CN106012105A - Method for preparing zirconium oxide nanometer fiber through bubble spinning - Google Patents
Method for preparing zirconium oxide nanometer fiber through bubble spinning Download PDFInfo
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- CN106012105A CN106012105A CN201610594189.0A CN201610594189A CN106012105A CN 106012105 A CN106012105 A CN 106012105A CN 201610594189 A CN201610594189 A CN 201610594189A CN 106012105 A CN106012105 A CN 106012105A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Fibers (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for preparing zirconium oxide nanometer fiber through bubble spinning. The method comprises the following concrete steps of at room temperature, firstly, dissolving zirconium salts into a solvent; then, performing mixing and stirring with nanometer particles for inhibiting the growth of zirconium oxide colloidal particles by using a dispersing agent; adding polymers to obtain a bubble spinning solution; inputting the spinning solution into a liquid storage pool of bubble spinning equipment; meanwhile, connecting a positive electrode spinning jet to a high-voltage power supply to perform bubble spinning; obtaining a composite nanometer fiber membrane on a negative electrode receiving plate; performing pre-oxidation in a baking oven; then, putting the composite nanometer fiber membrane into a vacuum box type furnace to be subjected to calcination treatment; then, putting the composite nanometer fiber membrane into a muffle furnace to be subjected to high-temperature calcination; finally obtaining the zirconium oxide nanometer fiber membrane. The method provided by the invention has the advantages that the preparation process is simple; the cost is low; the volume of production is great; the scale mass production can be conveniently realized; meanwhile, good high-temperature-resistant performance is realized; the application prospects are wide.
Description
Technical field
The present invention relates to high-temperature inorganic oxide fiber preparation field, be specifically related to a kind of air bubble spinning and prepare
The method of zirconia nanopowder fiber.
Background technology
Zirconium dioxide (ZrO2) is a kind of ceramic material with excellent mechanical performance, thermal property and photoelectric properties
Material.Along with the exploitation of advanced composite material and the application in high-technology field, oxide ceramics structure
Fiber is increasingly subject to pay attention to.Ceramic fibre has that relative weight is light, high temperature resistant, Heat stability is good, thermal conductivity
The advantages such as little, specific heat capacity is little, can be as the lightweight refracrory of function admirable and structural reinforcement material.Remove
Having outside the feature of high temperature resistant, high intensity, ceramic structure fiber also has corrosion resistance acutely temperature strong, anti-
The characteristics such as degree changes, heat-insulating property is good, volume is little, lightweight, are the engineering materials of a kind of high comprehensive performance
Material, can have in industry and Aeronautics and Astronautics field as the reinforcing agent of pottery, metal, plastics etc.
Important purposes.Research is prepared zirconia nanopowder fiber tool and is of great significance, the main table of applied research
The following aspects now:
1) high temperature resistant heat insulation material.Zirconium oxide fibre is the polycrystalline refractory fibre of a kind of function admirable, very
To using for a long time under the hyperthermal environments more than 1600 DEG C.The high-melting-point that Zirconium oxide fibre is had
It is made to have higher use temperature with more preferable than carbon fiber and other ceramic fibres with good chemical stability
High-temperature oxidation resistance.In all metal-oxides, zirconia ceramics has low heat conductivity
(1.6-2.1W/m K), which dictates that it is the ceramic fibre material that a kind of heat-insulating property is excellent.Zirconium oxide is fine
Dimension also has low high temperature steam pressure, the most non-volatile, thus does not results in pollution.Zirconium oxide fibre
In key areas such as war industry, aerospace industry, metallurgical industry, petrochemical industries, there is important application,
Such as the superhigh temperature adiabator on spacecraft surface, the high-temperature stable adiabator of guided missile and rocket engine, smelting
Heat-barrier material etc. in metal working industry high temperature furnace.
2) structural reinforcement material.Zirconic thermal coefficient of expansion (12 × 10-6K) is close with metal, glass etc.,
Zirconium oxide fibre can be used for strengthening the multiple matrixes such as metal, pottery, glass, resin as reinforcing agent,
Prepare the high temperature insulating composite [12] that shock resistance is excellent.
