out glass fiber through platinum alloy wire drawing orifice plate; Through oven dry, obtain finished product again.

Existing preparation technology with a kind of spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic arranged of the present invention further specifies with stretching its goods of technology making that reel off raw silk from cocoons, and its manufacturing processed comprises following steps:

(1), at first, preparation raw material is formed according to the spun glass by HS and energy-saving, emission-reducing, environment friendly and LV characteristic of above-mentioned first embodiment and various modification and example and to be calculated proportioning raw materials.

(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; Put into feeding warehouse to the predetermined raw material of (1) step preparation; From feeding warehouse, raw material is transported in the kiln of molten bath then, has got into behind the molten bath and carried out fusion and vent gas bubble, form liquid molten mass by preset temperature;

Following technology has two kinds of selections:

A kind of stretched formation the present invention has the spun glass finished product of HS and energy-saving, emission-reducing, environment friendly and LV characteristic in order directly to make the wire drawing hole of glass melt through platinum alloy, and this is direct pool kiln wiredrawing moulding process.

Another kind of is through ball making process, processes glass sphere, glass sphere is sent into the wire drawing hole of crucible and platinum alloy metal sheet again, and stretching forms the spun glass finished product that the present invention has HS and energy-saving, emission-reducing, environment friendly and LV characteristic.

So the present invention overcomes a conventional art difficult problem is arranged earlier, especially in technology is reeled off raw silk from cocoons in stretching to the viscosity ratio of three main operation stages of fusing, homogenizing row bubble and drawing and forming existing various in the technology of alkali, E class alkali-free and S grade high-strength glass significant substantive technical progress effect is arranged.

Use

Because the above-mentioned spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to the embodiment of the invention except being applied to aspects such as glasscloth, silk, felt, more is mainly used in the glass fiber compound material aspect.

The 5th embodiment

The third embodiment of the present invention discloses a kind of a kind of glass fiber compound material that adopts the spun glass manufacturing of the embodiment of the invention; This matrix material comprises plastic substrate and embeds the spun glass that the utilization in the plastic substrate is made according to above-mentioned spun glass; The nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in.

More than combine specific embodiment that the composition of spun glass of the present invention and the ME and the application of character and spun glass are described; Face characteristics down, the difference characteristics of the present invention just and prior art spun glass according to the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged of the embodiment of the invention:

The present invention creatively a kind of various characteristics of the glass fiber product that stretching glass technology produces and new compositional characteristic and the technique effect of generation and new LV characteristic, strength characteristic and characteristic of environmental protection of adopting, unifies in the technical scheme of an integral body first.

The present invention is a kind of to have the spun glass of HS and energy-saving, emission-reducing, environment friendly and LV characteristic in the spun glass field, to have the technical scheme of novelty to be: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide; Wherein, Count as weight percents, alumina content is 8-39% or 26-39% in this spun glass, and iron oxide content is 0.01-3%; Sodium oxide content is 0.01-8.8%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 1.9 times-4.1 times or 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.2 times-1.6 times or 1.3 times-1.49 times of content of magnesia.

The characteristic of technical scheme of the present invention has following level,

One of which; Glass fiber product characteristic and purposes as far as all prior aries; Be a kind of selection invention of the composition scope to aluminium, silicon, calcium, magnesium, iron, sodium and between silicon, calcium, the magnesium composition, the type of the change of the proportionlity of these technology essential factors invention.In the selection invention of the change of the present invention's factor proportion relation, its technical scheme is a silicon: calcium be 1.9-4.1 doubly or be preferably 2.0-3.6 doubly, calcium: magnesium be 1.2-1.6 doubly or be preferably 1.3 times-1.49 times scope.And all spun glass of prior art, the rarest wherein two end values of two factor proportion relations outside the scope of the invention, within the close limit that is chosen in all prior aries of the factor proportion relation that the present invention just is above-mentioned, have novelty.And in the spun glass purposes, in the technology, find to have produced new following product property, produced following unforeseeable technique effect.

