CN110078482A - A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre - Google Patents
A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre Download PDFInfo
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- CN110078482A CN110078482A CN201910425157.1A CN201910425157A CN110078482A CN 110078482 A CN110078482 A CN 110078482A CN 201910425157 A CN201910425157 A CN 201910425157A CN 110078482 A CN110078482 A CN 110078482A
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Abstract
The present invention provides a kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, steps are as follows: aluminium powder, aluminium salt, water being mixed, is heated to reflux to aluminium powder to react completely in 110~200 DEG C and obtains Aluminum sol；Aluminum sol obtained by the above method, silica solution, nanoparticulate dispersion and spin finish aid mixing are taken, the nanoparticulate dispersion is α-Al2O3Dispersion liquid, γ-Al2O3Dispersion liquid or α-Fe2O3The combination of one or more of dispersion liquid through aging concentration, spinning, is calcined to obtain the final product.The present invention reduces α-Al in ceramic fibre by adding nano particle2O3It is poor with the formation temperature of mullite crystalline phase, the ceramic of compact fiber of fibre length length, excellent in mechanical performance, high-purity can be made at a lower temperature.
Description
Technical field
The present invention relates to a kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, belongs to inorganic non-metallic material
Technical field.
Background technique
Alumina fibre is a kind of new ceramic material, and main component is aluminium oxide, and performance in an oxidizing environment is bright
It is aobvious to be better than metallic fiber, carbon fiber and non-oxidized substance fiber.Simultaneous oxidation Al-base ceramic continuous fiber has ultra-fine or even nanometer
The microstructure of grade, due to making it have good intensity and flexibility with this nanoscale microstructures, mechanical, metallurgy,
The industries such as chemical industry, petroleum, ceramics, glass, electronics are used widely.Ceramic alumina fiber has intensity height, hardness high, resistance to
It corrodes, anti abrasive advantage, but the ceramic fibre of high alumina content at high temperature easily grow up by crystal grain, leads to fiber dusting,
It is limited to apply in a high temperauture environment.For the performance for improving ceramic alumina fiber, second can be added in ceramic fibre
Phase (such as mullite phase), so as to improve the bending strength of ceramic fibre, wear resistance and fatigue resistance, while reducing fiber
Density, and the heat transfer of mullite crystalline phase and thermal expansion coefficient are low, creep resistant and thermal shock resistance are excellent, electrical insulating property and high temperature are strong
Spend it is excellent (referring to inorganic chemicals industry, 2013,45 (5): 21), thus Al2O3Mullite Multiphase ceramic fibre compensates for single crystalline substance
The deficiency of phase alumina ceramic fibre, practicability is stronger, and application range is wider.
The complex phase mullite-alumina of U.S. 3M (Minnesota Mining and Manufacturing) company invention
Ceramic fibre (referring to document: Composite Structures, 2018,204:578), crystalline phase be the rich aluminium of 53wt% not
Carry out stone (2Al2O3·SiO2) and 47wt% α-Al2O3, but Al cannot be reduced well without additive is introduced in preparation process2O3
The formation temperature of crystal phase, Al2O3The difference of crystal phase and mullite crystalline phase formation temperature makes mullite grains at relatively high temperatures
Growth, to influence consistency and mechanical property of gained complex phase ceramic fiber etc..Tension etc. will be by that will contain aluminium, element silicon
Mullite precursor fiber containing nitridation is calcined in ammonia atmosphere, be made nitrogenous Mullite Ceramic Fibres (referring to:
CN107473749A), by introducing nitrogen in mullite fiber, a variety of crystal phases are constructed, to obtain complex phase ceramic fiber.But this
Method uses ammonia during the sintering process, and risk is big and easily causes environmental pollution, and prepare with scale is difficult.
