CN105753330A - Alkali-resistant glass fiber composition, alkali-resistant glass fiber and preparation method thereof - Google Patents
Alkali-resistant glass fiber composition, alkali-resistant glass fiber and preparation method thereof Download PDFInfo
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- CN105753330A CN105753330A CN201610148964.XA CN201610148964A CN105753330A CN 105753330 A CN105753330 A CN 105753330A CN 201610148964 A CN201610148964 A CN 201610148964A CN 105753330 A CN105753330 A CN 105753330A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/001—Alkali-resistant fibres
- C03C13/002—Alkali-resistant fibres containing zirconium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- 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
- C03B37/022—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/001—Alkali-resistant fibres
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
Abstract
The invention provides an alkali-resistant glass fiber composition, an alkali-resistant glass fiber and a preparation method thereof, relates to the field of high-value recycling of industrial solid waste, the alkali-resistant glass fiber and GRC (glass fiber reinforced cement-based composite) products and aims at further developing a high-value treatment mode of blast furnace slag and fly ash and improving production and application of the alkali-resistant glass fiber.The preparation method includes: using, by weight, 20-66% of blast furnace slag, 0-15% of fly ash, 20-50% of quartz powder, 0-17% of quicklime, 0-20% of zircon powder and 0-25% of sodium carbonate as raw materials; calculating, weighing, mixing, founding, forming (or drawing), annealing and cooling.Novel alkali-resistant fiber glass has alkali resistance higher than alkali-free fiber glass (E glass) available on current market and close to and even exceeding Cem-fil alkali-resistant fiber glass (Cem-fil glass).
Description
Technical field
The invention belongs to industrial solid castoff application technology as the second resource field, relate to the alkaline-resisting of a kind of alkaline resistance properties excellence
Glass fibre and manufacture method thereof, be specifically related to a kind of alkali-resistant glass fibre composition with blast-furnace cinder-flyash as raw material,
Alkali-resistant glass fibre and the preparation method of alkali-resistant glass fibre.
Background technology
A kind of waste residue discharged from blast furnace when blast-furnace cinder is manUfaCtUre of pig iron.Often produce the 1t pig iron give off 0.25t ~
1.2t blast-furnace cinder, its discharge capacity is different with smelting process and change along with the grade of ore.Along with the development of China's steel and iron industry,
Blast-furnace cinder discharge capacity is increasing.Nearly 15 × 10 are piled up according to statistics blast-furnace cinder in 20157T, takes up an area about 1000km2, and this
Numeral is also showing a rising trend.In order to process these waste residues, country is annual spends a huge sum of money to build deslagging field, wastes a large amount of people
Power material resources.Therefore, the comprehensive utilization of blast-furnace cinder is extremely important.Present stage main Land use systems have production cement, concrete,
Slag brick and tile and building block, additionally slag rubble is mainly used in highway, airport, foundation engineering, railroad ballast, aggregate and drip
Blue or green road surface etc..
Flyash is to receive the flue gas after coal combustion to catch the fine ash got off, and is that the primary solids that coal-burning power plant discharges gives up
Thing, is one of industrial residue that the current discharge capacity of China is bigger, along with the development of power industry, the flyash discharge capacity of coal-burning power plant
Increase year by year.Use the situation of coal according to China, use 1t coal and about produce 250kg ~ 300kg flyash.Substantial amounts of flyash is not
Add process, airborne dust, atmosphere pollution will be produced；River can be caused to silt up if entering water system, and toxic chemical substance therein is also
Human body and biology can be worked the mischief.Present stage main Land use systems has makees the raw material of manufacture of cement or mixing material, for building
Road and backfill, recovery iron essence, recovery coal, production agricultural fertilizer etc..
Summing up above understanding, these solid waste of present stage are mainly simply used in cement, concrete, building block and road paving
The aspects such as pad, backfill.These Land use systems are more superficial, and the economic worth created is less, also can bring secondary pollution.Cause
This, the Land use systems of the high added value developing these Industrial Solid refuses has the highest social value and economic worth.
Alkali-resistant glass fibre, since twentieth century six the seventies is born, has been constantly subjected to countries in the world researcher and material
The attention of tradesman, successively occurs in that the Sai Mufeier fiber of Britain, the Asahi Glass fiber of Japan, Chinese ER13 etc. are various
Alkali-resistant glass fibre.But ZrO in these alkali-resistant glass fibres2Content is high, and the raw material used is preferred raw mineral materials, makes
Its fusing, wire-drawing temperature and production cost are higher.Meanwhile, along with the continuous expansion of alkali-resistant glass fibre application, new application
Mode is constantly occurring, active demand a kind of raw material in market is cheap, produce simple, the alkali-resistant glass fibre of function admirable.
