CN106219988B - A kind of preparation method of high-performance glass fiber - Google Patents
A kind of preparation method of high-performance glass fiber Download PDFInfo
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- CN106219988B CN106219988B CN201610536817.XA CN201610536817A CN106219988B CN 106219988 B CN106219988 B CN 106219988B CN 201610536817 A CN201610536817 A CN 201610536817A CN 106219988 B CN106219988 B CN 106219988B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
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Abstract
The preparation method of high-performance glass fiber disclosed by the invention, step include：Weigh the compound of silicon, aluminium, magnesium, calcium, zirconium, titanium, iron, cerium, yttrium, niobium, lithium, bismuth and boron, wherein water soluble compound is not less than the 10% of all compound integral molar quantities, then deionized water is added in, it is situated between by mill of zirconium oxide balls, successively through techniques such as ball milling, spray drying, calcining, isostatic pressed processing, melted, wire drawings.The present invention is made water soluble compound be evenly coated at other compound surfaces in the form of ion, nano-scale particle is then obtained after calcining by ball milling mixing and spray drying.In the case where the high-ratio surface of nano particle can act on and isostatic pressed is in close contact each component, significantly reduces the glass melting temperature and melting time of glass, so as to reduce energy consumption required when glass fibre produces.
Description
Technical field
The present invention relates to a kind of preparation methods of high-performance glass fiber, belong to materials science field.
Background technology
High-performance glass fiber has high tensile strength, elasticity modulus height, shock resistance compared with common alkali-free glass fibre
The excellent performances such as performance is good, chemical stability is good, the good, high temperature resistant of fatigue resistance, are widely used in space flight, aviation, weapons, warship
The fields such as ship, chemical industry, such as missile engine case, aerospace aircraft liner, gun stock, launching gun barrel, bulletproof armour, high-pressure bottle
Deng.With the continuous development of science and technology, high-performance glass fiber is in the demand of the industrial circles such as optical cable, high intensity, heat-resisting material
Amount is also constantly expanding.
The major country of production high-performance glass fiber and product have at present：Japan " T " fiber, France " R " fiber,
The serial fibers of " BM " of Russia and " HS " serial fiber of China.The mechanical property of these high-performance glass fibers is all very excellent
It is different, but since forming temperature is excessively high, production difficulty is big, can not accomplish scale production on modern tank furnace, be confined to military project more
Field.
In the 21st century, fiberglass industry flourishes, and market application constantly expands, and major glass fibre company all pushes away
The high-performance glass fiber of a new generation is gone out；The technology of glass fibre is also constantly progressive simultaneously.At present, optimal high property
Energy glass fibre is SiO2-Al2O3- MgO-CaO systems glass fibre；The S-998 high intensity SAMC glass produced such as PPG companies of the U.S.
Glass fiber, its preparation method include batch mixing-melted-wire drawing, i.e., directly the dispensing mixed are poured into platinum-rhodium crucible and be melted
24 it is small when, the glass metal that clarified, is homogenized adjusts the rotating speed of the temperature of glass metal, liquid level and wire drawing machine, directly draws
Go out continuous glass fibre.The glass melting temperature of the glass is 1600 DEG C, and wire-drawing temperature is 1500 DEG C, and monofilament nascent state intensity is
4500 ~ 4750 MPa, although this glass fibre has higher mechanical strength, this glass smelting temperature and wire drawing temperature
Degree is high, melting time is long, and energy consumption is very big, and huge trouble is brought to production technology.