For α-Al2O3/ mullite Multiphase ceramic fibre, due to forming mullite and α-Al2O3Crystal phase required temperature is obvious
Difference, α-Al2O3(1400 DEG C) of formation temperature of crystal phase are higher than the formation temperature (1300 DEG C) of mullite crystalline phase, and using not
Same precursor sol forms α-Al2O3It is different with the temperature difference of two kinds of crystal phases of mullite, and the presence of temperature difference can make not come
Stone grain growth influences consistency, mechanical property (including the mechanical property under high temperature) of fibrous material etc..It to be formed to reduce
Al2O3The temperature difference of crystal phase and mullite crystalline phase improves the performances such as consistency and the mechanics of fiber, proposes the present invention.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provides a kind of α-Al2O3The preparation of/mullite Multiphase ceramic fibre
Method.The present invention is by dispersion liquid of the addition containing nano particle into spinnability silicon/Aluminum sol system to reduce α-Al2O3It is brilliant
The formation temperature of phase, to reduce α-Al in complex phase ceramic fiber2O3It is poor with the formation temperature of mullite crystalline phase, it can be lower
At a temperature of be made fine and close, fibre length is longer, excellent in mechanical performance, high-purity α-Al2O3/ mullite Multiphase ceramic fibre.This
Invention dispersion liquid additive amount is less, and operating procedure is simply controllable, easily prepared, at low cost, it is easy to accomplish industrialization.
Technical scheme is as follows:
A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, comprising steps of
(1) aluminium powder, aluminium salt, water are uniformly mixed, mixed liquor is made；2~20h is heated to reflux to aluminium powder in 110~200 DEG C
Reaction completely, is obtained by filtration Aluminum sol；
(2) Aluminum sol made from step (1) method, silica solution, nanoparticulate dispersion and spin finish aid are uniformly mixed,
It is concentrated through aging and spinnability silicon/Aluminum sol is made；Then α-Al is obtained through spinning, calcining2O3/ mullite Multiphase ceramic fibre；Institute
Stating nanoparticulate dispersion is α-Al2O3Dispersion liquid, γ-Al2O3Dispersion liquid or α-Fe2O3One or more of dispersion liquid
Combination.
Preferred according to the present invention, in step (1), the aluminium salt is aluminium chloride, aluminum nitrate or aluminum sulfate.
Preferred according to the present invention, in step (1) mixed liquor, the molar concentration of the aluminium salt is 0.3~2mol/L.
Preferred according to the present invention, in step (1), the molar ratio of the aluminium salt and aluminium powder is 1:(1~6).
It is preferred according to the present invention, in step (1), 2~14h is heated to reflux in 150~180 DEG C and is reacted completely to aluminium powder.
Preferred according to the present invention, Aluminum sol described in step (1) is to contain Al13Micelle ([AlO4Al12(OH)24
(H2O)12]7+) alumina sol, particle size analysis≤10nm.
According to the present invention, in step (2), silica solution, α-Al2O3Dispersion liquid, γ-Al2O3Dispersion liquid, α-Fe2O3Dispersion liquid
Commercially available acquisition, nano particle size is 5-100nm in dispersion liquid.
Preferred according to the present invention, in step (2), the mass concentration of silica is 10-45%, α-in the silica solution
Al2O3α-Al in dispersion liquid2O3Mass concentration be 20-40%, γ-Al2O3γ-Al in dispersion liquid2O3Mass concentration be 20-
40%, α-Fe2O3α-Fe in dispersion liquid2O3Mass concentration be 10-40%.
Preferred according to the present invention, in step (2), the spin finish aid is polyvinyl alcohol, polyvinylpyrrolidone or poly-
The combination of one or more of ethylene oxide.
Preferred according to the present invention, in step (2), the mass ratio of Aluminum sol and silica solution is (10~15): 1.
Preferred according to the present invention, in step (2), the quality of nanoparticulate dispersion is Aluminum sol and silica solution gross mass
0.1~5%；Preferably, the quality of nanoparticulate dispersion is the 1~3% of Aluminum sol and silica solution gross mass.
It is preferred according to the present invention, in step (2), the quality of spin finish aid be Aluminum sol and silica solution gross mass 2~
15%.
Preferred according to the present invention, in step (2), the aging concentration is in the vacuum item of 30~40 DEG C, 0.095MPa
4~22h is concentrated under part.
Preferred according to the present invention, in step (2), the solid content of the spinnability silicon/Aluminum sol is 5~45wt%, 25
DEG C when viscosity be 5~1000Pa.s.
Preferred according to the present invention, in step (2), following any method is can be used in the spinning process:
I) gelatinous fibre is prepared using dry spinning；Spinning temperature is 30~40 DEG C, and relative humidity is 10~40%, receives silk
Rate is 80~110m/min；
Ii centrifugal drying silk) is carried out with 7000~10000 revs/min of revolving speed and prepares gelatinous fibre；Preferably, revolving speed 8000
~10000 revs/min；
Iii machine) is blown for 30~40 DEG C of the penetrating of spinnability colloidal sol of sky by fiber with the high pressure gas of 0.3~0.5MPa
Compression ring prepares gelatinous fibre in border；Preferably, the pressure of high pressure gas is 0.3~0.4MPa.