They are two years old; The new character that the present invention has disclosed the product of finding is migrated, and (i.e. each operation stage working method of special fusing through various spun glass, row's bubble, homogenizing, moulding, the drawing that reels off raw silk from cocoons, nature and characteristic and breaking tenacity the breaking tenacity (N/tex) when diameter be less than or equal to 9 micron of nominal diameter within 5 microns to 13 microns that can produce the goods of technical scheme of the present invention be the character of 0.45-1.3 for the invention type of new purposes.And can preferred breaking tenacity (N/tex) be the character of 0.75-1.3 under the lower and environmental protection in viscosity, energy-conservation prerequisite.Especially in new purposes; The present invention has found the new reduction viscosity temperature and the eutectic character of the product that prior art never disclosed; With melting process stage viscosity temperature, homogenizing, row's bubble; Clarification process stage viscosity temperature character, the viscosity temperature in the moulding process stage of the especially stretching of control through the platinum funnel, drawing.

(A), because having overcome a kind of key element to the sodium oxide in the spun glass that conventional art prejudice produces, one of discovery of the new character of product omits invention: the height of prior art, medium-alkali glass fibre; It all contains the sodium about 4-13%; Mainly be used for fluxing; Especially to the fluxing of silicon composition, form the reduction that to control viscosity of each operation stage.But the new property of the product of technical scheme of the present invention and discovery has been broken this technological prejudice, can be owing to the variation invention of the element relationship between silicon, calcium, the magnesium; In the purposes of spun glass, the product new property of generation is when sodium content is in 0-1%; Can be than low 150 ℃-250 ℃ of the viscosity temperature of several operation stages of the high soda glass fiber of prior art, this will produce a large amount of energy-conservation with help high-quality control, prevent that bushing hole that glass is made from blocking the calculus that produces, point is cut; Help arranging the bubble that the bubble technology controlling and process produces, produce the defective of a large amount of fracture of wires, especially for reducing quarrel point, calculus rate, bubble rate and viscosity; Drawing is crossed the hole that platinum leaks a plate, ensure that the diameter of product is even, the intensity of product; Especially the raising of the rate that manufactures a finished product of electronic grade product; The platform of the scope of a viscosity controller is provided, and technical scheme just of the present invention does not add the omission invention of sodium composition, than existing height, middle alkali product better technology controlling and process effect is arranged.

Prior art is in operation, if in case produce the defective of any one operation stage, the mode that in operation, all is easy to increase the temperature of each operation stage solves, but this just is prone to the molten bath is collapsed top, reduction of service life greatly very much.And the invention provides the viscosity variable range that a technology that helps controlling very much technology is controlled.Fundamentally solved the technical barrier of the product property (" the material property " promptly said in the industry) of the existing sodium that the insider thinks always (high sodium) spun glass " material property is short ".

(B), since the discovery of the new character of product two; Overcome the prejudice of conventional art; Produced a kind of key element of " boron oxide " technology essential factor that spun glass a kind of accounted for the E level alkali-free boron glass of global glass total amount 95% and omitted invention: existing E level alkali-free boron fiberglass; All adopted the boron composition of 8-15% content to make the fusing assistant composition; This is a kind of technological prejudice of alkali-free boron glass, and it utilizes the boron composition to form the fluxing of silicon, and could form the reduction control of the viscosity temperature of each operation stage of alkali free glass fibre.But the new property of technical scheme of the present invention and discovery; Broken this technological prejudice; Can in the alkali free glass fibre purposes, produce new product property owing to the variation invention of the element relationship between silicon, calcium, the magnesium; There is not boron oxide content when non-oxidation fluorine, sodium oxide (or only 0-1%) yet; Can be than the viscosity temperature with the product of the boron of 8-15% content of prior art, low 200 ℃-300 ℃ of several operation stages of spun glass, this will form one very on a large scale CONTROL PROCESS reach the new technology platform of more convenient control quality product; For this high-caliber no bubble, nothing quarrel point, the product no calculus defective, that the high-quality requirement of the uneven rate of as far as possible little diameter is arranged of requiring; To improving yield rate, quality product rate,, a kind of technology controlling and process scope and the technology controlling and process platform more much better than prior art are provided all especially for the viscosity of exhaust bubble and clarification, homogenizing process stage and moulding pull silk operation stage.

