CN108191234A - Tin-oxide doping red mud alkali resistant glass fibre and preparation method thereof - Google Patents
Tin-oxide doping red mud alkali resistant glass fibre and preparation method thereof Download PDFInfo
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- CN108191234A CN108191234A CN201810097004.4A CN201810097004A CN108191234A CN 108191234 A CN108191234 A CN 108191234A CN 201810097004 A CN201810097004 A CN 201810097004A CN 108191234 A CN108191234 A CN 108191234A
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/02—Pretreated ingredients
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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
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Abstract
The present invention relates to a kind of tin-oxides using solid waste red mud as raw material to adulterate red mud alkali resistant glass fibre and preparation method thereof.The glass fibre is formed as glass, and the mass percentage respectively formed is：SiO257 ~ 64%, SnO+SnO20.5 ~ 4%, Al2O38 ~ 12%, FeO+Fe2O39 ~ 13%, Na2O+K2O 3 ~ 7%, CaO 5 ~ 10%, MgO 1 ~ 5%, TiO21 ~ 3%, CaF20 ~ 1%, other 0 ~ 1%.It is raw material using red mud and fiber glass industry raw material, pre-processed by red mud, dispensing, homogenizing, melting, clarification homogenizing, wire drawing, the flows such as cooling, it is relatively low to prepare cost, excellent water-fast, caustic corrosion performance alkali-resistant glass fibre, improve glass high temperature viscosity and crystallization property simultaneously, it is easy to industrialized production, glass concrete can be applied to well（GRC）Product, pipeline winding product, mortar batch mixing and external-wall heat-insulation material etc..
Description
Technical field
The present invention relates to solid waste red mud recyclings and silicate glass material field, specifically, are related to one
Silicate alkali-resistant glass fibre that kind is prepared using red mud for raw material and preparation method thereof.
Background technology
Red mud is the pollution waste residue generated during industry aluminium processed, and the output ratio with aluminium oxide is 0.8 ~ 1.5t, China
Red mud accumulating amount has reached several hundred million tons, is one of the industrial solid castoff of current China's discharge capacity maximum, becomes and restricts aluminium industry
The bottleneck of sustainable and healthy development.But current red mud comprehensive utilization ratio only reaches 4%, to reach high usage and high added value
It utilizes, can not achieve at this stage.Since strong alkaline substance can be added in aluminium oxide preparation process, generate aluminium processed useless
Slag-red mud, has high alkali content, and leachate PH can cause seriously to endanger up to 12 ~ 13 to water resource, soil, air etc.
Evil.At present, on a large scale there are mainly two types of the methods of disposition red mud：Outdoor wet method, which is built a dam, stacks and is discharged into sea, but all no pair
Red mud problem thoroughly solves.Therefore, appropriate processing is carried out to red mud, carries out recycling, reduces pollution simultaneously, section
About resource is a green, the effective approach for solving red mud problem, thus increases utilization gesture to red mud must
Row.
Red mud resource utilization generally speaking mainly has the following aspects at present：Construction material（Cement, ceramics, glass
Deng）, soil conditioner, metal recovery, adsorbent（Water, gas）, catalytic action（Carrier, catalyst）.The above is summarized, is removed
Have outside larger application amount in construction material, be also in the laboratory research stage mostly.The better simply roadbase of red mud, cement are ripe
The admixture of material, brick block etc. utilizes, and the economic value of creation is relatively small, and high alkali content therein can also generate environment
Secondary pollution.