It is preferred according to the present invention, in step (2), the calcination condition are as follows: be warming up to the rate of 0.5~3 DEG C/min
150~280 DEG C, in 0.5~2h of this temperature, 450~600 DEG C then are warming up to the rate of 1~3 DEG C/min, it is warm herein
Degree 2~4h of heat preservation, then 900~1400 DEG C are warming up to the rate of 3~10 DEG C/min, in 0.5~2h of this temperature, then certainly
So cooling；In above-mentioned calcination process, nitrogen is passed through with the gas flow of 0.1~10L/min always.
Preferably, the calcination condition are as follows: be warming up to 150~280 DEG C with the rate of 0.5~2 DEG C/min, protected in this temperature
1~2h of temperature, is then warming up to 450~600 DEG C with the rate of 1~3 DEG C/min, in 2~3h of this temperature, then with 5~10 DEG C/
The rate of min is warming up to 900~1400 DEG C, in 0.5~1h of this temperature, then Temperature fall；In above-mentioned calcination process, one
Nitrogen is directly passed through with the gas flow of 0.1~5L/min.
The principle of the invention:
Sintering temperature can be reduced by introducing nano particle and sintering aid in the feed, refine crystal grain, and slow down crystal grain
Misgrowth, so that the ceramics of densification be made.The introducing of nano particle increases nucleation centre, and aluminium oxide nucleus can be made to add
Speed is formed, to reduce the nucleation barrier of aluminium oxide, it is easier to form target crystal phase, make α-Al2O3The formation temperature of crystal phase drops
It is low, reduce α-Al2O3It is poor with the formation temperature of two crystal phase of mullite, exist to slow down the mullite crystalline phase particle crystallized
Growing up under high temperature, while the formation of porous structure is also inhibited, keep gelatinous fibre easy to form uniform in later period sintering
Microstructure, mullite and α-Al2O3Two crystal phases are evenly distributed in ceramic fibre, to make mullite and α-Al2O3Crystal grain
Growth is mutually inhibited, and gained ceramic fibre is finer and close.
In addition to this, during the leading portion of sintering, in gelatinous fibre the volatilization of component (including water and organic matter) and point
Solution will cause the breakage of fibre structure, thus the nitrogen for being passed through appropriate throughput when sintering can effectively avoid as protective atmosphere
Because of fibre beakage caused by component volatilization, and the preferably specific calcination condition of the present invention, it is conducive to be made fine and close, mechanical property is excellent
Different, high-purity α-Al2O3/ mullite Multiphase ceramic fibre.
The utility model has the advantages that
1. nano particle additive amount is less in the method for the present invention, operating procedure is simply controllable, easily prepared, at low cost, easily
It is industrialized in realizing.
2. the fine and close α-Al haveing excellent performance can be made in the method for the present invention at a lower temperature2O3/ mullite Multiphase ceramics are fine
Dimension.The crystal phase group of obtained complex phase ceramic fiber becomes mullite and α-Al2O3, crystal grain is tiny, fiber high densification, microcosmic
Even tissue.Gained ceramic fibre is longer, up to 820m；Density is lower, is conducive to subsequent braiding；Excellent in mechanical performance (draw by highest
Intensity is stretched up to 2.5GPa), and 1200 DEG C of tensile strength can the temperature remains within the normal range the 70% of tensile strength, mechanical behavior under high temperature is excellent
It is different；And have many advantages, such as high surface activity, and it is easily compound with the matrix of metal or Types of Pottery, it can be used as Metal Substrate or ceramic base etc.
The reinforcement of composite material.
Detailed description of the invention:
Fig. 1 is 1 gained α-Al of the embodiment of the present invention2O3The XRD of/mullite Multiphase ceramic fibre；
Fig. 2 is 1 gained α-Al of the embodiment of the present invention2O3The SEM of/mullite Multiphase ceramic fibre；
Fig. 3 is 1 gained α-Al of the embodiment of the present invention2O3The high power SEM of/mullite Multiphase ceramic fibre；
Fig. 4 is 1 gained α-Al of the embodiment of the present invention2O3The TEM of/mullite Multiphase ceramic fibre；
Fig. 5 is 1 gained α-Al of the embodiment of the present invention2O3The photo of/mullite Multiphase ceramic fibre.