(C), since the discovery of the new product property of product three, overcome a kind of of traditional glass fiber and thought that strengthening aluminum oxide certainly leads to the technological prejudice that viscosity temperature significantly rises., medium-alkali glass fibre high-alkali like prior art; Can only add the aluminum oxide about 1-5%; And existing alkali-free boron fiberglass; Also generally only add 8% left and right sides aluminum oxide and improve intensity, added and will make the viscosity temperature of this each very high stage process higher, uncontrollable technology should reach the QT Quality Target of above-mentioned various glasses.Also think and to be added to 19-31% or 26-31% to aluminum oxide under can controlled cheaply processing condition, more can not be added to the content of 26-39%, to improve product strength.But the new glass fiber product character of technical scheme of the present invention and discovery; Broken this technological prejudice; The present invention at boracic not, do not contain sodium, not during fluorine-containing composition when 0-1% (or); When the large span when alumina content is 19% or 26% left and right sides changes; The viscosity that prior art is thought can significantly rise, but the variation of viscosity temperature of the present invention is merely 20 ℃-40 ℃ or 50 ℃, viscosity temperature also only rise (the 12 sample Comparative Examples of seeing attached list) about 40 ℃-80 ℃ when aluminum oxide is 31% left and right sides.

And viscosity temperature is than also low 100 ℃-200 ℃ of the glass fiber products that has added 10% sodium oxide or 8-15% boron oxide.This has proved the invention technical scheme of the factor proportion relationship change scope of silicon in the technical scheme of the present invention, calcium, magnesium; Ability and aluminum oxide produce a kind of new product property when 25% or 30% content; The eutectic character of the aluminium of a kind of new high alumina content that Here it is, silicon, magnesium, calcium, LV temperature unforeseeable that can produce high aluminium content help improving the quality of products and have concurrently simultaneously with energy-conservation technique effect because the technique effect (seeing the sample example of table 1, table 2) that a large amount of addings of aluminum oxide and then generation relatively more existing occurs when rising 1 times unforeseeable multiple having concurrently with the based article breaking tenacity.

The insider knows; The breaking tenacity value of glass depends primarily on the content of aluminum oxide; Aluminum oxide also plays topmost effect to intensity in the composition reticulated structure of product, be directly proportional with the content of aluminum oxide, but also be inversely proportional to boron content; Cause the goods composition uneven because boron can in fusing, volatilize in a large number, the composition reticulated structure is destroyed loose.

When the present invention especially reaches 19-28% owing to the content that can strengthen aluminum oxide; Breaking tenacity can be much higher than various prior art 50-100%; And since viscosity temperature also than only during the 1-25% alumina content low 150 ℃-250 ℃ of prior arts; When so if technical scheme of the present invention forms the viscosity of alkali-free high boron glass, that should be equivalent in addition to add aluminum oxide to the viscosity space that can dissolve of 29-39% and intensity rising than large space.(folding strength of this specification sheets and embodiment of the invention glass through being cut into sample little of 50mm * 50mm * 5mm, adopts the folding strength appearance, measures by standard GB/T3810,4-2006.) the high boron goods of alkali-free of prior art, because of the volatilization process of boron oxide composition, can cause the inequality of composition, the netted structural damage of material that aluminum oxide is participated in influences due intensity greatly.This is the time also relatively poor major reason of intensity that the high boron E of alkali-free level glass contains the 7-15% aluminum oxide.

And when high aluminium content being arranged, high-intensity character is arranged, have concurrently more energy-conservation, more low-cost and the processing range that bigger viscosity temperature is arranged, this be existing all glasses technology do less than.It can also control fusing in the melting process viscosity temperature stage, overcome calculus and prevent to produce the quarrel point that is not melted, and the diameter uniformity coefficient of spun glass is (because viscosity is low more when clarification and better control moulding; The soft more scope that control is arranged more of the glass fiber product of this operation stage, on the contrary viscosity is high more, and this operation stage glass fiber product is hard more; Bad more control; And viscosity at this moment is low more, help more under the peers will condition, under the stabilised quality prerequisite to the superfine control that equals less than the uniform diameter error of the spun glass of 9 micron diameters); And help strengthening draw speed, improve output.

(D), add red stone 0.01-4%; Be a kind of component invention, can form new function, promptly under new character of the present invention and the prerequisite that can produce energy-conservation, HS effect and increasing production capacity efficient; Can form the saving high-quality resource that upgrades, the technique effect that reduces cost greatly.

(E), add zirconium white 1-25%; It also is a kind of component invention; Can form the new alkaline-resisting functional character that not only has, and can have under energy-conservation prerequisite, under the low viscous prerequisite that control product quality level arranged; Under the prerequisite that cost does not rise, produce new alkali resistant glass fibre than the alkaline-resisting glass breaking tenacity rising 50-100% of prior art.