In order to reduce to greatest extent draw high-performance glass fiber when generated energy consumption, major glass fibre company and
Research Center's correction constantly optimizes the preparation method of glass fibre.The Advantex released such as U.S. Ovens-cornin companyTM
Glass fibre, its preparation method has done certain innovation in dispensing, i.e., in SiO2-Al2O3Draw on the basis of the component of-MgO-CaO
Enter substantial amounts of fluoride and alkali metal oxide, glass fibre, glass melting temperature are obtained by the technique of batch mixing-melted-wire drawing
For 1480 DEG C, crystallization ceiling temperature is 1204 DEG C, and wire-drawing temperature is 1260 DEG C, when melting time is 5 ~ 6 small；Although it significantly drops
Low glass fibre glass melting temperature and melting time, but its monofilament nascent state intensity is only 3100 ~ 3800 MPa.Meanwhile France
R- glass fibres and AdvantexTMGlass fibre is similar.Its preparation method is i.e. in SiO2-Al2O3Add on the basis of the component of-CaO
A certain amount of Na is added2O、K2The alkali compounds such as O obtain glass fibre by the technique of batch mixing-melted-wire drawing, temperature are melted
It spends for 1450 DEG C, wire-drawing temperature is 1280 DEG C, when melting time is 4 ~ 5 small；Although introduce a certain amount of Na+、K+It is greatly lowered
The glass melting temperature of glass, melting time and high temperature viscosity, and itself contains substantial amounts of Ca in matrix2+Improve the material of glass metal
Property, but its monofilament nascent state intensity is only 3200 ~ 3400 MPa.In addition, what Chinese Taishan glass fiber Ltd released
A kind of method for preparing environment-friendly high-modulus glass fiber, raw material include silica sand, pyrophillite, kaolin, alunite, quick lime,
Then magnesia and blast furnace slag obtain glass blocks by water quenching quenching at 1300 DEG C or more, gained glass blocks are put into
When remelting 4 ~ 5 is small again in electric furnace, continuous glass fibre is drawn using single hole wire-drawing crucible, glass melting temperature is 1470 DEG C, is drawn
Silk temperature is 1310 DEG C；Although water quenching quenching and high-temperature fusion cause compacter between glass particle component, drop significantly
Low glass melting temperature and melting time, but its drastically cool down under melt high temperature after each ion have little time to playback, cause holding one
Kind of high energy vitreousness, with irregular confusing array between Si-O keys and between Al-O key plasma associative keys, so as to drop
The low intensity of glass fibre, fiber nascent state intensity are only 3100 ~ 3500 MPa.
Therefore, ensureing that glass fibre is with high performance, continuing to optimize preparation method, effectively reduce high-performance
The energy consumption of glass fibre has great importance for batch production.
The content of the invention
The object of the present invention is to provide a kind of preparation methods of high-performance glass fiber, are ensureing glass fibre with high property
Can while, effectively reduce the temperature and time of glass smelting, generated energy consumption during so as to reduce glass smelting.
The preparation method of the high-performance glass fiber of the present invention, comprises the following steps：
（1）By the mole percent weighing of following raw material, the compound of 50 ~ 65% silicon, the chemical combination of 20 ~ 31% aluminium
Object, the compound of 6 ~ 11% magnesium, the compound of 3 ~ 5% calcium, the compound of 0.1 ~ 2% zirconium, the compound of 0.1 ~ 2% titanium, 0.1 ~ 0.5%
The compound of iron, the compound of 0.1 ~ 0.5% cerium, the compound of 0.1 ~ 0.5% yttrium, the compound of 0.1 ~ 0.5% niobium, 0.1 ~ 1% lithium
Compound, the compound of the compound of 0.1 ~ 1.5% bismuth and 0.1 ~ 0.5% boron, wherein water soluble compound is not less than all
The 10% of compound integral molar quantity；
（2）Weigh 4 ~ 5 times of zirconium oxide balls of above-mentioned raw material gross weight and 1 ~ 2 times of deionization of raw material gross weight
Water when ball milling mixing 12~24 is small, obtains mixture；
（3）The good mixture of above-mentioned ball milling by atomizer is spray-dried, deionized water is removed, obtains powder；
The inlet air temperature of spray drying is 180~300 DEG C, outlet air temperature is 30~100 DEG C；
（4）By the powder after above-mentioned spray drying when 700~900 DEG C of calcinings 1~3 are small, room temperature is subsequently cooled to；
（5）The good powder of above-mentioned calcining is put into rubber mold, in cold isostatic press under 100~300 MPa into
Row isostatic pressed obtains fine and close block；
（6）Compact block after above-mentioned isostatic pressed is put into crucible, it is small that 2 ~ 5 are melted at a temperature of being placed in 1400 ~ 1450 DEG C
When, the glass metal that is melted；
（7）The temperature of above-mentioned glass metal is down to 1250 ~ 1300 DEG C, starts wire drawing, adjustment wire drawing machine rotating speed for 1000 ~
1400 revs/min, it is drawn into 5 ~ 12 μm of continuous fiber.