Specific embodiment:
The present invention is described further combined with specific embodiments below, but the scope of the present invention is without being limited thereto.Simultaneously
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as without special theory
It is bright, commercially obtain.
Embodiment 1
A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, comprising steps of
(1) 16 hydrazine aluminum sulfate of 645g and 9.0g aluminium powder stir evenly after 1000mL deionized water is added, 150 DEG C of heating
Reflux 10h reacts completely to aluminium powder, obtains after cold filtration containing Al13The alumina sol of micelle, particle size analysis 3nm, i.e. aluminium
Colloidal sol.
(2) Aluminum sol and 10.0g silica solution (dioxide-containing silica 30wt%) for taking 115.67g step (1) to obtain exist
35 DEG C are uniformly mixed, and 2.0g α-Al is added2O3Dispersion liquid (α-Al2O3Content is 20wt%) and 10.0g polyethylene pyrrole network alkanone,
It is uniformly mixed, it is 35wt% that then aging, which is concentrated into solid content, under 38 DEG C, the vacuum condition of 0.095MPa, and viscosity is at 25 DEG C
Spinnability silicon/Aluminum sol is made in 1000Pa.s.
(3) dry spinning is used using above-mentioned spinnability silicon/Aluminum sol, environment temperature is 30 DEG C, relative humidity is
The gelatinous fibre of about 16 μm of diameter is made under conditions of 30%, gelatinous fibre is wrapped in by receipts silk with the receipts silk rate of 80m/min
On roller.
(4) above-mentioned gained gelatinous fibre is calcined, technical process are as follows: be warming up to 200 with the speed of 1.0 DEG C/min
DEG C, in this temperature 1h, 600 DEG C then are warming up to the speed of 1.0 DEG C/min, keeps the temperature 2h, then with the speed of 10 DEG C/min
1350 DEG C are warming up to, in this temperature 0.5h, then Temperature fall；In above-mentioned calcination process, always with the stream of 0.1L/min
Amount is passed through nitrogen.
α-Al obtained by the present embodiment2O3The XRD of/mullite Multiphase ceramic fibre is as shown in Figure 1, as shown in Figure 1, gained is made pottery
The crystal phase of porcelain fiber is mullite and α-Al2O3Crystal phase, without other crystal phases, purity is high, grain size 20-40nm.
α-Al obtained by the present embodiment2O3The SEM of/mullite Multiphase ceramic fibre is as shown in Fig. 2, as shown in Figure 2, gained is made pottery
The fibre diameter of porcelain fiber is 8.9 μm, and fiber is uniform.
α-Al obtained by the present embodiment2O3The high power SEM of/mullite Multiphase ceramic fibre is as shown in figure 3, obtained by as shown in Figure 3
Fiber is obviously made of two kinds of different crystal grain, and seamless between crystal grain.
α-Al obtained by the present embodiment2O3The TEM of mullite Multiphase ceramic fibre is as shown in figure 4, can have found mullite by Fig. 4
Crystal grain and the mutually embedding growth of alumina grain.
α-Al obtained by the present embodiment2O3The photo of Mullite Ceramic Fibres is as shown in figure 5, fiber continuity is good.
The crystalline phase of ceramic fibre obtained by the present embodiment is the rich aluminum-containing mullite (2Al of 58wt%2O3·SiO2) and 42wt%
α-Al2O3；Tensile strength is up to 2.5GPa, and it is 1.8GPa that average tensile, which stretches intensity, modulus 362GPa, at 1200 DEG C
It can keep 70% tensile strength, fibre length 820m.
Embodiment 2
A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, comprising steps of
(1) Aluminum sol prepare it is as described in Example 1.
(2) Aluminum sol and 5.0g silica solution (dioxide-containing silica 30wt%) for taking 115.67g step (1) to obtain are 35
DEG C be uniformly mixed, be added 3.5g γ-Al2O3Dispersion liquid (γ-Al2O3Content is 20wt%) and 3.0g polyethylene glycol oxide, mixing is
Even, it is 38wt% that then aging, which is concentrated into solid content, under 38 DEG C, the vacuum condition of 0.095MPa, and viscosity is at 25 DEG C
Spinnability silicon/Aluminum sol is made in 830Pa.s.