It is material indispensable in people's production, life as the glass of construction material important member, it is therein important
A member alkali-resistant glass fibre is even more widely applied as the reinforcing material in resistant material.Earliest alkali-proof glass is fine
Dimension originates in Britain, is mainly used in the toughening of cement concrete.Although research starting of the China in terms of alkali-proof glass is compared
It is early, but flow of research is slow, just there is certain achievement to the seventies.By China Building Materials Academy, Nanjing
Glass fibre studying and designing institute and the unremitting effort of related universities and colleges, producer, have finally developed a series of alkali-proof glasses
Component and technique, while in terms of the surface treatment of alkali-resistant glass fibre and achieve preferable achievement in research.Application at present
Alkali-resistant glass fibre be mainly silicate glass system, either external Sai Mufeier fibers（Cem-fil）, Pompeii it is prompt
（PPG）The PPG fibers and Asahi Glass fiber of company or the slightly worse alkali-free glass fibre of domestic alkali resistance（ER13）, all exist
One problem is exactly high zirconia content, minimum also to reach 6%, reaches as high as 20%, this results in material melting temperature, fiber
Forming temperature is all very high, and production technology is harsh, this is resulted in, and the production cost increases, limits pushing away for alkali-resisting glass fiber to a certain extent
Wide application.Therefore, it is necessary to a kind of inexpensive alkali-resistant glass fibres haveing excellent performance to introduce to the market.
It has been investigated that red mud main component is SiO2、Al2O3、CaO、MgO、Fe2O3, FeO etc., main oxides are
Silicate glass ingredient.SiO2For glass network former oxide, the important component of glass skeleton；Al2O3, iron oxidation
Object is network intermediate oxide, can enter glass network under certain condition in the form of tetrahedral structure, improves network polymerization degree,
And then improve water-fast, the alkaline energy of glass fibre.And it is demonstrated experimentally that alkaline-earth metal MgO, CaO etc. are glued except can reduce glass high temperature
It is outside one's consideration, a certain amount of addition has positive effect to the raising of glass fibre alkali resistance.
The preparation of red mud alkali resistant glass fibre and grinding for structure and performance are adulterated by experimental raw analysis and tin-oxide
Study carefully discovery, by the red mud of pretreatment, coordinated by adding the technical grades such as stannous oxide, dolomite, lime stone, commercial alumina
Material adjustment fiberglass component, can prepare processability and good thermal stability, water-fast, caustic corrosion function admirable, cost
It is relatively low, it is easy to the alkali-resistant glass fibre of large-scale industrial production.
Invention content
The problems such as present invention is for the high cost of current alkali-resistant glass fibre and red mud big accumulating amount provides a kind of to locate in advance
The tin-oxide that red mud is managed as raw material adulterates alkali-resistant glass fibre and preparation method thereof.Tin-oxide adulterates red mud alkali resistant glass fibers
Dimension is with SiO2、Al2O3、Fe2O3、RO（R=Mg、Ca、Sn）For key component, by adjusting red mud, lime stone, industry in raw material
Aluminium oxide, dolomite, silica flour, fluorite, magnesia, tin-oxide component ratio, to glass fibre alkaline resistance properties, crystallization speed
Rate and high temperature viscosity further improve, and obtain that cost is relatively low, and processability is good, alkali corrosion resistance performance with it is alkaline-resisting currently on the market
Glass fibre（AR glass fibres）Similar glass fibre, the alkali proof fiber can be used as fibre reinforced materials, be spiked into cement
In based composites, enhance the intensity and toughness of matrix.
Technical solution of the present invention is as follows：It is a kind of using red mud as the alkali-resistant glass fibre of raw material, by each raw material add
The adjustment of amount, and then glass fibre component is adjusted, it is glued with further improving fiber alkali resistance, crystallization rate and high temperature
Degree.The mass percentage of each raw material of proportion optimizing is as follows：Red mud 27 ~ 40% after pretreatment, dolomite 7 ~ 18%, stannous oxide
0.5 ~ 4%, commercial alumina 3 ~ 5%, silica flour 46 ~ 59%, magnesia 0 ~ 1%, lime stone 0 ~ 3%, fluorite 0 ~ 1%；By red mud
The flows such as pretreatment, dispensing, homogenizing, melting, clarification homogenizing, wire drawing, cooling, it is relatively low to prepare forming temperature, excellent water-fast, alkali
The inexpensive alkali-resistant glass fibre of corrosive nature.