They are three years old; Because the announcement and the discovery of the character of new said product; Overcome and planted prior art prejudice more than above-mentioned; In various glasses are produced in the utilization of the industrial applicability of resin composite materials and alkali proof cement composite material, produced following unforeseeable effect in the spun glass field:

(1) because having formed, the viscosity temperature temperature property can well promote the technique effect that improves production capacity with all even quickening draw speed of the control diameter of the molten quality of CONTROL PROCESS, bubble quality, moulding process.

(2) energy-saving effect more than 200 ℃ that descends of unforeseeable because viscosity temperature and because eutectic character adds a large amount of aluminium (being added to 31% from 1%), the breaking tenacity of the generation 2-3 technique effect doubly that can rise.

(3) since intensity rising 1-2 doubly, under equality strength, glass lightweight 1-2 doubly, producible thus spun glass can be less with 1-2 resource doubly, and energy-conservation, practice thrift logistics, practice thrift storage 1-2 unforeseeable technique effect doubly.

(4) the new technique effect of the present invention also is; Owing to can on iron oxide content, be used for the ambetti filamentary material of opaque or the various colors that transparency is not high, the raw material consumption that the composite resin material product strengthens high Fe content; Can practice thrift the high-quality spun glass raw material resources that reduce day by day, main spun glass raw materials cost descends 10 times.

(5) owing to adopted the invention of a kind of technology essential factor elliptical; To prior art like alkali-free glass fiber; And can be than prior art under the prerequisite of quality control of better calculus, quarrel point, bubble rate, diameter uniformity coefficient; Before technological temperature does not rise, reduce and energy-conservation prerequisite under, economize and omit the boron composition, can have fusing, row's bubble, moulding process each stage better character and can add more aluminum oxide and the breaking tenacity rising 1-2 that produces doubly; The technology controlling and process quality is good; Under the prerequisite that product production strengthens, the unforeseeable production effect of the clean environment firendly that no boron poison gas discharging produces, this has great environment protection significance for accounting for the alkali-free boron class E level glass of glass production capacity more than 90%.

(6) comparative advantages of the glass of the present invention of adding oxidation zirconium 1-25% are; More present all comprise alkaline-resisting glass with various glasses; Because can viscosity reduction degree temperature 150 ℃-300 ℃, thus can be energy-conservation, again because during the present invention's high-content aluminum oxide; The characteristic of the eutectic character of aluminium, silicon, calcium, magnesium; So aluminum oxide can be added to about 25-30%, the production technique of existing alkaline-resisting glass do not realize, because its product viscosity has determined fusing not high aluminium content; Arrange the bubble that holds one's breath; Form and not become glass to produce moulding process, and viscosity temperature and the existing common calcium sodium glass that only contains the aluminum oxide of 1-10%, boron glass, the alkaline-resisting viscosity temperature that contains the zirconium glass is lower or it is little to change, so the device fabrication alumina content that can utilize the alkaline-resisting glass of existing production is higher than the alkaline-resisting at present glass 1-2 alkaline-resisting glass that new high-intensity performance is arranged doubly up to the intensity of 20-30%.

(7) because during high-content aluminum oxide of the present invention; The characteristic of the eutectic character of aluminium, silicon, calcium, magnesium; So the breaking tenacity of glass can exceed 1-2 doubly than the existing about E level alkali-free boron glass more than 90% of glass ultimate production that especially accounts for; And energy-conservation, cost is low, more be significantly less than the expensive glass of S level, and intensity is higher.So with its spun glass of processing and resin composite materials; Rising 1-2 times HS can be arranged or the composite product of lightweight more than 1 times under equality strength; This matrix material to wind-power electricity generation is used and is made generating efficiency improve 60-100%; To various ships, automobile, vehicle, and intensity and the technique effect and the lightweight utilisation technology effect of the various vehicles, the unforeseeable effect of crucial technical progress is arranged all.

(8) because during the present invention's high-content aluminum oxide; The characteristic of the eutectic character of aluminium, silicon, calcium, magnesium; So the intensity of the present invention's alkaline-resisting glass can rise more than 1 times (because the viscometric properties of the alkaline-resisting glass product of prior art has determined it to realize not this purpose; It has melted not the composition of high-alumina, arranges the bubble that holds one's breath, and can not form the moulding process production of glass); Intensity for enhanced cement significantly strengthens, and being implemented in the application such as bridge, building and harbour and mending-leakage and industrial chemical engineering has unforeseeable effect.