In the present invention, the compound of the silicon is one or more of Ludox, ethyl orthosilicate and silica；
The compound of the aluminium is one or more of Aluminum sol, aluminum nitrate, aluminum acetate and alundum (Al2O3)；The change of the magnesium
Conjunction object is one or more of magnesium nitrate, magnesium acetate, magnesium carbonate and magnesia；The compound of the calcium is calcium nitrate, vinegar
One or more of sour calcium, calcium carbonate and calcium oxide；The compound of the zirconium is in zirconium nitrate, acetic acid zirconium and zirconium dioxide
One or more；The compound of the titanium is one or more of Titanium Nitrate, acetic acid titanium and titanium dioxide；The iron
Compound one or more of for ferric nitrate, ferric acetate, basic carbonate iron and di-iron trioxide；The compound of the cerium
For one or more of cerous nitrate, cerous acetate, cerous carbonate and ceria；The compound of the yttrium is yttrium nitrate, acetic acid
One or more of yttrium, yttrium carbonate and yttria；The compound of the niobium is nitric acid niobium, niobium oxalate and five aoxidizes two
One or more of niobium；The compound of the lithium is one kind or several in lithium nitrate, lithium acetate, lithium carbonate and lithia
Kind；The compound of the bismuth is one or more of bismuth nitrate, bismuth acetate, waltherite and bismuth oxide；The boron
Compound be one or both of boric acid and diboron trioxide.
In the present invention, the water soluble compound refers to Ludox, ethyl orthosilicate, Aluminum sol and various nitric acid
Salt, acetate, oxalates etc. can be dissolved in the compound of deionized water, including Ludox, ethyl orthosilicate, Aluminum sol, nitric acid
Aluminium, aluminum acetate, magnesium nitrate, magnesium acetate, calcium nitrate, calcium acetate, zirconium nitrate, acetic acid zirconium, Titanium Nitrate, acetic acid titanium, ferric nitrate, acetic acid
Iron, cerous nitrate, cerous acetate, yttrium nitrate, acetic acid yttrium, nitric acid niobium, niobium oxalate, lithium nitrate, lithium acetate, bismuth nitrate, bismuth acetate, boric acid
Deng.
The present invention has following beneficial features：
In preparation process, defoaming is played the role of in the introducing of niobium and cerium, beneficial to the clarification of glass metal, so as to not damage
In the case of glass fiber strength, effectively reduce the melting time of glass, reduce energy consumption cost；The introducing of bismuth is not influencing glass
In the case of intensity, the high temperature viscosity and forming temperature of glass can be effectively reduced, so as to reduce the glass melting temperature of glass, reduce glass
The melting time of glass.Meanwhile the present invention employs the water soluble compound that mole percent is not less than 10% in raw material, leads to
Ball milling mixing and drying process with atomizing are crossed, water soluble compound is made to be evenly coated at other compound surfaces in the form of ion,
Then nano-scale particle is obtained after calcining；In the case where the high-ratio surface of nano particle can act on and isostatic pressed makes each component
It is in close contact, significantly reduces the glass melting temperature and melting time of glass, so as to reduce energy required when glass fibre produces
Consumption.
Specific embodiment
With reference to example, the invention will be further described.