3) chemical resistant material.Zirconium oxide fibre has the chemical resistance of excellence to strong acid, highly basic etc..
Such as, when temperature is up to 700 DEG C, Zirconium oxide fibre has spy for melted alkali metal chloride and carbonate
Different corrosion resistance [13].
4) other application.Zirconium oxide fibre is additionally operable to gas, liquid separates and purification, and oxygen content measures,
Catalytic reaction membrane material etc..
Bubble electrostatic spinning is the spining technology put forward by mechanics principle and mathematical method, the most both at home and abroad
Also there is no like product.This equipment has some basic features of bubble Static Spinning, it is also possible to without electrostatic
Under the conditions of complete spinning process, the most also using electrostatic as auxiliary device, bubble can be carried out prestretched, then
Spinning process is completed under airflow function.Air bubble liquid-membrane (thickness of film is at thousand of ran) at electrostatic or
Being stretched under the effect of air-flow, thickness can drop to the 1/4 1/8 of original thickness, at uneven electricity after bubbles burst
Under the effect of field and airflow field, stretching forms nanofiber further.Which overcomes bubble Static Spinning bubble
Size is difficult to control to, interactional shortcoming between bubble, and a lot of times of output increased, and the preparation being rare is received
The high technology equipment of rice fiber.It can not only overcome the easily blocking of conventional electrostatic spinning process, difficult cleaning,
The shortcoming of Multi needle static interference etc., but also can allow for solution exists the graininess additives such as microgranule,
And it is capable of the mass production of nanofiber or nanosphere to a certain extent.
Therefore, there is resistant to elevated temperatures inorganic oxide zirconium nanofiber imperative with air bubble spinning spinning apparatus, suitable
Answer market demand, it is therefore necessary to provide the preparation method of the standby zirconia nanopowder fiber of a kind of resistance to bubble spinning,
To solve problem of the prior art.
Summary of the invention
In view of this, it is an object of the invention to provide the preparation method of a kind of inorganic oxide zirconium nanofiber.
For achieving the above object, the present invention provides following technical scheme:
A kind of air bubble spinning prepares the method for zirconia nanopowder fiber, and it includes step:
(1) under room temperature, zirconates is dissolved in a solvent by a certain percentage, then rely on dispersant and suppression oxygen
Change oxide or inorganic salt particle mix and blend according to a certain percentage that zirconium micelle is grown up, dissolve a polymer in molten
In agent, heated and stirred obtains spinning solution；
(2) in the spinning solution obtained the liquid storage tank being entered into air bubble spinning equipment, simultaneously will just
Pole spinning head connects high voltage power supply and carries out air bubble spinning, and negative pole receives plate in succession, in room temperature 20-30 DEG C and relatively
Under conditions of humidity 30-60%, described air bubble spinning solution is carried out air bubble spinning, it is thus achieved that nascent composite fibre
Film；
(3) being pre-oxidized in an oven by the nascent composite cellulosic membrane obtained, temperature is 90-300 DEG C, in advance
Oxidization time is 60-180min；Then vacuum calcining in vacuum box type stove, temperature is 500-900 DEG C, very
Reciprocal of duty cycle is 0.09-0.2MPa, and heating rate is 1-10 DEG C/min；It is sintered in Muffle furnace again, forges
Burning temperature and be 900-1800 DEG C, heating rate is 1-10 DEG C/min；Finally cool down to obtain zirconia nanopowder fiber.