Chemical composition main in blast-furnace cinder is SiO2、Al2O3, CaO, MgO, MnO, FeO, S etc., wherein CaO,
SiO2、Al2O3Resultant accounts for more than the 90% of weight.The main oxides of power plants flyash consists of: SiO2、Al2O3、
FeO、Fe2O3、CaO、TiO2Deng.These components are the basic components of glass fibre, and wherein, CaO, MgO and ferriferous oxide are to raising
The alkali resistance of glass fibre has positive role.
Being found by experimental analysis, alkali-resistant glass fibre composition with blast-furnace cinder-flyash as raw material is also made by it
Standby alkali-resistant glass fibre fiber has feasibility.
Summary of the invention
The present invention is directed to the above-mentioned problems in the prior art, it is provided that a kind of using blast-furnace cinder adding coal ash as former
The preparation method of alkali-resistant glass fibre composition, alkali-resistant glass fibre and the alkali-resistant glass fibre of material.This alkali-resistant glass fibre group
Compound and fiber thereof have the resistance to acids and bases of excellence, as the reinforcing material of glass fiber reinforced cement based composites or other
Corrosion resistant material is useful.Meanwhile, blast-furnace cinder and flyash is made to have had again new utilization ways and space.
The present invention is by reasonably regulating the raw material such as blast-furnace cinder, flyash, silica flour, quick lime and soda ash, zirconium Ying Fen
Ratio as glass composition, and then become glass composition, it is possible to solve the problems referred to above well.
Technical solution of the present invention is as follows:
A kind of alkali-resistant glass fibre composition, it is characterised in that include the raw material of following mass percent: blast-furnace cinder 20 ~
66%, flyash 0 ~ 15%, silica flour 20 ~ 50%, quick lime 0 ~ 17%.
Further, above-mentioned alkali-resistant glass fibre composition, also include raw material zirconium English powder and soda ash, material quality percentage
Ratio consists of: blast-furnace cinder 0 ~ 66%, flyash 0 ~ 15%, silica flour 20 ~ 50%, quick lime 0 ~ 17%, zirconium English powder 0 ~ 20%, soda ash 0
~25%。
Described blast-furnace cinder is the blast-furnace cinder through pretreatment, and processing mode is: be homogenized in advance, grinding, crosses 200 mesh
Sieve, mixing homogenizing, and under the air atmosphere of 600～900 DEG C, process 2～3h.
Described flyash is the blast-furnace cinder through pretreatment, and processing mode is: be homogenized in advance, mixing homogenizing, and 600
～under the air atmosphere of 900 DEG C, process 2～3h.
The forming temperature of described alkali-resistant glass fibre composition is less than 1280 DEG C, its forming temperature and the difference of liquidus temperature
More than 80 DEG C.Forming temperature is also referred to as spinning temperature, is glass viscosity temperature when reaching about 1000 dPa.s.
A kind of alkali-resistant glass fibre prepared by above-mentioned alkali-resistant glass fibre composition, it is characterised in that as glass group
Become, to be converted into the mass percent of oxide, all contain following component: SiO250 ~ 70%, CaO 10 ~ 24%, Al2O3 0.5~
14%, MgO 1 ~ 7%, Na2O+K2O 0 ~ 0.8%, TiO20.1 ~ 0.8%, ferriferous oxide 0.1 ~ 0.9%, other 0 ~ 0.5%, wherein
" 0 " represents that content is infinitely close to 0 and is not 0.
Described Na2O+K2O is the two resultant, Na therein2O、K2O forms as glass, respectively at alkali-resistant glass fibre
In mass percent be Na2O 0 ~ 0.5%, K2O 0 ~ 0.5%, wherein " 0 " represents that content is infinitely close to 0 and is not 0.
Further, above-mentioned comprise the alkali-resistant glass fibre that zirconium English powder and soda ash alkali-resistant glass fibre composition prepare,
Form as glass, to be converted into the mass percent of oxide, containing following component: SiO250 ~ 65%, CaO 10 ~ 24%,
Al2O30.5 ~ 14%, MgO 2 ~ 7%, Na2O+K2O 0 ~ 15%, ZrO20 ~ 15%, TiO20.1 ~ 0.9%, ferriferous oxide 0.1 ~
0.5%, other 0 ~ 0.5%, wherein " 0 " represent content be infinitely close to 0 and be not 0.
Described Na2O+K2O, Na therein2O、K2O forms as glass, the quality hundred in alkali-resistant glass fibre respectively
Proportion by subtraction is Na2O 0 ~ 15%, K2O 0 ~ 0.5%, wherein " 0 " represents that content is infinitely close to 0 and is not 0.
In the above-mentioned alkali-resistant glass fibre of the present invention, described SiO2Content preferably 55 ~ 65%, further preferred 56.5 ~
62%；Described CaO content preferably 15 ~ 22%；Described Al2O3Content preferably 0.5 ~ 6%；Described content of MgO preferably 2 ~ 6.5%；
Containing ZrO2Composition, described ZrO2Content preferably 10 ~ 15%.