Its four, technical scheme of the present invention and existing all spun glass technology relatively have and are disclosed and disclosed new product property; And this character can't be inferred in advance, prediction and reasoning are come out; And overcome the technological prejudice of traditional glass technology, and having solved people thirst for solution in industry above-mentioned significant problem, technical scheme has produced " matter " and " amount " the two variation; Explain that technical scheme is non-obvious; Have outstanding substantive distinguishing features, have significant technical progress, creative.

A technical characterictic is formed the technical scheme a kind of fiberglass products more than the embodiment statement; Just say; All have the spun glass technology all not have the multiple new product feature of using above compositional characteristic and process method to form earlier, can in a kind of glass fiber product, combine together.Its novelty is very clear and definite.

Especially be; The invention of its novel technical project has produced unforeseeable technique effect, has solved the further specifying as follows of a technological great difficult problem of water-fast mud matrix material of resin composite materials and the chemical building etc. of people spun glass and especially electronics, chemical industry, engineering, the vehicles and wind-powered electricity generation industries that thirst for for a long time solving in glass fiber industry and that not have achieving success:

One of which; In the production technique, existing E level boron glass (account for existing global glass total amount 90%), boracic reaches 8-12%; And because a large amount of volatilizations (boron of 10% content is for example arranged; The boron composition raw material that will add 25-30%, the boron composition of volatilization 15-20% when in fusing, producing fluxing action), produce the boron poisonous gas.And the present invention can not add boron, can also be with lower viscosity temperature fusing, so can fundamentally solve the environmental issue in the E level boron glass production more than 90% that accounts for global glass output now.And the fluorine glass is because the volatilization of fluorine is bigger, though can the viscosity reduction degree, poison gas is too big; Environmental protection is not all right fully; Existing little this production line production, and the present invention can solve the production technology scheme of no boron, free-floride, (1) contributes to the solution to the environmental protection difficult problem of the whole world 90% above production capacity; (2) because a bigger viscosity controller scope is arranged, lifting is of great importance to controllable quality; (3) as preceding explain can owing to the decline of technology controlling and process viscosity under the original equipment state, promote production capacity about 20%; (4) can be owing to boracic not, and make the former molten bath just cold repair about 10 years that took cold repair in about 3 years, thus improve equipment life and utilization ratio; (5) because as previously mentioned, can promote intensity 1-2 doubly, and cost is not high, can very large economic implications be arranged to composite product HS, light-weighted application.

Its two, energy-saving and cost-reducing because can be 150 ℃-300 ℃ of same viscosity degradation low melting temperatures, again because maximum energy consumption district in the high-temperature zone, so can energy efficient 30-40%, this also is the technical solution scheme of the hang-up of glass industry.

Its three owing to reduce energy consumption 30-40%, also just reduced Carbon emission 30-40%.

Its four because technical scheme of the present invention can make viscosity temperature reduce, the especially decline of the viscosity during the high alumina component content; When moulding, can help controlling the diameter uniformity coefficient of glass, this rises favourable to intensity, again because the boron composition, the fluorine composition can volatilize and influence greatly that glass forms evenly; Destroy netted structure, cause strength degradation, and the present invention can be when ensureing the melt viscosity temperature; Need not add the composition of boron or fluorine, so help the rising of intensity.And owing to 200 ℃-300 ℃ of the temperature heads with viscosity the time; And under original equipment processing condition; Relatively the aluminium content of prior art can be added 10-20% on the original basis and can also keep same viscosity, so under the condition of original energy consumption and equipment, viscosity, (being added by 1-10% like aluminum oxide is 19% or 26% owing to aluminum oxide can be added; Or 26-31%; Or add be 31-39%), for various industry, transport facility and chemical engineering glass and new forms of energy wind energy glass blade composite, also be the solution of a great difficult problem.To the alkali-free glass fiber and the S level glass of the high boron of prior art, also can be owing to the raising of intensity, and the lifting that produces practical economic worth.