The preprocess method of the pretreatment red mud is as follows：Red mud is dried to removal under 100 DEG C ~ 250 DEG C air atmospheres
Grinding is sieved after moisture（Granularity is less than 250um）, red mud keeps the temperature 2 ~ 5 under 500 DEG C ~ 700 DEG C air atmospheres after mixing is homogenized
Hour.
In addition, this patent glass fibre is preferably with Fe2O3Content improves, and increases glass fibre alkali resistance.Fe2O3Quality
Percentage composition is rapidly reduced to 930 DEG C from 960 DEG C for 10.2% recrystallization temperature, and corresponding forming temperature increases sharply from 1240 DEG C
To 1279 DEG C；Limit Fe2O3/ SiO2Mass percent C2 is 0.15 ~ 0.20, controls devitrification of glass rate.
Above-mentioned tin-oxide adulterates alkali-resistant glass fibre, is formed as glass, is converted into oxide mass percentage, by with
It is lower into being grouped as：SiO257 ~ 64%, SnO+SnO20.5 ~ 4%, Al2O38 ~ 12%, FeO+Fe2O3 9 ~ 13%, Na2O+K2O 3~
7%, CaO 5 ~ 10%, MgO 1 ~ 5%, TiO21 ~ 3%, CaF20 ~ 1%, other 0 ~ 1%；Also, ratio C 1=(SnO+SnO2）/
SiO2It is 0.008 ~ 0.070.
The preparation method of the tin-oxide doping red mud alkali resistant glass fibre of the present invention, includes the following steps：（1）By red mud
Grinding is sieved after moisture removal is removed in drying under 100 DEG C ~ 250 DEG C air atmospheres（Granularity is less than 250um）, red mud mix
After change 2 ~ 5 hours are kept the temperature under 500 DEG C ~ 700 DEG C air atmospheres.（2）By step（1）The red mud of middle pretreatment and stannous oxide powder
End, dolomite, silica flour, commercial alumina, fluorite, lime stone, magnesia are put into fire resisting appearance by corresponding proportion after mixing
In device, 3 ~ 6h of heat preservation is melted at 1400 DEG C ~ 1500 DEG C and obtains being homogenized clear glass metal, then higher than forming temperature（Molding
It is 10 that temperature, which takes viscosity of glass metal,3Corresponding temperature during dPa.s）Company is drawn by casing or bushing at 20 ~ 35 DEG C or so
Continuous glass fibre, then cooling obtain alkali-resistant glass fibre（Precursor）, average fibre diameter is less than 30 microns.
Structural analysis test is carried out to above-mentioned alkali-resistant glass fibre, material phase analysis is carried out using XRD.For aspect of performance, adopt
With differential thermal test and water-fast, alkaline test, thermal stability and chemical stability are analyzed；Using rotation high-temperature viscosimeter,
Thermal gradient furnace measures glass forming temperature T respectively with petrographic microscopelg3（It is about 10 to refer generally to glass viscosity3Temperature during dPa.s）
With crystallization ceiling temperature Tuc（Liquidus temperature）, by two temperatures it is poor >=80 DEG C, ensure the continuous drawing of glass fibre.
Beneficial effects of the present invention：（1）The alkali-resisting glass fiber obtained through above-mentioned preparation method, red mud amount is up in raw material
To 40%, red mud dosage is improved, reduce the pollution of environment reduces alkali-resisting glass fiber production cost simultaneously.（2）The alkali-proof glass is fine
It is excellent to tie up alkali resistance, comparison after tested is found, suitable with AR glass alkaline resistance properties, while has good processability, heat surely
It is qualitative, it can be applicable to that GRC etc. is a variety of to be required in corrosion-resistant composite material.（3）Raw material in this patent other than red mud are work
Industry grade batch enables the invention to preferably be applied in actual industrial production.