In the above-mentioned alkali-resistant glass fibre of the present invention, described other by the oxide that unavoidably introduces of use raw material become
Point, including zinc oxide, zirconium oxide and sulfide etc., its weight percentage is 0 ~ 0.5%, and wherein " 0 " represents described oxide
Gross weight is infinitely close to 0 and is not 0；
The manufacture method of the alkali-resistant glass fibre of the present invention comprises the following steps:
(1) pretreatment of raw material: use the mode of homogenizing field or homogenizing storehouse blast-furnace cinder to be carried out pre-homogenizing, then by Blast Furnace Ore
Slag carries out grinding, crosses 200 mesh sieves, mixing homogenizing, and processes 2 ~ 3h under the air atmosphere of 600～900 DEG C；Flyash is used
The mode of homogenizing field or homogenizing storehouse carries out pre-homogenizing, carries out mixing homogenizing afterwards, and locates under the air atmosphere of 600～900 DEG C
Reason 2～3h.
(2) by the raw material through pretreatment according to proportioning weighing, mixing, put in refractory container, at 1450～1550 DEG C
The glass metal that melted 3 ~ 5h is uniformly clarified, then regulation temperature of glass liquid is to higher than forming temperature 15～20 DEG C, by leaking
Plate or injection sheath are drawn into the fiber of diameter≤20 μm, then through organic matter coating and and restraint, obtain alkali-resistant glass fibre.
From set forth above, in the present invention, the major oxide constituents of alkali-resistant glass fibre composition is: SiO2 、
Al2O3、CaO、MgO、Na2O+K2O、ZrO2.The effect in glass of each oxide is now described and its content is defined as above-mentioned model
The reason enclosed.By the further Optimal improvements to above glass composition, form as glass, add percentage by weight be 0 ~
The ZrO of 15%2, and other components of corresponding regulation, such as Na2O etc., improve it resistance under conditions of guarantee production is feasible further
Alkalescence energy.
Before this, it should be noted that the main component of selected blast-furnace cinder and flyash is also SiO2 、CaO、
MgO、Al2O3Deng oxide, and weight resultant all accounts for more than 85%, is the basic components of glass fibre, and this is for the invention provides
The biggest foundation.Blast-furnace cinder used herein preferably comprises following components in percentage by weight: SiO229 ~ 40%, Al2O3
6 ~ 18%, CaO 31 ~ 45%, MgO 5 ~ 15%, Na2O 0.3 ~ 0.5%, K2O 0.20 ~ 0.25%, ferriferous oxide 0.2 ~ 0.9%, S
0.20 ~ 0.7%, TiO20.35~0.9%.Used flyash preferably comprises following components in percentage by weight: SiO245 ~ 55%,
Al2O325 ~ 40%, CaO 3 ~ 9%, MgO 0.4 ~ 1%, Na2O 0.3 ~ 0.7%, K2O 0.5 ~ 1.5%, ferriferous oxide 0.5 ~ 5%, S
0.20 ~ 0.8%, TiO2 0.45~1.5%。
In the present invention, blast-furnace cinder and fine coal ash composition are not carried out strict restriction.Because the place of production and producer
The fluctuation of its composition of the difference of formula is relatively big, but is found by substantial amounts of experiment, and most blast-furnace cinder all meets SiO2+
Al2O3+ CaO+MgO weight percentage >=90%, major part flyash all meets SiO2+ Al2O3+ CaO+MgO >=85%, is carried out
After the pretreatment such as corresponding homogenizing, calcining, add appropriate auxiliary material, adjust both ratios, just can be used for processability excellent
Different glass fibre.
SiO2As network skeleton basic in silicate fiber glass, its performance had important impact.It is to protect
The resistance to acid attack performance of card glass and the principal element of mechanical strength, increase SiO in glass2Content can improve the acidproof of glass
Property and mechanical strength.On the other hand, if the interpolation SiO of excess2, then melt temperature and the glass metal viscosity of glass can uprise,
Found relatively difficult, and the alkali resistance of glass reduces.SiO in the present invention2Content be 50 ~ 70%, preferably 55 ~ 65%, enter one
Step preferably 56.5 ~ 62%.If SiO2Content is not enough less than the mechanical performance of 50% glass and acid resistance, if SiO2Content
More than 70%, then melt temperature and viscosity are the highest, difficult forming, and cost is greatly improved.
Al2O3It is the network intermediate of aluminosilicate fibre glass, adds a small amount of Al in glass2O3Can significantly drop
Low tendency towards devitrification improves the liquidus temperature of glass, can also improve mechanical strength and the durability of glass simultaneously, if Al2O3Content mistake
Height, can substantially increase the viscosity of glass metal, and the recrystallization temperature simultaneously also resulting in glass raises, and causes founding and wire drawing of glass
Difficulty, additionally research finds the Al of excess2O3The alkali resistance that can make glass declines.In the present invention, due to blast-furnace cinder and flyash
In all contain Al2O3, on the premise of considering to make full use of these solid waste, determine in glass ingredient through substantial amounts of experiment
Al2O3Content, 0.5 ~ 14%, is more preferably 0.5 ~ 6%, if Al2O3Content higher than 14%, the alkali resistance to glass
Energy forms adverse effect with fiber.