Preferably, in above-mentioned air bubble spinning prepares the method for zirconia nanopowder fiber, in described step (1),
Zirconates is the one in zirconium oxychloride, zirconium nitrate, acetylacetone,2,4-pentanedione zirconium, zirconium carbonate, zirconium iso-propoxide, acetic acid zirconium
Or two kinds；Solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetic acid, formic acid, water,
One or both in ethanol etc.；Dispersant is sodium tripolyphosphate, sodium hexameta phosphate, sodium pyrophosphate, three second
One in base hexyl phosphoric acid, sodium lauryl sulphate, methyl anyl alcohol, polyethylene glycol 200 or 400；Press down
Oxide that oxygenerating zirconium micelle is grown up or inorganic salt particle be zirconium oxide, aluminium oxide, yittrium oxide, magnesium oxide,
One or both in calcium oxide, magnesium sulfate, the particle diameter of described granule is 5-150nm；Polymer is polyethylene
One in alcohol, polyacrylonitrile, polyether sulfone, polyvinylpyrrolidone, Kynoar, polylactic acid；?
Stirring mixes and adjusts system pH eventually is 1.0～5.0, and the content of granular powder is 0～10wt%, bubble
Spinning fluid viscosity is 1000～5000mPa s.
Preferably, in above-mentioned air bubble spinning prepares the method for zirconia nanopowder fiber, in described step (2),
Spinning process mesohigh is set to 15KV～40KV, receiving position distance air bubble spinning unit 10cm～
40cm。
Preferably, in above-mentioned air bubble spinning prepares the method for zirconia nanopowder fiber, in described step (3),
One during noble gas is nitrogen or argon in vacuum box type stove；Muffle furnace calcination process can with step-by-step processing,
The calcination processing of next temperature section it is further continued between being incubated one section after being raised to a certain temperature.
Preferably, in above-mentioned air bubble spinning prepares the method for zirconia nanopowder fiber, described pliable and tough high-strength oxygen
The hot strength changing zirconium nano fibrous membrane reaches 20-100MPa, smooth surface, described pliable and tough high-strength zirconium oxide
Fibre diameter in nano fibrous membrane is 5nm-10 μm, by the zirconium oxide of average grain size 5～500nm
Grain composition.
Preferably, in above-mentioned air bubble spinning prepares the method for zirconia nanopowder fiber, described zirconia nanopowder
The crystal formation of fiber product is the one in Tetragonal, Emission in Cubic or mixed phase.
From technique scheme it can be seen that preparation technology of the present invention is simple, low cost, yield are big, it is simple to
Scale is produced in batches, the most also has good resistance to elevated temperatures, has broad application prospects.
Compared with prior art, the method have the advantages that
(1) present invention prepares inorganic oxide zirconium nanofiber with air bubble spinning method, and preparation technology is simple, one-tenth
This is low, yield is big, it is simple to scale is produced in batches, not only greatly simplifies the preparation process of spinning liquid,
And significantly improve yield.
(2) present invention by oxide or the inorganic salt particle of a small amount of different-grain diameter of employing is, it is possible to the most square
Just realize the inhibitory action that zirconium oxide micelle is grown up, and the application demand of different field can be met.
(3) present invention is by using multisection type calcination process, in an oven through vacuum environment after pre-oxidation
Calcining, then secondary air calcination in Muffle furnace, greatly ensure that the light of zirconia nanopowder fiber surface
Sliding seriality.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to enforcement
In example or description of the prior art, the required accompanying drawing used is briefly described, it should be apparent that, describe below
In accompanying drawing for the present invention be only some embodiments of the present invention, for those of ordinary skill in the art
From the point of view of, on the premise of not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the nascent composite fibre that air bubble spinning of the present invention prepares that the method for zirconia nanopowder fiber prepares
Field scanning ultramicroscope (SEM) photo.
Fig. 2 is the zirconia nanopowder fiber that air bubble spinning of the present invention prepares that the method for zirconia nanopowder fiber prepares
Field scanning ultramicroscope (SEM) photo.
Fig. 3 be air bubble spinning of the present invention prepare zirconia nanopowder fiber method prepare as-spun fibre and four directions
The XRD figure of phase yttrium stable zirconium oxide nanofiber.
Fig. 4 is the step schematic diagram that air bubble spinning of the present invention prepares the method for zirconia nanopowder fiber.