Description of the drawings
The XRD spectrum of Fig. 1 sample examples 1-5.
SEM schemes after 4 caustic corrosion of Fig. 2 samples example.
4 fiber SEM of Fig. 3 samples example schemes.
The present invention is described in further detail in the following with reference to the drawings and specific embodiments.
Specific embodiment
For a better understanding of the present invention, below by the alkaline-resisting of specific embodiment the present invention is further explained embodiment
Glass fibre.First, to glass the reasons why regulation content in the effect of each constituent and above range.But present disclosure
It is not limited only to embodiment, embodiment is not construed as the restriction to the scope of this patent, and in compositing range, " % " refers to quality " % ",
The numberical range that " ~ " represents, it is lower limiting value, upper limit value to refer to comprising " ~ " front and rear numerical value recorded.
In the present invention, considered critical is not carried out for red mud component and type.Embodiment uses the Bayer of Shandong Aluminum Plant
Method red mud by largely analyzing detection, largely meets weight percentage SiO2+Al2O3+ CaO+MgO+ ferriferous oxides >=
82%, after carrying out a series of pretreatment to it, appropriate admixture adjustment glass proportioning is added, it is excellent to prepare alkaline resistance properties
Glass fibre.
Red mud is dried under 100 DEG C ~ 250 DEG C air atmospheres to grinding after removing moisture removal to be sieved（Granularity is less than 250um）, will
Red mud keeps the temperature 2 ~ 5 hours after carrying out mixing homogenizing under 500 DEG C ~ 700 DEG C air atmospheres.
Red mud and other raw material components fluorescence analysis tables are shown in Table 1 after processing.
SiO2It is network skeleton in silicate glass, forms the basis of glass.SiO2As Network former oxide,
With [SiO in glass network4] face body structural unit form glass network, can increase viscosity of glass metal and reduce tendency towards devitrification,
Improve the performances such as water-fast, the alkaline and thermal stability of glass.But adding too much, can make that glass melting point is higher, and viscosity is too big, clear
Clearly, homogenizing is difficult, and heat consumption is caused to increase.SiO in this patent2Content is in 57 ~ 64%, preferably 59 ~ 62%, through overtesting glass
Processability and chemical stability etc. all meet the production and application of product.If SiO2Content is less than 50%, forms glass
The oxide of body is reduced, and water-fast, alkaline to glass can be had an adverse effect；Content is more than 65%, can increase viscosity of glass metal
Add, be unfavorable for glass fibre production.
Al2O3It, under given conditions, can [AlO for the network intermediate oxide of glass4] structural unit into networking
Network structure increases the viscosity of glass metal, reduces crystallization ability, and the certain promotion of the thermal stability and chemical stability to glass is made
With being best glass stabilizer.Al2O3SiO is greater than to glass viscosity effect2, content, which crosses conference, reduces glass melting speed
Degree extends clarification, homogenising time.Al in the present invention2O3For content 8 ~ 12%, processability and chemical stability of glass etc. are good
It is good, all meet the production and application of product.
Fe in ferriferous oxide2O3For the network intermediate oxide of glass, partly play the role of connecting glass network,
Make glass network finer and close, although too high levels can influence the heat penetration and tendency towards devitrification of glass, it is unfavorable that fiber is produced, one
Quantitative addition improves glass structure extent of polymerization to a certain extent.Ferriferous oxide content is 9 ~ 13% in the present invention, preferably
9 ~ 12%, while devitrification of glass and glass forming ability is controlled, improve the chemical stability and thermal stability of glass.
TiO2As network intermediate oxide, in the presence of body is formed, network structure is improved, a certain amount of addition can
To reduce the coefficient of expansion and forming temperature, chemical stability is improved, excessive addition can promote crystallization, reduce glass forming ability.
TiO in this patent2Content meets the production and application of product 1 ~ 3%.