Embodiment 1：
By mole percent weigh 50% Ludox, 31% Aluminum sol, 10% magnesium nitrate, 4% calcium carbonate, 1% zirconium nitrate,
0.5% titanium dioxide, 0.5% ferric nitrate, 0.5% cerous nitrate, 0.5% yttrium carbonate, 0.3% nitric acid niobium, 0.2% lithium acetate, 1% bismuth nitrate
And 0.5% boric acid.5 times of zirconium oxide balls of raw material gross weight and 2 times of deionized water of raw material gross weight are weighed simultaneously,
When ball milling mixing 24 is small, mixture is obtained.The good mixture of ball milling by atomizer is spray-dried, removes deionization
Water obtains powder；The inlet temperature of spray drying is 200 DEG C, and outlet temperature is 30 DEG C.Then by the complete powder of above-mentioned spray drying
Body is placed in electric furnace, when 800 DEG C of calcinings 2 are small, cools to room temperature with the furnace.Then the good powder of above-mentioned calcining is put into rubber die
In tool, fine and close block is obtained with the pressure isostatic pressed of 200 MPa, the compact block after isostatic pressed is put into crucible, is placed in
Be melted at 1450 DEG C 3 it is small when, the glass metal that is melted.The temperature of glass metal is finally down to 1300 DEG C, starts wire drawing, adjustment
Wire drawing machine rotating speed is 1000 revs/min, is drawn into 12 μm of continuous fiber.
Glass monofilament strength detection method：With sampler and testing bar take between leakage hole and bobbins without frayed
Single fiber records strength note with UTM-11-20 and surveys strength, surveyed with measuring microscope under conditions of 800 times of magnifying powers automatically
Measure fibre diameter；Test condition：Strength test, 10 mm of selected fibre length, 8 mm/min of rate of extension, environment temperature 22~
25 DEG C, humidity 40~55%；Thus the fibre single thread tensile strength measured is about 4910 MPa.Glass fibre elasticity modulus is tested
Method：Using sonic method, i.e., precursor one end that full platinum wire-drawing crucible is drawn is welded in rosin on copper core loudspeaker, other end folder
Son is fixed, and two fixed points distance is 100 cm, and loudspeaker are connected on audio signal generator, measurement audio signal generator transmitting
With receiving frequency when signal reaches minimum.Elasticity modulus is calculated according to frequency, the glass fibre elasticity modulus thus measured is
90.05 GPa。
Embodiment 2：
25% silica, 31% Ludox, 19% Aluminum sol, 12% aluminum nitrate, 3% magnesium nitrate, 3% are weighed by mole percent
Magnesium carbonate, 2% calcium carbonate, 1% calcium acetate, 1.5% acetic acid zirconium, 0.1% acetic acid titanium, 0.1% Titanium Nitrate, 0.2% basic carbonate iron, 0.2%
Cerous carbonate, 0.3% cerous nitrate, 0.3% yttrium nitrate, 0.2% yttrium carbonate, 0.1% nitric acid niobium, 0.2% niobium oxalate, 0.1% anhydrous lithium acetate,
0.1% lithium carbonate, 0.2% waltherite, 0.1% bismuth nitrate and 0.3% boric acid.4 times of zirconium oxide of raw material gross weight is weighed simultaneously
1 times of deionized water of abrading-ball and raw material gross weight, when ball milling mixing 12 is small, obtains mixture.The good mixture of ball milling is led to
It crosses atomizer to be spray-dried, removes deionized water, obtain powder；The inlet temperature of spray drying is 180 DEG C, outlet temperature
For 40 DEG C.Then the complete powder of above-mentioned spray drying is placed in electric furnace, when 700 DEG C of calcinings 3 are small, cools to room temperature with the furnace.
Then the good powder of above-mentioned calcining is put into rubber mold, fine and close block is obtained with the pressure isostatic pressed of 100 MPa, will etc.