Detailed description of the invention
The invention discloses the preparation method of a kind of inorganic oxide zirconium nanofiber.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out in detail
Thin description, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole
Embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creative work
On the premise of the every other embodiment that obtained, broadly fall into the scope of protection of the invention.
As indicated at 4, a kind of air bubble spinning prepares the method for zirconia nanopowder fiber, including:
(1) under room temperature, zirconates is dissolved in a solvent by a certain percentage, then rely on dispersant and suppression oxygen
Change oxide or inorganic salt particle mix and blend according to a certain percentage that zirconium micelle is grown up, dissolve a polymer in molten
In agent, heated and stirred obtains spinning solution；
(2) take in the above-mentioned liquid storage tank being input to air bubble spinning equipment, positive pole spinning head is connected high pressure simultaneously
Power supply carries out air bubble spinning, and negative pole receives plate in succession, at room temperature 20-30 DEG C and the bar of relative humidity 30-60%
Under part, described air bubble spinning solution is carried out air bubble spinning, it is thus achieved that nascent composite cellulosic membrane；
Being pre-oxidized in an oven by the nascent composite cellulosic membrane obtained, temperature is 90-300 DEG C, during pre-oxidation
Between be 60-180min；Then vacuum calcining in vacuum box type stove, temperature is 500-900 DEG C, and vacuum is
0.09-0.2MPa, heating rate is 1-10 DEG C/min；It is sintered in Muffle furnace again, calcining heat
For 900-1800 DEG C, heating rate is 1-10 DEG C/min；Finally cool down to obtain zirconia nanopowder fiber.
In described step (1), zirconates is zirconium oxychloride, zirconium nitrate, acetylacetone,2,4-pentanedione zirconium, zirconium carbonate, isopropyl
One or two kinds of in alcohol zirconium, acetic acid zirconium etc.；Solvent is N,N-dimethylformamide, N, N-dimethyl second
One or both in amide, acetic acid, formic acid, water, ethanol etc.；Dispersant is sodium tripolyphosphate, six inclined
Sodium phosphate, sodium pyrophosphate, triethyl group hexyl phosphoric acid, sodium lauryl sulphate, methyl anyl alcohol, Polyethylene Glycol
One in 200 or 400；Oxide or inorganic salt particle that inhibited oxidation zirconium micelle is grown up are zirconium oxide, oxygen
Change in aluminum, yittrium oxide, magnesium oxide, calcium oxide, magnesium sulfate etc. one or both, the particle diameter of described granule
For 5-150nm；Polymer is polyvinyl alcohol, polyacrylonitrile, polyether sulfone, polyvinylpyrrolidone, poly-inclined fluorine
One in ethylene, polylactic acid etc.；Final stirring mixes and adjusts system pH is 1.0～5.0, granular powder
The content of body is 0～10wt%, and air bubble spinning fluid viscosity is 1000～5000mPa s.
In described step (2), spinning process mesohigh is set to 15KV～40KV, receiving position distance gas
Bubble electrospinning unit 10cm～40cm.
In described step (3), a kind of during in vacuum box type stove, noble gas is nitrogen or argon；Muffle furnace is forged
Burning process can be further continued for next temperature section with step-by-step processing between being incubated one section after being raised to a certain temperature
Calcination processing.
The hot strength of described flexible high-strength zirconia nanofiber membrane reaches 20-100MPa, smooth surface,
Fibre diameter in described flexible high-strength zirconia nanofiber membrane is 5nm-10 μm, by average grain size
The zirconia particles composition of 5～500nm.
The crystal formation of described zirconia nanopowder fiber product is the one in Tetragonal, Emission in Cubic or mixed phase.