Alkaline earth oxide（CaO、MgO）It is network modifying oxide, suitable addition can reduce glass high temperature and glue
Degree is beneficial to fusing and molding, increases the performances such as water-fast, the alkaline and thermal stability of glass.If too high levels, glass can be reduced
The mechanical strength and chemical stabilization of glass, and content is too low that glass smelting can be made difficult.Alkali-metal-oxide content in the present invention
6 ~ 15%, it is made to meet the production requirement of glass fibre.
Alkali metal oxide（Na2O、K2O、Li2O）Mainly as network outer body, free oxygen is provided, rises and destroys network structure
Effect, this make its be conducive to reduce glass viscosity, help to clarify, be homogenized and be molded, become glass fibre production cosolvent,
But content excessively can be unfavorable to structure, reduces the performances such as the water-fast of glass, alkali and thermal stability.Alkali metal oxide in this patent
Content 3 ~ 7% meets the production and application of alkali-resistant glass fibre.
Due to the more difficult clarification of alkali-proof glass, homogenizing, suitable tin-oxide is introduced in this patent, can ensure glass metal matter
Amount simultaneously, improves original glass forming ability.SnO2Belong to network intermediate oxide（SnO can be converted into high temperature air
The SnO of stable structure2）, 1630 DEG C of fusing point, 1800 DEG C of boiling point is volatile.Sn is High field side injection, has stronger network
Aggtegation, a certain amount of addition can improve the materializations such as chemical stability and optical property with reinforcing glass network polymerization degree
Energy；SnO is the oxide that appraises at the current rate simultaneously, and free electron can be provided during appraising at the current rate, ferriferous oxide is had an impact.In the present invention
SnO dosages are mainly the high temperature viscosity and alkaline resistance properties for improving glass in 0.5 ~ 4%, preferably 0.5 ~ 2.5%, full simultaneously
Foot prepares the working condition and application demand of alkali-resistant glass fibre.
CaF2Belonging to cosolvent, appropriate addition can reduce glass solution surface tension and viscosity, glass metal is contributed to clarify,
Homogenizing increases heat penetration.CaF in the present invention2Dosage is mainly the high temperature viscosity for improving glass 0 ~ 1%, and satisfaction prepares resistance to
The working condition of alkali containing glass fibre.
In addition, due to the solid waste of raw material red mud complicated component, MnO, P can be introduced into glass2O5Impurity are waited, are contained
For amount 0 ~ 1%, content is relatively low, is found by experiment test, smaller to glass fibre qualitative effects.
By the Bayer process red mud of pretreatment and stannous oxide powder, lime stone, dolomite, silica flour, magnesia, industrial oxygen
Change aluminium, fluorite by corresponding proportion mixing, uniformly after, be put into refractory container 1400 ~ 1500 DEG C be melted heat preservation 3 ~ 6h obtain
Change clear glass metal, then higher than forming temperature（It is 10 that forming temperature, which takes viscosity of glass metal,3Corresponding temperature during dPa.s
Degree）Continuous fiber is drawn into using casing or bushing at 20 ~ 35 DEG C or so, then cooling obtains alkali-resistant glass fibre（Precursor）,
Average fibre diameter is less than 30 microns.
1 ~ 5 raw material of embodiment composition is shown in Table 2.
1 ~ 5 sample of embodiment composition is shown in Table 3.
1 ~ 5 sample performance of embodiment is shown in Table 4.
Each sample is prepared as follows in table.
First, to become in table 3 in a manner of glass composition, by the red mud of pretreatment, batch mixing is equal in proportion with other batches
It is even, preparing glass charge is made.3 ~ 6h of heat preservation is melted at 1400 ~ 1500 DEG C to obtain being homogenized clear glass metal, pours into graphite jig
The both bulk glasses sample containing a small amount of bubble is obtained, then keeping the temperature 2 ~ 4 hours at 600 ~ 700 DEG C anneals, and eliminating heat should
Power.