CaO belongs to alkaline earth oxide, serves as important Network modifier in fibrous glass, introduces CaO and is mainly
Improve the alkaline resistance properties of glass, hardness and mechanical strength, and can reduce the viscosity of glass metal.The CaO of excess can make glass
The crystallization of glass increases.In the present invention, the content of CaO is 10 ~ 24%, preferably 15% ~ 22%.If CaO content is less than 10%, no
Reduction viscosity can be played very well, improve the effect of alkali resistance.CaO content increases higher than 24% crystallization making glass, glass
Acid resistance also can reduce.
MgO belongs to alkaline earth oxide, also acts as Network modifier, acts on close with CaO, uses a small amount of MgO to take
Tendency towards devitrification can be reduced for part CaO, improve processability.In the present invention, MgO is mainly introduced by blast-furnace cinder, alkaline-resisting
Content in glass fiber compound is 1 ~ 7%, preferably 2 ~ 6.5%, ensure that its performance and production technology during this scope.
Na2O and K2O is alkali metal oxide, serves as important Network modifier in fibrous glass, melts reducing glass
Body viscosity plays an important role with improving devitrification of glass tendency, and Na2O and K2The mixed alkali effect of O can increase largely
The durability of glass.But the field intensity of alkali metal ion is low, the structure of glass is played depolymerisation, reduces the mechanicalness of glass
Energy and water resistance.In the present invention, Na2O and K2The introducing of O is to be introduced the most on a small quantity or in order to adjust by raw materials such as blast-furnace cinders
The processability of joint glass is quantitatively introduced Na by soda ash2O's.Na2O+K2The resultant of O 0 ~ 15%, described Na2The weight percent of O
Content is 0 ~ 15%, described K2The weight percentage of O is 0 ~ 0.5%.This content is conducive to viscosity and the shaping of regulation glass
Performance, is particularly adding ZrO2Rear reduction viscosity and raising forming ability.
ZrO2It is to improve the alkali resistance of glass, acid resistance and the main component of resistance to water.Excess containing ZrO2Glass can be made
Liquidus temperature raise, melted difficulty, easy crystallization, be difficult to produce fiber.ZrO in the present invention2Containing measuring 0 ~ 15%, preferably 10 ~
15%.It is found through experiments, if ZrO in the present invention2Content more than 15%, then the easy split-phase of glass or crystallization, and liquid phase
Temperature uprises, and is difficult to found and be molded, and production cost raises.
Additionally, due to the present invention use composition fluctuation or the more industrial solid castoff of impurity (blast-furnace cinder and
Flyash) as raw material components, so the alkali-resistant glass fibre composition of the present invention can contain above-mentioned composition (SiO2、
Al2O3、CaO、MgO、Na2O+K2O、ZrO2Composition beyond), as being improved alkali resistance and reducing the TiO of liquidus temperature effect2、
Fe2O3、P2O5、MnO、CeO2, the organic trace element that can not exempt from the composition such as SrO, Cl and solid waste or noble metal etc..But preferably
Above-mentioned Main Ingredients and Appearance resultant reaches more than 97%, the composition of in particular up to more than 99%.So can avoid substantial amounts of impurity
It is mixed into and affects the performance of glass or fiber or make the problems such as production instability.
Beneficial effects of the present invention:
The present invention has carried out simple pretreatment to blast-furnace cinder and flyash, and with they former as alkali-resistant glass fibre
Material, turns waste into wealth, and pre-processes the content of blast-furnace cinder more than 30%, reach as high as 66%, pre-treating fly ash in glass composition
Content up to 15%, substantially increase the utilization rate of blast-furnace cinder and flyash, be that a kind of Industrial Solid refuse high value reclaims profit
By mode, improve the value of these solid waste, expanded their Land use systems, contribute to realization and economize on resources, protect
The social benefit in retaining ring border and environmental benefit.Meanwhile, alkali-proof glass and fiber thereof that the present invention produces have good corrosion resistance, molten
System, wire-drawing temperature are low, and the features such as raw material is cheap reduce the production cost of alkali-resisting glass fiber, contribute to alkali-resisting glass fiber and GRC goods
Promote the use of.The present invention has the highest use value and economical, societal benefits.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction analysis collection of illustrative plates of embodiment 1-7 sample；
Fig. 2 is that the Fourier of embodiment 1-7 sample changes infrared spectrogram；
Fig. 3 is the DSC differential thermal test curve of embodiment 1-2 sample；
Fig. 4 is the DSC differential thermal test curve of embodiment 3-5 sample；
Fig. 5 is the DSC differential thermal test curve of embodiment 6-7 sample；
Fig. 6 is the scanning electron microscope (SEM) photograph of embodiment 6 sample institute drawn fiber；
Fig. 7 is embodiment 4 bulk sample alkali corrosion resistance surface scan Electronic Speculum figure after 168 hours；
Fig. 8 is embodiment 3 bulk sample acid corrosion-resistant surface scan Electronic Speculum figure after 168 hours.