As shown in Figure 1 to Figure 3, Fig. 1 is the method system that air bubble spinning of the present invention prepares zirconia nanopowder fiber
Field scanning ultramicroscope (SEM) photo of the nascent composite fibre obtained.Fig. 2 is air bubble spinning of the present invention
Prepare the field scanning ultramicroscope (SEM) of zirconia nanopowder fiber that the method for zirconia nanopowder fiber prepares
Photo.Fig. 3 is the as-spun fibre and four that air bubble spinning of the present invention prepares that the method for zirconia nanopowder fiber prepares
The XRD figure of side's phase yttrium stable zirconium oxide nanofiber.
Preparation technology of the present invention is simple, low cost, yield are big, it is simple to scale is produced in batches, the most also has
There is good resistance to elevated temperatures, have broad application prospects.
Compared with prior art, the method have the advantages that
(1) present invention prepares inorganic oxide zirconium nanofiber with air bubble spinning method, and preparation technology is simple, one-tenth
This is low, yield is big, it is simple to scale is produced in batches, not only greatly simplifies the preparation process of spinning liquid,
And significantly improve yield.
(2) present invention by oxide or the inorganic salt particle of a small amount of different-grain diameter of employing is, it is possible to the most square
Just realize the inhibitory action that zirconium oxide micelle is grown up, and the application demand of different field can be met.
(3) present invention is by using multisection type calcination process, in an oven through vacuum environment after pre-oxidation
Calcining, then secondary air calcination in Muffle furnace, greatly ensure that the light of zirconia nanopowder fiber surface
Sliding seriality.
Below in conjunction with specific embodiment, the application is elaborated, but the case study on implementation of the present invention is not limited to
This.
Embodiment one
A kind of as-spun fibre is the method that the air bubble spinning of polyacrylonitrile (PAN) prepares zirconia nanopowder fiber,
Its process route is as follows:
(1) first 1g zirconium oxychloride (Cl2OZr) is dissolved in 1gN-N dimethyl acetylamide (DMAC)
In solvent, it is then added in water-bath in the case of 60 DEG C stir into perfect solution state；Simultaneously by polypropylene
Nitrile 1.5g (PAN) is dissolved in 12.5gN-N dimethyl acetylamide (DMAC) solvent, is then added to water
Bath stirs in the case of 90 DEG C perfect solution state；Again two kinds of solution mixing, add 0.2gZrO2
Nanoparticle stabilizers and 0.3g Polyethylene Glycol, finally uniform stirring 3h in ultrasonic stirrer, becomes
Whole air bubble spinning solution；
(2) spinning liquid is joined in the spinning solution groove that rotation bubble spins, positive pole spinning head is connected simultaneously
High voltage power supply carries out air bubble spinning, and negative pole receives plate in succession, and receiving range is 12cm, in room temperature 26 DEG C and phase
Under conditions of humidity 50%, high-pressure electrostatic is set to 15KV, carries out air bubble spinning, it is thus achieved that nano fibrous membrane；
(3) carrying out the nano fibrous membrane obtained in an oven pre-oxidizing 1h, temperature is 90 DEG C；Then exist
Calcining in nitrogen environment in vacuum box type stove, temperature is 600 DEG C, and vacuum is 0.1MPa, and heating rate is
3℃/min；Being sintered in Muffle furnace, calcining heat is 1000 DEG C again, and heating rate is 3 DEG C/min,
2h it is incubated after 1000 DEG C；Finally cool down to obtain zirconia nanopowder fiber.
Inorganic oxide zirconium nanofiber diameter prepared by this example is uniform, seriality good, has the most soft
Toughness.As-spun fibre is as it is shown in figure 1, final zirconia nanopowder fiber is as in figure 2 it is shown, fiber product surface
Smooth densification, does not has obvious pore and crackle；The average diameter of fiber product is 86nm, by average crystal grain
The nano zircite granule composition of a size of 30nm；Fig. 3 is respectively as-spun fibre and zirconium oxide in this example and receives
The XRD figure spectrum of rice fiber.