(3) dry spinning is used using above-mentioned spinnability silicon/Aluminum sol, environment temperature is 30 DEG C, relative humidity is
The gelatinous fibre of about 17 μm of diameter is made under conditions of 30%, gelatinous fibre is wrapped in by receipts silk with the receipts silk rate of 80m/min
On roller.
(4) above-mentioned gained gelatinous fibre is calcined, technical process are as follows: be warming up to 200 with the speed of 1.0 DEG C/min
DEG C, in this temperature 1h, be then warming up to 600 DEG C with the speed of 1.0 DEG C/min, in this temperature 2h, then with 10 DEG C/
The speed of min is warming up to 1350 DEG C, in this temperature 0.5h, then Temperature fall；In above-mentioned calcination process, always with 5L/
The flow of min is passed through nitrogen.
The crystal phase of ceramic fibre made from the present embodiment is mullite and α-Al2O3, fibre diameter is 9.7 μm, and stretch-proof is strong
Degree is up to 2.01GPa, and it is 1.67GPa that average tensile, which stretches intensity,.
Embodiment 3
A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, comprising steps of
(1) 80.5g aluminium chloride and 9.0g aluminium powder stir evenly after 1000mL deionized water is added, and 180 DEG C are heated to reflux 14h
It reacts to aluminium powder, obtains after cooling, filtering containing Al completely13The alumina sol of micelle, particle size analysis 8nm, i.e. Aluminum sol.
(2) Aluminum sol and 10.0g silica solution (dioxide-containing silica 30wt%) for taking 142.7g step (1) to obtain are 35
DEG C be uniformly mixed, be added 3.0g α-Fe2O3Dispersion liquid (α-Fe2O3Content is 20wt%) and 5.0g polyethylene pyrrole network alkanone, mixing
Uniformly, it is 30wt% that then aging, which is concentrated into solid content, under 38 DEG C, the vacuum condition of 0.095MPa, and viscosity is at 25 DEG C
Spinnability silicon/Aluminum sol is made in 580Pa.s.
(3) dry spinning is used using above-mentioned spinnability silicon/Aluminum sol, environment temperature is 35 DEG C, relative humidity is
The gelatinous fibre of about 16 μm of diameter is made under conditions of 20%, gelatinous fibre is wrapped in by receipts silk with the receipts silk rate of 110m/min
On roller.
(4) calcine technology is the same as embodiment 1.
The crystal phase of ceramic fibre made from the present embodiment is mullite and α-Al2O3, fibre diameter is 8.9 μm, and stretch-proof is strong
Degree is up to 1.8GPa, and it is 1.7GPa that average tensile, which stretches intensity,.
Embodiment 4
A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, comprising steps of
(1) preparation of Aluminum sol is the same as embodiment 3.
(2) Aluminum sol and 10.0g silica solution (dioxide-containing silica 30wt%) for taking 142.7g step (1) to obtain are 35
DEG C be uniformly mixed, be added 3.0g α-Al2O3Dispersion liquid (α-Al2O3Content is 20wt%) and 20.0g polyvinylpyrrolidone, it mixes
It closes uniformly, it is 29wt% that then aging, which is concentrated into solid content, under 38 DEG C, the vacuum condition of 0.095MPa, and viscosity is at 25 DEG C
Spinnability silicon/Aluminum sol is made in 300Pa.s.
(3) dry spinning is used using above-mentioned spinnability silicon/Aluminum sol, environment temperature is 30 DEG C, relative humidity is
The gelatinous fibre of about 15 μm of diameter is made under conditions of 30%, gelatinous fibre is wrapped in by receipts silk with the receipts silk rate of 80m/min
On roller.
(4) above-mentioned gained gelatinous fibre is calcined, specific embodiment are as follows: be warming up to the speed of 1.0 DEG C/min
200 DEG C, in this temperature 1h, be then warming up to 600 DEG C with the speed of 2 DEG C/min, in this temperature 2h, then with 10 DEG C/
The speed of min is warming up to 1400 DEG C, in this temperature 0.5h, then Temperature fall；In above-mentioned calcination process, always with
The flow of 0.5L/min is passed through nitrogen.
The crystal phase of ceramic fibre made from the present embodiment is mullite and α-Al2O3, fibre diameter is 8.4 μm, and stretch-proof is strong
Degree is up to 1.92GPa, and it is 1.83GPa that average tensile, which stretches intensity,.
Embodiment 5
A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, comprising steps of
(1) preparation of Aluminum sol is the same as embodiment 3.