Detailed description of the invention
Below by specific embodiment, the present invention program is further explained, only it should be noted that following embodiment
Being to aid in those skilled in the art and be better understood from the present invention, protection scope of the present invention is not appointed by following example
What constraint.
First, to specifications in processing mode blast-furnace cinder and flyash are pre-processed, so that its composition is the most steady
Fixed.Blast-furnace cinder pretreatment mode is: be homogenized in advance, grinding, crosses 200 mesh sieves, and mixing is homogenized, and at the air gas of 600～900 DEG C
2～3h are processed under atmosphere.Flyash pretreatment mode is: be homogenized in advance, mixing homogenizing, and locates under the air atmosphere of 600～900 DEG C
Reason 2～3h.Luminoscope detects the oxide components in pretreated blast-furnace cinder and flyash, and combines in the present invention and use
Other industrial mineral material compositions be shown in Table 1, in table 1, the unit of each oxide components content refers to weight percent for " % "
Ratio.
TablePre-process blast-furnace cinder and pre-treating fly ash and other raw-material key component tables
Embodiment 1-7 alkali-resistant glass fibre composition, mass percent, raw material composition is shown in Table 2；
The alkali-resistant glass fibre prepared by alkali-resistant glass fibre composition in embodiment 1-7, forms as glass, to be converted into oxygen
The mass percent of compound, becomes to be grouped into and is shown in Table 2:
The preparation method of the alkali-resistant glass fibre of embodiment 1-7 in the present invention, step is:
(1) pretreatment of raw material: use the mode of homogenizing field or homogenizing storehouse blast-furnace cinder to be carried out pre-homogenizing, then by Blast Furnace Ore
Slag carries out grinding, crosses 200 mesh sieves, mixing homogenizing, and processes 2 ~ 3h under the air atmosphere of 600～900 DEG C；Flyash is used
The mode of homogenizing field or homogenizing storehouse carries out pre-homogenizing, carries out mixing homogenizing afterwards, and locates under the air atmosphere of 600～900 DEG C
Reason 2～3h.
(2) by the raw material through pretreatment according to mixing ratio weighing, mix with batch mixer, afterwards by joining of mixing
Close material loading platinum crucible to be placed in high-temperature electric smelting furnace, at the glass metal that 1450～1550 DEG C of melted 3 ~ 5h are uniformly clarified,
Then regulation temperature of glass liquid is to higher than forming temperature 15～20 DEG C, is drawn into diameter≤20 μm by bushing or injection sheath
Fiber, then through organic matter coating and and restraint, obtain alkali-resistant glass fibre.
The correlated performance test of the embodiment 1-7 alkali-resistant glass fibre in the present invention: according to existing method, with embodiment 1-
The alkaline-resisting both bulk glasses that 7 alkali-resistant glass fibre compositions prepare is test object, reflects prepared by the embodiment of the present invention
Alkali-resistant glass fibre performance, specific as follows:
The batch mixed loading platinum crucible is placed in high-temperature electric smelting furnace, at a temperature of 1450 DEG C ~ 1550 DEG C, melts 3
The glass metal uniformly clarified for ~ 5 hours, pours into the glass metal clarified afterwards and obtains in graphite jig containing less bubble
Both bulk glasses.It is subsequently placed in annealing furnace, at a temperature of 600 DEG C ~ 700 DEG C, is incubated 1-2 hour, obtain removing internal stress
Both bulk glasses sample.Carry out cutting or after grinding by glass specimen, carry out density, fluorescent component analysis, Fourier change red
External spectrum analysis, DSC differential thermal analysis, XRD diffraction, acid and alkali-resistance test, spinning temperature and the mensuration of liquidus temperature, monofilament draw real
Test with acid and alkali corrosion after the detection such as ESEM morphology observation.Wherein, density, fluorescent component analysis, acid and alkali-resistance, forming temperature
Testing with liquidus temperature, result is as shown in table 2.It addition, table 2 also list comparative example 1 and 2 glass composition and performance data
(comparative example 1 is E glass and comparative example 2 is typical case's cem-fil glass).
Wherein, density is to use the rectangular block shape sample of rule to utilize Archimedes principle to measure gained, from table 2 Midst density
Numerical value, it can be seen that the density of embodiments of the invention sample is all higher than E glass, even greater than cem-fil glass, illustrates to implement
Example glass structure relatively compact, is conducive to improving decay resistance.