Compact block after static pressure is put into crucible, be placed at 1430 DEG C be melted 2.5 it is small when, the glass metal that is melted.Finally by glass
Glass liquid temperature degree is down to 1280 DEG C, starts wire drawing, adjustment wire drawing machine rotating speed is 1200 revs/min, is drawn into 10 μm of continuous fiber.
Glass monofilament strength detection method：With sampler and testing bar take between leakage hole and bobbins without frayed
Single fiber records strength note with UTM-11-20 and surveys strength, surveyed with measuring microscope under conditions of 800 times of magnifying powers automatically
Measure fibre diameter.Test condition：Strength test, 10 mm of selected fibre length, 8 mm/min of rate of extension, environment temperature 22~
25 DEG C, humidity 40~55%；Thus the fibre single thread tensile strength measured is about 4893 MPa.Glass fibre elasticity modulus is tested
Method：Using sonic method, i.e., precursor one end that full platinum wire-drawing crucible is drawn is welded in rosin on copper core loudspeaker, other end folder
Son is fixed, and two fixed points distance is 100 cm, and loudspeaker are connected on audio signal generator, measurement audio signal generator transmitting
With receiving frequency when signal reaches minimum.Elasticity modulus is calculated according to frequency, the glass fibre elasticity modulus thus measured is
89.17 GPa。
Embodiment 3：
24% silica, 25% Ludox, 10% ethyl orthosilicate, 11% Aluminum sol, 9% nitric acid are weighed by mole percent
Aluminium, 4% magnesium nitrate, 3% magnesium carbonate, 4% magnesium acetate, 2% calcium carbonate, 3% calcium acetate, 0.5% zirconium nitrate, 0.5% acetic acid zirconium, 0.5% 2
Zirconium oxide, 0.1% Titanium Nitrate, 0.1% basic carbonate iron, 0.1% ferric nitrate, 0.2% cerous carbonate, 0.3% cerous nitrate, 0.1% yttrium carbonate,
0.2% nitric acid niobium, 0.3% niobium oxalate, 0.6% lithium acetate, 0.4% lithium carbonate, 0.5% bismuth nitrate, 0.2% bismuth acetate, 0.1% waltherite
And 0.3% boric acid.Weigh 4.5 times of zirconium oxide balls of raw material gross weight and 1.5 times of deionization of raw material gross weight simultaneously
Water when ball milling mixing 12 is small, obtains mixture.The good mixture of ball milling is spray-dried by atomizer, go from
Sub- water, obtains powder；The inlet temperature of spray drying is 300 DEG C, and outlet temperature is 100 DEG C.Then it is above-mentioned spray drying is complete
Powder 900 DEG C calcining 1 it is small when, cool to room temperature with the furnace.Then the good powder of above-mentioned calcining is put into rubber mold, with
The pressure isostatic pressed of 300 MPa obtains fine and close block, and the compact block after isostatic pressed is put into crucible, is placed at 1400 DEG C
Be melted 2 it is small when, the glass metal that is melted.Temperature of glass liquid is finally down to 1260 DEG C, starts wire drawing, adjusts wire drawing machine rotating speed
For 1250 revs/min, 7 μm of continuous fiber is drawn into.