In this patent, the fibre-forming performance of experiment test fiber is drawn by laboratory monofilament.It will homogenizing, clear melting glass
Glass is supplied in casing, and fiber is pulled straight from the nozzle of its bottom surface.And pass through the monofilament that scanning electron microscopic observation is drawn
Surface topography.Monofilament pattern such as Fig. 3.
Glass test block is subjected to density measurement, glass density uses Archimedes's drainage, medium is done using deionized water
It measures, measures 3 times and be averaged.
Glass test block is subjected to crushing grinding, obtains grain size less than 75um glass powders and 180 ~ 250um particles.To each examination
Sample carries out XRD, SEM, water-fast, alkali resistance, differential thermal, forming temperature and liquidus temperature test analysis.
XRD material phase analysis measures as follows.Grain size is less than 75um glass powders sample and carries out material phase analysis, radiographic source is copper
Target, the condition of scanning：10 ° ~ 80 ° of scanning angle, 0.02 ° of step-length.Test result shows that all samples do not occur crystallization peak,
Only " steamed bun peak ", it is in glassy state to illustrate sample.
SEM tests are following to be measured.Sample is sprayed after a layer thickness is about 10nm gold, is put under scanning electron microscope and is seen
It examines.To being found after glass sample surface topography after alkali corrosion resistance and the test of glass fiber single filament surface topography：Sample table after corrosion
Face occurs generating compared with multiple cracks, illustrates that watch crystal structure is destroyed by after alkali liquid corrosion（Pattern such as Fig. 2 after caustic corrosion）；Glass
Glass fibre single thread surfacing, no significant defect, diameter are less than 30um（Monofilament pattern such as Fig. 3）.
Alkali resistance measures as follows.By particle sample（Diameter phi=180 ~ 250um）1.00g is put into centrifuge tube, injects mixed base
Solution（The Na of the NaOH and 0.5mol/L of concentration 1mol/L2CO3Solution 1:1 volume mixture）Sample is submerged, etch 25h at 80 DEG C
It is dried 24 hours using being put into 100 DEG C of baking ovens after pure water eccentric cleaning afterwards, measures and compare mass loss.
Water resistance measures as follows.By particle sample（Diameter phi=180 ~ 250um）1.00g is put into centrifuge tube, injection pure water leaching
No sample, dried 24 hours after etch heat preservation 25h using being put into 100 DEG C of baking ovens after pure water eccentric cleaning at 80 DEG C, measure and compare
Compared with mass loss.
Differential thermal analysis measures as follows.Glass powder is put into alumina crucible first, by being carried out to alumina crucible
Heating detects the Process of absorption or liberation of heat variation in sample temperature-rise period on DTA differential thermal analysis collection of illustrative plates, glass is obtained by energy absorption difference
Glass transition temperature (Tg), crystallization initial temperature（Tx）, the thermal stability of glass is further analyzed, reacts the change of glass structure
Change.
Thermal stability parameter △ T1=Tx-Tg numerical value is bigger, and thermal stability is stronger.
Forming temperature measures as follows.Test block glass breaking to suitable size is put into alumina crucible, it is bent according to DTA
Line instructs, and heated oxide aluminium crucible makes sample become molten condition to 1450 DEG C, and the molding of multiple samples is measured using rotary process
Temperature（Viscosity is 103Temperature during dPa.s）.
Liquidus temperature measures as follows.Powder sample is taken, is filled into platinum boat, reaches suitable bulk density state.It will
Platinum boat puts into advance heating, and maximum temperature is in 1250 DEG C of thermal gradient furnace, and air atmosphere keeps the temperature 2 ~ 4 hours.Take out sample
After being cooled to room temperature in air, liquidus temperature is determined by petrographic microscope.
Forming temperature is calculated with liquidus temperature difference according to the two value.