(2) Aluminum sol and 10.0g silica solution (dioxide-containing silica 30wt%) for taking 142.7g step (1) to obtain are 35
DEG C be uniformly mixed, be added 3.0g α-Al2O3Dispersion liquid (α-Al2O3Content is 20wt%) and 13.3g polyvinylpyrrolidone, it mixes
It closes uniformly, it is 30wt% that then aging, which is concentrated into solid content, under 38 DEG C, the vacuum condition of 0.095MPa, and viscosity is at 25 DEG C
Spinnability silicon/Aluminum sol is made in 220Pa.s.
(3) dry spinning is used using above-mentioned spinnability silicon/Aluminum sol, environment temperature is 30 DEG C, relative humidity is
The gelatinous fibre of about 16 μm of diameter is made under conditions of 10%, gelatinous fibre is wrapped in by receipts silk with the receipts silk rate of 110m/min
On roller.
(4) above-mentioned gained gelatinous fibre is calcined, specific embodiment are as follows: be warming up to the speed of 1.0 DEG C/min
200 DEG C, in this temperature 1h, 300 DEG C then are warming up to the speed of 1.0 DEG C/min, in this temperature 2h, then with 1.0
DEG C/speed of min is warming up to 600 DEG C, in this temperature 2h, 900 DEG C are warming up to the speed of 5 DEG C/min, is protected in this temperature
Warm 1h is warming up to 1350 DEG C with the speed of 10 DEG C/min, in this temperature 0.5h, then Temperature fall；Above-mentioned calcination process
In, nitrogen is passed through with the flow of 0.5L/min always.
The crystal phase of ceramic fibre made from the present embodiment is mullite and α-Al2O3, fibre diameter is 8.7 μm, and stretch-proof is strong
Degree is up to 1.83GPa, and it is 1.76GPa that average tensile, which stretches intensity,.
Embodiment 6
A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, comprising steps of
(1) 16 hydrazine aluminum sulfate of 645g and 9.0g aluminium powder stir evenly after 1000mL deionized water is added, 170 DEG C of heating
Reflux 8h reacts completely to aluminium powder, obtains after cooling, filtering containing Al13The alumina sol of micelle, particle size analysis 5nm, i.e. aluminium
Colloidal sol.
(2) Aluminum sol and 10.0g silica solution (dioxide-containing silica 30wt%) for taking 115.67g step (1) to obtain exist
35 DEG C are uniformly mixed, and 2.0g α-Al is added2O3Dispersion liquid (α-Al2O3Content is 20wt%) and 10.0g polyethylene glycol oxide, mixing
Uniformly, it is 13wt% that then aging, which is concentrated into solid content, under 38 DEG C, the vacuum condition of 0.095MPa, and viscosity is at 25 DEG C
Spinnability silicon/Aluminum sol is made in 10Pa.s.
(3) centrifugal drying silk is carried out with 9000 revs/min of revolving speed using above-mentioned spinnability silicon/Aluminum sol and prepares gelatinous fibre.
(4) above-mentioned gained gelatinous fibre is calcined, specific embodiment are as follows: be warming up to the speed of 1.0 DEG C/min
600 DEG C, 1350 DEG C are warming up in this temperature 2h, then with the speed of 10 DEG C/min, it is then natural in this temperature 0.5h
Cooling.In above-mentioned calcination process, nitrogen is passed through with the flow of 8L/min always.
The crystal phase of ceramic fibre made from the present embodiment is mullite and α-Al2O3, fibre diameter is 4.9 μm, and stretch-proof is strong
Degree is up to 1.62GPa, and it is 1.48GPa that average tensile, which stretches intensity,.
Embodiment 7
A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, comprising steps of
(1) 16 hydrazine aluminum sulfate of 645g and 18.0g aluminium powder stir evenly after 1200mL deionized water is added, and 180 DEG C add
Heat reflux 6h reacts completely to aluminium powder, obtains after cooling, filtering containing Al13The alumina sol of micelle, particle size analysis 4nm, i.e.,
Aluminum sol.
(2) Aluminum sol and 10.0g silica solution (dioxide-containing silica 30wt%) for taking 115.67g step (1) to obtain exist
35 DEG C are uniformly mixed, and 1.7g γ-Al is added2O3Dispersion liquid (γ-Al2O3Content is 20wt%) and 10.0g polyethylene glycol oxide, it mixes
It closes uniformly, it is 13.8wt% that then aging, which is concentrated into solid content, under 38 DEG C, the vacuum condition of 0.095MPa, and viscosity is at 25 DEG C
Spinnability silicon/Aluminum sol is made in 13Pa.s.