Glass monofilament strength detection method：With sampler and testing bar take between leakage hole and bobbins without frayed
Single fiber records strength note with UTM-11-20 and surveys strength, surveyed with measuring microscope under conditions of 800 times of magnifying powers automatically
Measure fibre diameter；Test condition：Strength test, 10 mm of selected fibre length, 8 mm/min of rate of extension, environment temperature 22~
25 DEG C, humidity 40~55%；Thus the fibre single thread tensile strength measured is about 4876 MPa.Glass fibre elasticity modulus is tested
Method：Using sonic method, i.e., precursor one end that full platinum wire-drawing crucible is drawn is welded in rosin on copper core loudspeaker, other end folder
Son is fixed, and two fixed points distance is 100 cm, and loudspeaker are connected on audio signal generator, measurement audio signal generator transmitting
With receiving frequency when signal reaches minimum.Elasticity modulus is calculated according to frequency, the glass fibre elasticity modulus thus measured is
88.86 GPa。
Embodiment 4：
25% silica, 30% Ludox, 10% ethyl orthosilicate, 10% Aluminum sol, 10% nitric acid are weighed by mole percent
Aluminium, 2% magnesium nitrate, 3% magnesium carbonate, 1% magnesium acetate, 2% calcium carbonate, 1% calcium acetate, 0.1% zirconium dioxide, 2% titanium dioxide, 0.1%
Basic carbonate iron, 0.2% cerous carbonate, 0.2% yttrium nitrate, 0.1% yttrium carbonate, 0.2% nitric acid niobium, 0.3% niobium oxalate, 0.6% lithium acetate,
0.4% lithium carbonate, 1% bismuth nitrate, 0.2% bismuth acetate, 0.3% waltherite and 0.3% boric acid.Weigh the 4.3 of raw material gross weight simultaneously
1.3 times of deionized water of zirconium oxide balls again and raw material gross weight, when ball milling mixing 18 is small, obtains mixture.By ball milling
Good mixture is spray-dried by atomizer, is removed deionized water, is obtained powder；The inlet temperature of spray drying is
270 DEG C, outlet temperature is 33 DEG C.Then the complete powder of above-mentioned spray drying is cooled to the furnace room when 900 DEG C of calcinings 1 are small
Temperature.Then the good powder of above-mentioned calcining is put into rubber mold, fine and close block is obtained with the pressure isostatic pressed of 300 MPa,
Compact block after isostatic pressed is put into crucible, be placed at 1420 DEG C be melted 2.2 it is small when, the glass metal that is melted.Finally
Temperature of glass liquid is down to 1250 DEG C, starts wire drawing, adjustment wire drawing machine rotating speed is 1300 revs/min, is drawn into 5 μm of continuous fibre
Dimension.
Glass monofilament strength detection method：With sampler and testing bar take between leakage hole and bobbins without frayed
Single fiber records strength note with UTM-11-20 and surveys strength, surveyed with measuring microscope under conditions of 800 times of magnifying powers automatically
Measure fibre diameter；Test condition：Strength test, 10 mm of selected fibre length, 8 mm/min of rate of extension, environment temperature 22~
25 DEG C, humidity 40~55%；Thus the fibre single thread tensile strength measured is about 4801 MPa.Glass fibre elasticity modulus is tested
Method：Using sonic method, i.e., precursor one end that full platinum wire-drawing crucible is drawn is welded in rosin on copper core loudspeaker, other end folder
Son is fixed, and two fixed points distance is 100 cm, and loudspeaker are connected on audio signal generator, measurement audio signal generator transmitting
With receiving frequency when signal reaches minimum.Elasticity modulus is calculated according to frequency, the glass fibre elasticity modulus thus measured is
88.03GPa。
Embodiment 5：
65% Ludox, 20% alundum (Al2O3), 7% magnesia, 3% calcium oxide, 1.5% titanium dioxide are weighed by mole percent
Zirconium, 0.5% titanium dioxide, 0.5% di-iron trioxide, 0.2% ceria, 0.5% yttrium dioxide, 0.5% niobium pentaoxide, 0.8%
Lithia, 0.4% bismuth oxide and 0.1% diboron trioxide.4.6 times of zirconium oxide balls of raw material gross weight are weighed simultaneously
Deionized water with 1.6 times of raw material gross weight, when ball milling mixing 16 is small, obtains mixture.The good mixture of ball milling is passed through
Atomizer is spray-dried, and is removed deionized water, is obtained powder；The inlet temperature of spray drying is 270 DEG C, and outlet temperature is
34℃.Then the complete powder of above-mentioned spray drying is placed in electric furnace, when 900 DEG C of calcinings 1 are small, cools to room temperature with the furnace.So
The good powder of above-mentioned calcining is put into rubber mold afterwards, fine and close block is obtained with the pressure isostatic pressed of 300 MPa, will be waited quiet
Compact block after pressure is put into crucible, be placed at 1445 DEG C be melted 5 it is small when, the glass metal that is melted.Finally by glass metal
Temperature is down to 1330 DEG C, starts wire drawing, adjustment wire drawing machine rotating speed is 1270 revs/min, is drawn into 8 μm of continuous fiber.