Table 2
Alkali-resistant glass fibre alkaline resistance properties test in the embodiment of the present invention, owing to fibre weight is the least, uses alkali-resistant glass fibre group
Compound is prepared as alkali-proof glass, then uses powder method and the two kinds of method tests of block method, and method is as follows:
Powder method: particle diameter is immersed in the NaOH solution that percentage by weight is 5%, at 80 DEG C at the glass powder of 0.2 ~ 0.3mm
Lower insulation 168 hours, centre was once rocked every 24 hours, cleans one time with distilled water, then surpass with distilled water after taking-up
Sound isolates residual powder after cleaning 20-30 minute, dries 24 hours at 110 DEG C, and (after immersion, quality is damaged to calculate its weight-loss ratio
Vector mass ratio front with immersion, unit is " % "), each sample carries out three Duplicate Samples simultaneously, averages.
Block method: use diamond custting machine that glass sample cuts into the regular square that size is about 10mm × 5mm × 5mm
Shape block, accurately measures and records its length, width and height size, is immersed in afterwards in the NaOH solution that percentage by weight is 5%, 80
It is incubated 168 hours at DEG C.Clean one time with distilled water after taking-up, then with after distilled water ultrasonic cleaning 20-30 minute at 110 DEG C
Drying 24 hours, (unit interval, the weight-loss ratio of per surface area glass blocks, unit is [g/(cm to calculate its dissolution rate2*
Min)]), each sample carries out three Duplicate Samples simultaneously, averages.
Acid resistance test is also to use powder method and block method to carry out simultaneously, and the acid solution used is 1mol/L's
HCl.Concrete grammar is identical with above-mentioned alkali resistance test.
Acid-alkali-corrosive-resisting result from table 2 is it can be seen that the acid resistance of glass is with E glass and cem-fil in embodiment
Glass, in an order of magnitude, is on close level.The alkaline resistance properties of embodiment is higher than E glass, suitable with cem-fil glass.
The mensuration of forming temperature is to use to rotate high-temperature viscosimeter mensuration.Bulk sample is crushed to appropriately sized, dress
Enter in aluminum oxide crucible, put into high temperature viscosity instrument burner hearth, according to last endotherm peak temperature scope of DSC curve, add
Platinum rotor, to 1450 DEG C, is put in melten glass liquid by heat, starts test, along with the control of temperature of glass liquid declines, and viscosity
Become larger, until measuring viscosity is 103Temperature during dPa.s, is forming temperature.
Liquidus temperature test is to use thermal gradient furnace and determination of polarized light microscopy.By filling out of the glass specimen strip of pulverizing
It is charged in platinum boat, then platinum boat is put into the appointment position of the high-temperature gradient furnace rising to equilibrium temperature in advance.Gradient furnace is
High-temperature is 1250 DEG C, is incubated 2 ~ 5 hours in air atmosphere.Afterwards, take out sample, cool down in atmosphere, shown by polarisation
Micro mirror determines liquidus temperature point, then utilizes thermocouple to measure this temperature in thermal gradient furnace to be liquidus temperature.
The difference (forming temperature-liquidus temperature) of forming temperature and liquidus temperature is to subtract each other institute according to numerical value both
?.By forming temperature in table 2 and liquidus temperature and the difference between the two numerical value it can be seen that the forming temperature of embodiments of the invention
It is respectively less than 1270 DEG C of cem-fil glass, the difference of forming temperature and liquidus temperature also both greater than 80 DEG C, meet spinning requirement.
Wire drawing experiment is by uniform for cooperation glass fiber compound, puts into laboratory monofilament drawing device and melts, protects
Temperature obtains clarifying uniform glass metal for 2 hours, adjusts the temperature to higher than forming temperature about 15 DEG C, it is thus achieved that optimal wire drawing state,
Carry out wire drawing, and check its diameter and surface condition with ESEM.
In the present invention, the X-ray diffraction analysis collection of illustrative plates of embodiment sample is as it is shown in figure 1, embodiment sample as seen from Figure 1
Product are amorphous glass.
The Fourier of embodiment sample changes infrared spectrogram as in figure 2 it is shown, by can be seen that in Fig. 2 that embodiment sample exists
Wave number is 467cm-1、705cm-1、968cm-1Near there is absworption peak, they respectively corresponding Si-O flexural vibrations, T-O key (T=
Si, Al) stretching vibration, Si-O stretching vibration.So, can be seen that this embodiment sample is glassy silicate from this collection of illustrative plates
Glass.Fig. 3-Fig. 5 illustrates the DSC differential thermal analysis curve of embodiment 1-7 sample, as can be seen from the figure the Glass Transition temperature of sample
Degree Tg, first crystallization peak temperature TcWith last endotherm peak temperature Tm, for subsequent forming temperature, liquidus temperature test or property
Form the basis can be analyzed.Fig. 6 is the surface sweeping Electronic Speculum figure of embodiment 6 glass sample institute drawn fiber in the present invention, as seen from Figure 6
Fiber surface is bright and clean, and diameter can reach below 10 μm.Fig. 7 is embodiment 4 both bulk glasses sample alkali corrosion resistance table after 168 hours
Surface scan Electronic Speculum figure.Fig. 8 is embodiment 3 both bulk glasses sample acid corrosion-resistant surface scan Electronic Speculum figure after 168 hours.