(3) above-mentioned spinnability silicon/Aluminum sol is blown machine by fiber and sprays into temperature by the high pressure gas for being 0.4MPa with pressure
In the air environment that degree is 38 DEG C, gelatinous fibre is made.
(4) above-mentioned gained gelatinous fibre is calcined, specific embodiment are as follows: be warming up to 600 with the speed of 2 DEG C/min
DEG C, 1350 DEG C are warming up in this temperature 2h, then with the speed of 10 DEG C/min, in this temperature 0.5h, is then dropped naturally
Temperature.In above-mentioned calcination process, nitrogen is passed through with the flow of 0.1L/min always.
The crystal phase of ceramic fibre made from the present embodiment is mullite and α-Al2O3, fibre diameter is 5.2 μm, and stretch-proof is strong
Degree is up to 1.71GPa, and it is 1.58GPa that average tensile, which stretches intensity,.
Claims (10)
1. a kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre, comprising steps of
(1) aluminium powder, aluminium salt, water are uniformly mixed, obtain mixed liquor；It is completely anti-to aluminium powder that 2~20h is heated to reflux in 110~200 DEG C
It answers, Aluminum sol is obtained by filtration；
(2) Aluminum sol made from step (1) method, silica solution, nanoparticulate dispersion and spin finish aid is taken to be uniformly mixed, through old
Change to be concentrated and spinnability silicon/Aluminum sol is made；Then α-Al is obtained through spinning, calcining2O3/ mullite Multiphase ceramic fibre；It is described to receive
Rice grain dispersion liquid is α-Al2O3Dispersion liquid, γ-Al2O3Dispersion liquid or α-Fe2O3The group of one or more of dispersion liquid
It closes.
2. α-Al according to claim 12O3The preparation method of/mullite Multiphase ceramic fibre, which is characterized in that step
(1) in, including one or more in the following conditions:
A) aluminium salt is aluminium chloride, aluminum nitrate or aluminum sulfate；
B) in mixed liquor, the molar concentration of the aluminium salt is 0.3~2mol/L；
C) aluminium salt and the molar ratio of aluminium powder are 1:(1~6)；
D) 2~14h is heated to reflux in 150-180 DEG C to react completely to aluminium powder.
3. α-Al according to claim 12O3The preparation method of/mullite Multiphase ceramic fibre, which is characterized in that step
(1) Aluminum sol described in is to contain Al13The alumina sol of micelle, particle size analysis≤10nm.
4. α-Al according to claim 12O3The preparation method of mullite Multiphase ceramic fibre, which is characterized in that step
(2) mass concentration of silica is 10-45%, α-Al in silica solution described in2O3α-Al in dispersion liquid2O3Mass concentration
For 20-40%, γ-Al2O3γ-Al in dispersion liquid2O3Mass concentration be 20-40%, α-Fe2O3α-Fe in dispersion liquid2O3Matter
Amount concentration is 10-40%.
5. α-Al according to claim 12O3The preparation method of mullite Multiphase ceramic fibre, which is characterized in that step
(2) spin finish aid described in is the group of one or more of polyvinyl alcohol, polyvinylpyrrolidone or polyethylene glycol oxide
It closes.
6. α-Al according to claim 12O3The preparation method of mullite Multiphase ceramic fibre, which is characterized in that step
(2) in, including one or more in the following conditions:
A) mass ratio of Aluminum sol and silica solution is (10~15): 1；
B) quality of dispersion liquid is the 0.1~5% of Aluminum sol and silica solution gross mass；Preferably, the quality of dispersion liquid is that aluminium is molten
The 1~3% of glue and silica solution gross mass；
C) quality of spin finish aid is the 2~15% of Aluminum sol and silica solution gross mass.
7. α-Al according to claim 12O3The preparation method of mullite Multiphase ceramic fibre, which is characterized in that step
(2) in, aging concentration is to carry out aging under 30~40 DEG C, the vacuum condition of 0.095MPa 4~22h is concentrated.
8. α-Al according to claim 12O3The preparation method of mullite Multiphase ceramic fibre, which is characterized in that step
(2) in, the viscosity when solid content of the spinnability silicon/Aluminum sol is 5~45wt%, 25 DEG C is 5~1000Pa.s.