Glass monofilament strength detection method：With sampler and testing bar take between leakage hole and bobbins without frayed
Single fiber records strength note with UTM-11-20 and surveys strength, surveyed with measuring microscope under conditions of 800 times of magnifying powers automatically
Measure fibre diameter；Test condition：Strength test, 10 mm of selected fibre length, 8 mm/min of rate of extension, environment temperature 22~
25 DEG C, humidity 40~55%；Thus the fibre single thread tensile strength measured is about 4800 MPa.Glass fibre elasticity modulus is tested
Method：Using sonic method, i.e., precursor one end that full platinum wire-drawing crucible is drawn is welded in rosin on copper core loudspeaker, other end folder
Son is fixed, and two fixed points distance is 100 cm, and loudspeaker are connected on audio signal generator, measurement audio signal generator transmitting
With receiving frequency when signal reaches minimum.Elasticity modulus is calculated according to frequency, the glass fibre elasticity modulus thus measured is
87.76 GPa。
Claims (1)
1. a kind of preparation method of high-performance glass fiber, it is characterised in that comprise the following steps：
（1）By the mole percent weighing of following raw material, the compound of 50 ~ 65% silicon, the compound of 20 ~ 31% aluminium, 6 ~
The change of the compound of 11% magnesium, the compound of 3 ~ 5% calcium, the compound of 0.1 ~ 2% zirconium, the compound of 0.1 ~ 2% titanium, 0.1 ~ 0.5% iron
Close object, the compound of 0.1 ~ 0.5% cerium, the compound of 0.1 ~ 0.5% yttrium, the compound of 0.1 ~ 0.5% niobium, the chemical combination of 0.1 ~ 1% lithium
The compound of object, the compound of 0.1 ~ 1.5% bismuth and 0.1 ~ 0.5% boron, wherein water soluble compound are not less than all compounds
The 10% of integral molar quantity；The compound of the silicon is one or more of Ludox, ethyl orthosilicate and silica；Institute
The compound for the aluminium stated is one or more of Aluminum sol, aluminum nitrate, aluminum acetate and alundum (Al2O3)；The chemical combination of the magnesium
Object is one or more of magnesium nitrate, magnesium acetate, magnesium carbonate and magnesia；The compound of the calcium is calcium nitrate, acetic acid
One or more of calcium, calcium carbonate and calcium oxide；The compound of the zirconium is in zirconium nitrate, acetic acid zirconium and zirconium dioxide
It is one or more of；The compound of the titanium is one or more of Titanium Nitrate, acetic acid titanium and titanium dioxide；The iron
Compound is one or more of ferric nitrate, ferric acetate, basic carbonate iron and di-iron trioxide；The compound of the cerium is
One or more of cerous nitrate, cerous acetate, cerous carbonate and ceria；The compound of the yttrium for yttrium nitrate, acetic acid yttrium,
One or more of yttrium carbonate and yttria；The compound of the niobium is nitric acid niobium, niobium oxalate and niobium pentaoxide
One or more of；The compound of the lithium is one or more of lithium nitrate, lithium acetate, lithium carbonate and lithia；
The compound of the bismuth is one or more of bismuth nitrate, bismuth acetate, waltherite and bismuth oxide；The change of the boron
It is one or both of boric acid and diboron trioxide to close object；
（2）Weigh 4 ~ 5 times of zirconium oxide balls of above-mentioned raw material gross weight and 1 ~ 2 times of deionized water of raw material gross weight, ball
When mill mixing 12~24 is small, mixture is obtained；
（3）The good mixture of above-mentioned ball milling by atomizer is spray-dried, deionized water is removed, obtains powder；Spraying
Dry inlet air temperature is 180~300 DEG C, outlet air temperature is 30~100 DEG C；
（4）By the powder after above-mentioned spray drying when 700~900 DEG C of calcinings 1~3 are small, room temperature is subsequently cooled to；
（5）The good powder of above-mentioned calcining is put into rubber mold, carried out in cold isostatic press under 100~300 MPa etc.