Embodiment two
A kind of as-spun fibre is the method that the air bubble spinning of polyvinyl alcohol (PVA) prepares zirconia nanopowder fiber,
Its process route is as follows:
(1) first 1.5g acetic acid zirconium is dissolved in 3g deionized water, then stirs under room temperature state
Perfect solution state；Polyvinyl alcohol 4.5g (PVA) is dissolved in 42g deionized water simultaneously, is subsequently adding
In the case of 90 DEG C, perfect solution state is stirred in water-bath；Again two kinds of solution mixing, add 0.5g oxygen
Change yttrium (Y2O3) nanoparticle stabilizers and 0.5g Polyethylene Glycol, finally uniformly stir in ultrasonic stirrer
Mix 2h, become final air bubble spinning solution；
(2) spinning liquid is joined in the spinning solution groove that rotation bubble spins, positive pole spinning head is connected simultaneously
High voltage power supply carries out air bubble spinning, and negative pole receives plate in succession, and receiving range is 15cm, in room temperature 26 DEG C and phase
Under conditions of humidity 40%, high-pressure electrostatic is set to 25KV, carries out air bubble spinning, it is thus achieved that nano fibrous membrane；
(3) carrying out the nano fibrous membrane obtained in an oven pre-oxidizing 0.5h, temperature is 90 DEG C；Then exist
Calcining in nitrogen environment in vacuum box type stove, temperature is 500 DEG C, and vacuum is 0.1MPa, and heating rate is
2℃/min；Being sintered in Muffle furnace, calcining heat is 900 DEG C again, and heating rate is 3 DEG C/min；
Finally cool down to obtain zirconia nanopowder fiber.
The present invention prepares inorganic oxide zirconium nanofiber with air bubble spinning method, preparation technology is simple, low cost,
Yield is big, it is simple to scale is produced in batches, not only greatly simplifies the preparation process of spinning liquid, Er Qiexian
Work improves yield；By using oxide or the inorganic salt particle of a small amount of different-grain diameter to be, it is possible to the most square
Just realize the inhibitory action that zirconium oxide micelle is grown up, and the application demand of different field can be met；
By using multisection type calcination process, calcine through vacuum environment after pre-oxidation in an oven, then secondary
Air calcination in Muffle furnace, greatly ensure that the smooth and continuous of zirconia nanopowder fiber surface.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment,
And without departing from the spirit or essential characteristics of the present invention, it is possible to realize in other specific forms
The present invention.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, but the most each enforcement
Mode only comprises an independent technical scheme, and this narrating mode of description is only for clarity sake,
Those skilled in the art should be using description as an entirety, and the technical scheme in each embodiment can also be through
Appropriately combined, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (6)
1. the method that an air bubble spinning prepares zirconia nanopowder fiber, it is characterised in that: include step:
(1) under room temperature, zirconates is dissolved in a solvent by a certain percentage, then rely on dispersant and suppression
Oxide that zirconium oxide micelle is grown up or inorganic salt particle mix and blend according to a certain percentage, polymer is molten
In solvent, heated and stirred obtains spinning solution；
(2), in the spinning solution obtained the liquid storage tank being entered into air bubble spinning equipment, will simultaneously
Positive pole spinning head connects high voltage power supply and carries out air bubble spinning, and negative pole receives plate in succession, in room temperature 20-30 DEG C and
Under conditions of relative humidity 30-60%, described air bubble spinning solution is carried out air bubble spinning, it is thus achieved that nascent multiple
Condensating fiber film；
(3) being pre-oxidized in an oven by the nascent composite cellulosic membrane obtained, temperature is 90-300 DEG C,
Preoxidation time is 60-180min；Then vacuum calcining in vacuum box type stove, temperature is 500-900 DEG C,
Vacuum is 0.09-0.2MPa, and heating rate is 1-10 DEG C/min；It is sintered in Muffle furnace again,
Calcining heat is 900-1800 DEG C, and heating rate is 1-10 DEG C/min；Finally cool down to obtain zirconia nanopowder fibre
Dimension.