Its five, the high boron goods of the alkali-free of prior art the composition of boron as necessary 8-15% content, because of the volatilization process of boron oxide composition, can cause the inequality of composition, the netted structural damage of material that aluminum oxide is participated in influences due intensity greatly.This is the also relatively poor major reason of intensity under the situation of the alkali-free high boron glass aluminum oxide that contains 7-15%.And, can cause the instability of diameter for requiring the high electronic-grade glass of difference in diameter, form the very big influence of quality.A kind of omission invention technical scheme to the boron key element of present technique scheme also just can solve this technical barrier.

They are six years old; Because creationary technical combinations scheme of the present invention; Can be in the viscosity advantage in homogenizing, Pai Pao, clarification process stage; Can form various products, especially the diameter deviation value of electronic-grade fiber ± on 10% technology or the higher processing requirement one product quality that not only can accelerate wire drawing efficient but also can more help the technique platform of controlling quality and more help the electronic-grade glass rises, especially in the decline (promptly can control softness) of the viscosity in technological forming stage of the platinum hole that stretched; Not only help controlling not fracture of wire; Keep the toughness of plasticity to help quality control, and under the original equipment state, the unforeseeable technique effect that can have the yield efficiency about 20% to rise.

Just can not form so the present invention is not simple reasoning from logic of a kind of usefulness of thinking or simple experiment afterwards, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; Sodium oxide, red stone, aluminum oxide, silicon oxide, quicklime, Natural manganese dioxide in the predetermined requisite special scope is arranged or also have titanium oxide, barytic composition and predetermined silicon oxide, quicklime, Natural manganese dioxide between the innovative technology scheme of composition of specific proportions relation.So have novelty.

And nearly ten to 20 years, the enterprise of thousands of family of the composite industry of global glass fiber industry, energy industry, traffic, chemical industry and technician up to ten thousand, all a plurality of difficult problems that never succeed studying that serious hope solves.Since the people that the invention solves the technology trends of industry thirst for solving and the great technical barrier of never succeeing and this specification sheets are mentioned also have many other people to thirst for solving and do not succeed do not add the boron oxide composition that environmental protection harm is arranged the time; The present invention except that the existence of viscosity advantage and strength advantage; Can produce a large amount of energy-conservation of practicality, environmental protection improves production capacity; Reduce cost; When reducing Carbon emission and being applied to matrix material, owing to the glass breaking tenacity can significantly rise, so can enlarge the intensity effect of matrix material; Promote its lightweight, it is the great technical contribution to the difficult problem of industry and professional that very big technique effects such as practical value are arranged in wind power industry.

Above-mentioned unforeseeable technique effect; All be because adopted and the different techniques scheme that has all glasses technology compositions now; Especially adopted selection invention technical scheme to the proportionlity between silicon, magnesium, the calcium; With a kind of new product property of inventing when purposes is glass and matrix material that changes, reduce like the viscosity of each operation stage, also have eutectic characteristic etc. and the breaking tenacity characteristic that produces etc. of the technical scheme of the present invention of aluminium, silicon, calcium, magnesium; And, just in new purposes, producing unforeseeable above-mentioned technique effect to the omission invention technical scheme that the boron composition of prior art requires.The character of these technical products can't inferred in advance; Unpredictable; And overcome many technological prejudice, and produced the variation of " matter " and " amount " of above-mentioned technique effect, explain that technical scheme is non-obvious; Have outstanding substantive distinguishing features and significant technical progress, creative.

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 possibly utilize the technology contents of above-mentioned announcement to change or be modified to the equivalent embodiment of equivalent variations, can implement have spun glass and the preparation method and the glass fiber compound material of HS and energy-saving, emission-reducing, environment friendly and LV characteristic by demands of different and performance.It is thus clear that, hold within the every content that does not break away from technical scheme of the present invention, the especially claim, to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.

Claims

1. spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in, it is characterized in that:

This glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein, and meter as weight percents; Alumina content is 8-39% in this spun glass, and iron oxide content is 0.01-3%, and sodium oxide content is 0.01-8.8%; Boron oxide content is 0-10%, and content of magnesia is 8.1-20%, and fluorine oxide content is 0-1%; The content of silicon oxide is 1.9 times-4.1 times of calcium oxide content, and the content of quicklime is 1.2 times-1.6 times of content of magnesia.

2. the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to claim 1; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%, it is characterized in that: the breaking tenacity when its diameter is less than or equal to 9 microns (N/tex) is 0.45-1.3.