As shown in Table 4, each sample forming temperature in embodiment is less than 1280 DEG C, and forming temperature and liquidus temperature difference are big
In 80 DEG C.
Water-fast etch mass loss rate is less than 0.45%, and optimal water-fast sample mass loss is 0.31%；Alkaline-resisting etch matter
Amount loss rate is less than 1.5%, and optimal alkaline-resisting sample mass loss is 1.07%, and alkali resistance is suitable with AR alkali-resistant glass fibres.
Above-mentioned performance parameter and its assay method are known to the art technology talent.
Industrial applicibility：This patent is illustrated through the above, this patent can be proved using red mud as material system
Standby tin dope alkali-resistant glass fibre has feasibility, and can be achieved on by existing production technology, of the invention is alkaline-resisting
Glass fibre has preferable practicability in GRC composite materials, battery separator, exterior-wall heat insulation etc. require resistant material.
Claims (10)
1. one kind is using solid waste red mud as raw material, the alkali-resistant glass fibre of doped tin oxide, it is characterized in that, as glass group
Into being converted into oxide mass percentage, consist of the following compositions：SiO257 ~ 64%, SnO+SnO20.5 ~ 4%, Al2O3 8~
12%, FeO+Fe2O3 9 ~ 13%, Na2O+K2O 3 ~ 7%, CaO 5 ~ 10%, MgO 1 ~ 5%, TiO21 ~ 3%, CaF20 ~ 1%, other 0
~1%；
Also, ratio C 1=(SnO+SnO2）/ SiO2It is 0.008 ~ 0.070.
2. alkali-resistant glass fibre as described in claim 1, it is characterized in that, Fe2O3Mass percent is 10.2% recrystallization temperature
930 DEG C are rapidly reduced to from 960 DEG C, corresponding forming temperature is rapidly increased to 1279 DEG C from 1240 DEG C；Limit Fe2O3/ SiO2Matter
It is 0.15 ~ 0.20 to measure percentage C2, controls devitrification of glass rate.
3. alkali-resistant glass fibre as claimed in claim 2, it is characterized in that：The glass high temperature viscosity is 103Institute is right during dPa.s
The temperature answered is less than 1280 DEG C, is more than 80 DEG C with crystallization ceiling temperature difference.
4. alkali-resistant glass fibre as claimed in claim 2, it is characterized in that：Sample is in the aqueous slkali of PH=11 ~ 13.5, at 80 DEG C
Etch 25h, alkaline-resisting etch mass loss rate are less than 1.5%.
5. alkali-resistant glass fibre as claimed in claim 2, it is characterized in that：Sample is in pure water solution, etch 25h at 80 DEG C,
Water-fast etch mass loss rate is less than 0.45%.
6. alkali-resistant glass fibre as claimed in claim 1 or 2, it is characterized in that：Described other are unavoidably to be drawn by raw material
The oxide entered, including MnO, SrO, Li2O, CuO and sulfide, it is 0 ~ 1% to add up to mass percentage, in content " 0 "
Represent infinite tendency 0 but be 0.
7. alkali-resistant glass fibre as claimed in claim 1 or 2, it is characterized in that：The tin-oxide includes SnO and Sn2O two
Kind oxide, Sn4+/Sn2+≥18.5；The ferriferous oxide includes FeO and Fe2O3Two oxides, Fe3+/Fe2+≥11.2。
8. the preparation method of alkali-resistant glass fibre as claimed in claim 1 or 2, includes the following steps：
（1）The pretreatment of red mud：Red mud is dried under 100 DEG C ~ 250 DEG C air atmospheres to grinding after removing moisture removal to be sieved（Granularity
Less than 250um）, red mud is carried out after mixing homogenizing to keep the temperature 2 ~ 5 hours under 500 DEG C ~ 700 DEG C air atmospheres；
（2）By step（1）The red mud of middle pretreatment and stannous oxide powder, dolomite, lime stone, silica flour, commercial alumina,
After magnesia, fluorite are by corresponding proportion mixing homogenizing, it is put into refractory container and is obtained in 1400 DEG C ~ 1500 DEG C 3 ~ 6h of melted heat preservation
Clear glass metal is homogenized, then higher than forming temperature（It is 10 that general forming temperature, which takes glass viscosity,3It is corresponding during dPa.s
Temperature）Continuous fiber is drawn into using bushing or casing at 20 ~ 35 DEG C or so, cooling obtains alkali-resistant glass fibre（Precursor）,
Average fibre diameter is less than 30 microns.