Static pressure obtains fine and close block；
（6）Compact block after above-mentioned isostatic pressed is put into crucible, at a temperature of being placed in 1400 ~ 1450 DEG C be melted 2 ~ 5 it is small when, obtain
To the glass metal of melting；
（7）The temperature of above-mentioned glass metal is down to 1250 ~ 1300 DEG C, starts wire drawing, adjustment wire drawing machine rotating speed is 1000 ~ 1400
Rev/min, it is drawn into 5 ~ 12 μm of continuous fiber.
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| CN108320938A (en) * | 2018-03-16 | 2018-07-24 | 浙江上陶电气有限公司 | Fuse disconnecting switch |
| CN112777939A (en) * | 2021-01-12 | 2021-05-11 | 江青鞠 | Glass fiber with high corrosion resistance and preparation method thereof |
| CN112624621A (en) * | 2021-01-14 | 2021-04-09 | 曹贝贝 | Glass fiber with high heat resistance and preparation method thereof |
| CN114085039B (en) * | 2022-01-18 | 2022-04-01 | 山东墨匠新材料科技有限公司 | High-strength high-modulus glass fiber composition, and production method and application of glass fiber |
| CN114592341B (en) * | 2022-03-11 | 2023-03-17 | 北京理工大学 | Method for modifying bulletproof fiber fabric by using aluminum oxide |
| CN117492131A (en) * | 2023-11-02 | 2024-02-02 | 创昇光电科技(苏州)有限公司 | High-temperature-resistant optical fiber with high alumina content and fiber grating |
| CN117603568B (en) * | 2024-01-22 | 2024-03-22 | 广东骊虹包装有限公司 | High-strength stretch-proof packaging bag and production process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248637A (en) * | 1991-04-24 | 1993-09-28 | Asahi Glass Company Ltd. | Highly heat resistant glass fiber and process for its production |
| US5972500A (en) * | 1997-08-28 | 1999-10-26 | Johns Manville International, Inc. | Non-linear multicomponent glass fibers from linear primaries |
| CN103172265A (en) * | 2013-04-09 | 2013-06-26 | 中国计量学院 | High-strength glass fiber and preparation method thereof |
| CN104445965A (en) * | 2014-05-15 | 2015-03-25 | 江西大华云通玻纤有限公司 | High-performance glass fiber |
| CN104769038A (en) * | 2012-11-05 | 2015-07-08 | 出光兴产株式会社 | Polycarbonate resin composition and molded article |
Family Cites Families (1)
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| JPS4986638A (en) * | 1972-12-25 | 1974-08-20 |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248637A (en) * | 1991-04-24 | 1993-09-28 | Asahi Glass Company Ltd. | Highly heat resistant glass fiber and process for its production |
| US5972500A (en) * | 1997-08-28 | 1999-10-26 | Johns Manville International, Inc. | Non-linear multicomponent glass fibers from linear primaries |
| CN104769038A (en) * | 2012-11-05 | 2015-07-08 | 出光兴产株式会社 | Polycarbonate resin composition and molded article |
| CN103172265A (en) * | 2013-04-09 | 2013-06-26 | 中国计量学院 | High-strength glass fiber and preparation method thereof |
| CN104445965A (en) * | 2014-05-15 | 2015-03-25 | 江西大华云通玻纤有限公司 | High-performance glass fiber |
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