3. the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to claim 1, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; It is characterized in that: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein, and meter as weight percents; Alumina content is 19-39% in this spun glass; Iron oxide content is 0.01-3%, and sodium oxide content is 0.01-2%, and boron oxide content is 0-10%; Content of magnesia is 8.1-20%; Fluorine oxide content is 0-1%, and the content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1550 ℃-1700 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1620 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1480 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1160 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.6-1.3.

4. the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to claim 1, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; It is characterized in that: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein, and meter as weight percents; Alumina content is 8-30% in this spun glass; Iron oxide content is 0.01-3%, and sodium oxide content is 0.01-2%, and boron oxide content is 0-10%; Content of magnesia is 8.1-20%; Fluorine oxide content is 0-1%, and the content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1500 ℃-1640 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1230 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.45-1.1.

5. the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to claim 1, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; It is characterized in that: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein, and meter as weight percents; Alumina content is 8-19% in this spun glass; Iron oxide content is 0.01-3%, and sodium oxide content is 0.01-2%, and boron oxide content is 0-10%; Content of magnesia is 8.1-20%; Fluorine oxide content is 0-1%, and the content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1500 ℃-1580 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1520 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1310 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1160 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.45-0.7.

6. the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to claim 1, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; It is characterized in that: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein, and meter as weight percents; Alumina content is 8-39% in this spun glass; Iron oxide content is 0.01-3%, and sodium oxide content is 0.01-2%, and boron oxide content is 0-10%; Content of magnesia is 8.1-20%; Fluorine oxide content is 0-1%, and the content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1550 ℃-1700 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1450 ℃-1620 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1210 ℃-1480 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1330 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.45-1.3.

7. the spun glass that HS and energy-saving, emission-reducing, environment friendly and LV characteristic are arranged according to claim 1, the nominal diameter of this spun glass within 5 microns to 13 microns, the deviate of this glass fiber diameter be nominal diameter ± 15% in; It is characterized in that: this glass fiber package is salic, silicon oxide, Natural manganese dioxide and quicklime, red stone, sodium oxide, wherein, and meter as weight percents; Alumina content is 26-39% in this spun glass; Iron oxide content is 0.01-3%, and sodium oxide content is 0.01-2%, and boron oxide content is 0-10%; Content of magnesia is 8.1-20%; Fluorine oxide content is 0-1%, and the content of silicon oxide is 2.0 times-3.6 times of calcium oxide content, and the content of quicklime is 1.3 times-1.49 times of content of magnesia; This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1610 ℃-1710 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1500 ℃-1640 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1310 ℃-1490 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1200 ℃-1340 ℃; The breaking tenacity (N/tex) of this spun glass when diameter is less than or equal to 9 microns is 0.75-1.3.

8. glass fiber compound material, this matrix material comprise plastic substrate and embed the glass fiber compound material that the utilization in the plastic substrate requires each spun glass of 1-7 to make according to aforesaid right.

9. according to each described preparation method that the spun glass of HS and energy-saving, emission-reducing, environment friendly and LV characteristic is arranged of claim 1-7; The nominal diameter of this spun glass is within 5 microns to 13 microns; The deviate of this glass fiber diameter is in nominal diameter ± 15%, it is characterized in that:

Step 1; According to each described glass fiber formula of claim 1-8 dispose required various sodium oxide in the predetermined requisite special scope, red stone, aluminum oxide, silicon oxide, quicklime, Natural manganese dioxide are arranged or also have titanium oxide, barytic composition and predetermined silicon oxide, quicklime, Natural manganese dioxide between the raw material of innovative technology scheme of composition of specific proportions relation; Stir afterwards in temperature of fusion fusing through mixing corresponding to each glass fiber formula; Form the spun glass liquid of predetermined viscosity, homogenizing is clarified again; Discharge bubble, form flowable molten mass;

10. method according to claim 9 is characterized in that:

This spun glass is 10 in viscosity ^0.5Temperature when (handkerchief second) is 1530 ℃-1700 ℃; Viscosity is 10 ¹Temperature when (handkerchief second) is 1430 ℃-1620 ℃; Viscosity is 10 ²Temperature when (handkerchief second) is 1180 ℃-1480 ℃; Viscosity is 10 ³Temperature when (handkerchief second) is 1070 ℃-1320 ℃.