9. α-Al according to claim 12O3The preparation method of mullite Multiphase ceramic fibre, which is characterized in that step
(2) in, following any method is can be used in the spinning process:
I) gelatinous fibre is prepared using dry spinning；Spinning temperature is 30~40 DEG C, and relative humidity is 10~40%, receives silk rate
For 80~110m/min；
Ii centrifugal drying silk) is carried out with 7000~10000 revs/min of revolving speed and prepares gelatinous fibre；Preferably, revolving speed be 8000~
10000 revs/min；
Iii machine) is blown for 30~40 DEG C of the penetrating of spinnability colloidal sol of air ring by fiber with the high pressure gas of 0.3~0.5MPa
Gelatinous fibre is prepared in border；Preferably, the pressure of high pressure gas is 0.3~0.4MPa.
10. α-Al according to claim 12O3The preparation method of mullite Multiphase ceramic fibre, which is characterized in that step
(2) in, the calcination condition are as follows:
150~280 DEG C are warming up to the rate of 0.5~3 DEG C/min, in 0.5~2h of this temperature, then with 1~3 DEG C/min
Rate be warming up to 450~600 DEG C, be warming up to 900~1400 in 2~4h of this temperature, then with the rate of 3~10 DEG C/min
DEG C, in 0.5~2h of this temperature, then Temperature fall；In above-mentioned calcination process, always with the gas stream of 0.1~10L/min
Amount is passed through nitrogen；
Preferably, the calcination condition are as follows: 150~280 DEG C are warming up to the rate of 0.5~2 DEG C/min, in this temperature 1
Then~2h is warming up to 450~600 DEG C with the rate of 1~3 DEG C/min, in 2~3h of this temperature, then with 5~10 DEG C/min
Rate be warming up to 900~1400 DEG C, in 0.5~1h of this temperature, then Temperature fall；In above-mentioned calcination process, always
Nitrogen is passed through with the gas flow of 0.1~5L/min.
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| CN112744847A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Production process of aluminum sol and aluminum sol prepared by production process |
| CN113563101A (en) * | 2021-08-20 | 2021-10-29 | 山东鲁阳浩特高技术纤维有限公司 | Inorganic fiber foamed ceramic and preparation method thereof |
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| CN115259845A (en) * | 2022-06-27 | 2022-11-01 | 东华大学 | Preparation method of flexible continuous mullite filament |
| CN115262033B (en) * | 2022-06-27 | 2024-06-28 | 东华大学 | Preparation method of compact continuous alpha-alumina fiber material |
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| CN112744848A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Production process of aluminum sol and aluminum sol prepared by production process |
| CN112744847A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Production process of aluminum sol and aluminum sol prepared by production process |
| CN112744848B (en) * | 2019-10-31 | 2023-03-10 | 中国石油化工股份有限公司 | Production process of aluminum sol and aluminum sol prepared by production process |
| CN112744847B (en) * | 2019-10-31 | 2023-03-10 | 中国石油化工股份有限公司 | Production process of aluminum sol and aluminum sol prepared by production process |
| CN111235644A (en) * | 2020-03-18 | 2020-06-05 | 山东鲁阳浩特高技术纤维有限公司 | Spinning solution for preparing mullite fiber and application thereof |
| CN111235644B (en) * | 2020-03-18 | 2022-03-04 | 山东鲁阳浩特高技术纤维有限公司 | Spinning solution for preparing mullite fiber and application thereof |
| CN113563101A (en) * | 2021-08-20 | 2021-10-29 | 山东鲁阳浩特高技术纤维有限公司 | Inorganic fiber foamed ceramic and preparation method thereof |
| CN114162844A (en) * | 2021-12-07 | 2022-03-11 | 中南大学 | Precursor composite sol for alumina/mullite dual-phase fiber and preparation method thereof |
| CN114162844B (en) * | 2021-12-07 | 2023-06-02 | 中南大学 | Precursor composite sol for alumina/mullite biphase fiber and preparation method thereof |
| CN115262033A (en) * | 2022-06-27 | 2022-11-01 | 东华大学 | Preparation method of compact continuous alpha-alumina fiber material |
| CN115259845A (en) * | 2022-06-27 | 2022-11-01 | 东华大学 | Preparation method of flexible continuous mullite filament |
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