By referring to embodiment and accompanying drawing, the several special cases that comprise in the present invention are discussed in detail, it can be seen that this
Bright have the biggest feasibility., also to point out in the case of without departing from the scope of the invention and thought, these embodiments are meanwhile
Can carry out changing and revise.
By above content, being not difficult to find out, the present invention utilizes the alkali-resistant glass fibre that blast-furnace cinder and flyash are raw material,
And preparation method thereof can adapt to existing production technology, can quantify produce, its product can be used for GRC cement base composite wood
The anticorrosive fields such as material, battery separator, have industrial applicibility.
Claims (10)
1. an alkali-resistant glass fibre composition, it is characterised in that include the raw material of following mass percent: blast-furnace cinder 20～
66%, flyash 0～15%, silica flour 20～50%, quick lime 0～17%.
Alkali-resistant glass fibre composition the most according to claim 1, it is characterised in that also include raw material zirconium English powder and pure
Alkali, material quality percentage consists of: blast-furnace cinder 0～66%, flyash 0～15%, silica flour 20～50%, quick lime 0～
17%, zirconium English powder 0～20%, soda ash 0～25%.
Alkali-resistant glass fibre composition the most according to claim 1 and 2, it is characterised in that: described blast-furnace cinder is warp
Crossing the blast-furnace cinder of pretreatment, processing mode is: be homogenized in advance, grinding, crosses 200 mesh sieves, and mixing is homogenized, and at 600～900 DEG C
2～3h are processed under air atmosphere.
Alkali-resistant glass fibre composition the most according to claim 1 and 2, it is characterised in that: described flyash is for passing through
Pretreatment blast-furnace cinder, processing mode is: be homogenized in advance, mixing homogenizing, and under the air atmosphere of 600～900 DEG C process 2～
3h。
5. according to the alkali-resistant glass fibre composition described in any one of Claims 1 to 4, it is characterised in that: described alkaline-resisting glass
The forming temperature of glass fiber composition is less than 1280 DEG C, and its forming temperature is more than 80 DEG C with the difference of liquidus temperature.
6. the alkali-resistant glass fibre prepared by the alkali-resistant glass fibre composition described in claim 1, it is characterised in that make
Form for glass, to be converted into the mass percent of oxide, all contain following component: SiO250～70%, CaO 10～
24%, Al2O30.5～14%, MgO 1～7%, Na2O+K2O 0～0.8%, TiO20.1～0.8%, ferriferous oxide 0.1～0.9%,
Other 0～0.5%, wherein " 0 " represent content be infinitely close to 0 and be not 0；
Described Na2O+K2O is the two resultant, Na therein2O、K2O forms as glass, respectively in alkali-resistant glass fibre
Mass percent is Na2O 0～0.5%, K2O 0～0.5%, wherein " 0 " represents that content is infinitely close to 0 and is not 0.
7. the alkali-resistant glass fibre prepared by the alkali-resistant glass fibre composition described in claim 2, it is characterised in that make
Form for glass, to be converted into the mass percent of oxide, containing following component: SiO250～65%, CaO 10～24%,
Al2O30.5～14%, MgO 2～7%, Na2O+K2O 0～15%, ZrO20～15%, TiO20.1～0.9%, ferriferous oxide 0.1
～0.5%, other 0～0.5%, wherein " 0 " represent content be infinitely close to 0 and be not 0；
Described Na2O+K2O is the two resultant, Na therein2O、K2O forms as glass, respectively in alkali-resistant glass fibre
Mass percent is Na2O 0～15%, K2O 0～0.5%, wherein " 0 " represents that content is infinitely close to 0 and is not 0.
8. according to the alkali-resistant glass fibre described in claim 6 or 7, it is characterised in that: described SiO2Content be 55～65%,
Further preferred 56.5～62%；Described CaO content is 15～22%；Described Al2O3Content is 0.5～6%；Described MgO
Content is 2～6.5%；Containing ZrO2Composition, described ZrO2Content be 10～15%.
9. according to the alkali-resistant glass fibre described in claim 6 or 7, it is characterised in that: described other are by being used raw material not
Can avoid the oxide components introduced, including zinc oxide, zirconium oxide and sulfide, its weight percentage is 0～0.5%, wherein
" 0 " represents that the gross weight of described oxide is infinitely close to 0 and is not 0.