9. the preparation method of alkali-resistant glass fibre as claimed in claim 8, it is characterized in that, step（2）Middle raw materials are pressed
Mass percent includes：27 ~ 40 % of red mud after pretreatment, stannous oxide 0.5 ~ 4%, 7 ~ 18 % of dolomite, lime stone 0 ~ 3%, stone
English powder 46 ~ 59%, commercial alumina 3 ~ 5%, magnesia 0 ~ 1%, fluorite 0 ~ 1%.
10. the preparation method of alkali-resistant glass fibre as claimed in claim 9, it is characterized in that, red mud contains after the pretreatment
The component of following mass percent：SiO23 ~ 23%, Al2O35 ~ 22%, FeO+Fe2O36 ~ 35%, Na2O+K2O 2 ~ 13%, CaO+
MgO 5 ~ 30%, TiO21 ~ 9%, other 0 ~ 1%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942200A (en) * | 2019-04-24 | 2019-06-28 | 济南大学 | A kind of preparation method of changed red mud alkali-resistant glass fibre |
| CN109956672A (en) * | 2019-04-24 | 2019-07-02 | 济南大学 | A kind of preparation method for the trade waste alkali-resistant glass fibre that intermediate oxide is modified |
| CN109970349A (en) * | 2019-04-24 | 2019-07-05 | 济南大学 | A kind of method that the trade waste that ferriferous oxide is modified prepares alkali-resistant glass fibre |
| CN110028250A (en) * | 2019-06-05 | 2019-07-19 | 济南大学 | A method of aluminosilicate alkali-resistant glass fibre is prepared using red mud |
| CN111302641A (en) * | 2020-02-28 | 2020-06-19 | 泉州市派腾新材料科技有限公司 | Preparation method of alkali-corrosion-resistant glass fiber material |
| CN113072304A (en) * | 2021-04-25 | 2021-07-06 | 泰安顺茂新材料技术有限公司 | Alkali-resistant fiber glass composition and preparation method thereof |
| CN114956542A (en) * | 2022-01-23 | 2022-08-30 | 烟台华正科信新材科技有限公司 | Basalt scale |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942200A (en) * | 2019-04-24 | 2019-06-28 | 济南大学 | A kind of preparation method of changed red mud alkali-resistant glass fibre |
| CN109956672A (en) * | 2019-04-24 | 2019-07-02 | 济南大学 | A kind of preparation method for the trade waste alkali-resistant glass fibre that intermediate oxide is modified |
| CN109970349A (en) * | 2019-04-24 | 2019-07-05 | 济南大学 | A kind of method that the trade waste that ferriferous oxide is modified prepares alkali-resistant glass fibre |
| CN110028250A (en) * | 2019-06-05 | 2019-07-19 | 济南大学 | A method of aluminosilicate alkali-resistant glass fibre is prepared using red mud |
| CN111302641A (en) * | 2020-02-28 | 2020-06-19 | 泉州市派腾新材料科技有限公司 | Preparation method of alkali-corrosion-resistant glass fiber material |
| CN113072304A (en) * | 2021-04-25 | 2021-07-06 | 泰安顺茂新材料技术有限公司 | Alkali-resistant fiber glass composition and preparation method thereof |
| CN114956542A (en) * | 2022-01-23 | 2022-08-30 | 烟台华正科信新材科技有限公司 | Basalt scale |
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