Air bubble spinning the most according to claim 1 prepares the method for zirconia nanopowder fiber, its feature
Be: in described step (1), zirconates be zirconium oxychloride, zirconium nitrate, acetylacetone,2,4-pentanedione zirconium, zirconium carbonate,
One or two kinds of in zirconium iso-propoxide, acetic acid zirconium；Solvent is N,N-dimethylformamide, N, N-diformazan
One or both in yl acetamide, acetic acid, formic acid, water, ethanol etc.；Dispersant be sodium tripolyphosphate,
Sodium hexameta phosphate, sodium pyrophosphate, triethyl group hexyl phosphoric acid, sodium lauryl sulphate, methyl anyl alcohol, poly-
One in ethylene glycol 200 or 400；Oxide or inorganic salt particle that inhibited oxidation zirconium micelle is grown up are
One or both in zirconium oxide, aluminium oxide, yittrium oxide, magnesium oxide, calcium oxide, magnesium sulfate, described
The particle diameter of granule is 5-150nm；Polymer is polyvinyl alcohol, polyacrylonitrile, polyether sulfone, polyvinyl pyrrole
One in alkanone, Kynoar, polylactic acid；Final stirring mixing and adjust system pH be 1.0～
5.0, the content of granular powder is 0～10wt%, and air bubble spinning fluid viscosity is 1000～5000mPa s.
Air bubble spinning the most according to claim 1 prepares the method for zirconia nanopowder fiber, its feature
Be: in described step (2), spinning process mesohigh is set to 15KV～40KV, receiving position away from
From air bubble spinning unit 10cm～40cm.
Air bubble spinning the most according to claim 1 prepares the method for zirconia nanopowder fiber, its feature
It is: in described step (3), a kind of during in vacuum box type stove, noble gas is nitrogen or argon；Muffle
Stove calcination process can be further continued for next temperature with step-by-step processing between being incubated one section after being raised to a certain temperature
The calcination processing of degree section.
Air bubble spinning the most according to claim 1 prepares the method for zirconia nanopowder fiber, its feature
It is: the hot strength of described flexible high-strength zirconia nanofiber membrane reaches 20-100MPa, surface light
Sliding, the fibre diameter in described flexible high-strength zirconia nanofiber membrane is 5nm-10 μm, by average brilliant
The zirconia particles composition of particle size 5～500nm.
Air bubble spinning the most according to claim 1 prepares the method for zirconia nanopowder fiber, its feature
It is: the crystal formation of described zirconia nanopowder fiber product is the one in Tetragonal, Emission in Cubic or mixed phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610594189.0A CN106012105B (en) | 2016-07-26 | 2016-07-26 | A kind of method that air bubble spinning prepares zirconia nanopowder fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610594189.0A CN106012105B (en) | 2016-07-26 | 2016-07-26 | A kind of method that air bubble spinning prepares zirconia nanopowder fiber |
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| CN107675275A (en) * | 2017-11-17 | 2018-02-09 | 苏州大学 | Two-dimensional ultrathin material and preparation method thereof |
| CN113702471A (en) * | 2021-08-30 | 2021-11-26 | 吉林大学 | YSZ-based mixed potential NO2Sensor and preparation method thereof |
| CN114988870A (en) * | 2022-06-20 | 2022-09-02 | 中国地质大学（北京） | Preparation method of zirconium oxide cellucotton |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107675275A (en) * | 2017-11-17 | 2018-02-09 | 苏州大学 | Two-dimensional ultrathin material and preparation method thereof |
| CN107675275B (en) * | 2017-11-17 | 2020-11-03 | 苏州大学 | Two-dimensional ultrathin material and preparation method thereof |
| CN113702471A (en) * | 2021-08-30 | 2021-11-26 | 吉林大学 | YSZ-based mixed potential NO2Sensor and preparation method thereof |
| CN113702471B (en) * | 2021-08-30 | 2022-06-21 | 吉林大学 | YSZ-based mixed potential NO2Sensor and preparation method thereof |
| CN114988870A (en) * | 2022-06-20 | 2022-09-02 | 中国地质大学（北京） | Preparation method of zirconium oxide cellucotton |
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