10. the preparation method of the alkali-resistant glass fibre described in an any one of claim 6～9, it is characterised in that include following
Step:
(1) pretreatment of raw material: use the mode of homogenizing field or homogenizing storehouse blast-furnace cinder to be carried out pre-homogenizing, then by Blast Furnace Ore
Slag carries out grinding, crosses 200 mesh sieves, mixing homogenizing, and processes 2～3h under the air atmosphere of 600～900 DEG C；Flyash is adopted
Carry out pre-homogenizing by the mode of homogenizing field or homogenizing storehouse, carry out mixing homogenizing afterwards, and under the air atmosphere of 600～900 DEG C
Process 2～3h；
(2) by the raw material through pretreatment according to proportioning weighing, mixing, put in refractory container, at 1450～1550 DEG C melted 3
～the glass metal that 5h is uniformly clarified, then regulation temperature of glass liquid is to higher than forming temperature 15～20 DEG C, by bushing or
Injection sheath is drawn into the fiber of diameter≤20 μm, then through organic matter coating and and restraint, obtain alkali-resistant glass fibre.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106810063A (en) * | 2017-01-10 | 2017-06-09 | 江苏省冶金设计院有限公司 | A kind of method and system for producing mineral fibres as raw material with metallurgical slag |
| CN107213699A (en) * | 2017-06-07 | 2017-09-29 | 常州市瑞泰物资有限公司 | A kind of preparation method of coated filter material |
| CN108840574A (en) * | 2018-09-21 | 2018-11-20 | 辽宁新洪源环保材料有限公司 | A kind of 50,000 tons of spun yarn tank furnace glass compositions |
| CN109133654A (en) * | 2018-09-21 | 2019-01-04 | 辽宁新洪源环保材料有限公司 | A kind of high-performance perlite fiber and preparation method thereof |
| CN109626832A (en) * | 2019-01-16 | 2019-04-16 | 河南光远新材料股份有限公司 | A kind of production technology of alkali-free glass fibre yarn |
| CN110590170A (en) * | 2019-09-30 | 2019-12-20 | 九和同创碳金(宁夏)新材料科技有限公司 | Fly ash-based inorganic fiber and preparation method thereof |
| CN110627418A (en) * | 2019-09-06 | 2019-12-31 | 三河市纳诺科斯机电产品制造有限公司 | Inorganic fiber product prepared from fly ash, slag and sludge discharged by waste incineration power plant and preparation process thereof |
| CN111892302A (en) * | 2020-09-03 | 2020-11-06 | 泰山玻璃纤维有限公司 | Low-cost glass fiber composition with good alkali resistance and glass fiber |
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| CN104261686A (en) * | 2014-09-05 | 2015-01-07 | 巨石集团有限公司 | Alkali-resistant glass fiber composition |
| CN104591543A (en) * | 2014-12-31 | 2015-05-06 | 济南大学 | Boron-free high-performance glass fiber and preparation method thereof |
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| CN104261686A (en) * | 2014-09-05 | 2015-01-07 | 巨石集团有限公司 | Alkali-resistant glass fiber composition |
| CN104591543A (en) * | 2014-12-31 | 2015-05-06 | 济南大学 | Boron-free high-performance glass fiber and preparation method thereof |
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| CN106810063A (en) * | 2017-01-10 | 2017-06-09 | 江苏省冶金设计院有限公司 | A kind of method and system for producing mineral fibres as raw material with metallurgical slag |
| CN107213699A (en) * | 2017-06-07 | 2017-09-29 | 常州市瑞泰物资有限公司 | A kind of preparation method of coated filter material |
| CN108840574A (en) * | 2018-09-21 | 2018-11-20 | 辽宁新洪源环保材料有限公司 | A kind of 50,000 tons of spun yarn tank furnace glass compositions |
| CN109133654A (en) * | 2018-09-21 | 2019-01-04 | 辽宁新洪源环保材料有限公司 | A kind of high-performance perlite fiber and preparation method thereof |
| CN109133654B (en) * | 2018-09-21 | 2022-08-09 | 辽宁新洪源环保材料有限公司 | High-performance perlite fiber and preparation method thereof |
| CN108840574B (en) * | 2018-09-21 | 2022-11-22 | 辽宁新洪源环保材料有限公司 | Glass composition for 5 ten thousand ton spun yarn tank furnace |
| CN109626832A (en) * | 2019-01-16 | 2019-04-16 | 河南光远新材料股份有限公司 | A kind of production technology of alkali-free glass fibre yarn |
| CN110627418A (en) * | 2019-09-06 | 2019-12-31 | 三河市纳诺科斯机电产品制造有限公司 | Inorganic fiber product prepared from fly ash, slag and sludge discharged by waste incineration power plant and preparation process thereof |
| CN110590170A (en) * | 2019-09-30 | 2019-12-20 | 九和同创碳金(宁夏)新材料科技有限公司 | Fly ash-based inorganic fiber and preparation method thereof |
| CN111892302A (en) * | 2020-09-03 | 2020-11-06 | 泰山玻璃纤维有限公司 | Low-cost glass fiber composition with good alkali resistance and glass fiber |
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Application publication date: 20160713 |