CN110483099A - A method of improve continuous zirconia fiber intensity and can prehensile - Google Patents
A method of improve continuous zirconia fiber intensity and can prehensile Download PDFInfo
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- CN110483099A CN110483099A CN201910789180.9A CN201910789180A CN110483099A CN 110483099 A CN110483099 A CN 110483099A CN 201910789180 A CN201910789180 A CN 201910789180A CN 110483099 A CN110483099 A CN 110483099A
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
Abstract
The present invention relates to a kind of intensity for improving continuous zirconia fiber and can the method for prehensile continuous zirconia fiber fast transfer to 1200-1500 DEG C of high-temperature area is stayed for some time, be then immediately placed under room temperature environment cooling.By the present invention treated continuous zirconia fiber, continuous zirconia fiber monofilament tensile strength is 2-3 times of intensity after slow temperature program processing after treatment, and mechanical property significantly improves.
Description
Technical field
The present invention relates to it is a kind of improve continuous zirconia fiber intensity and can prehensile method more particularly to one kind adopt
High-intensitive continuous zirconia fiber is prepared with poly- acetylacetone,2,4-pentanedione zirconium system, and carries out processing and improves the strong of continuous zirconia fiber
Degree and can prehensile method, belong to inorganic non-metallic oxide fibre field of material technology.
Background technique
Zirconium oxide fibre is a kind of structure enhancing with very big application potential and functional composite material, have fusing point it is high,
Outstanding advantages of thermal conductivity is low, thermal capacitance is small, acid-alkali-corrosive-resisting, excellent in mechanical performance, high-temperature vapour force down, by countries in the world
Extensive concern and fall over each other to study, in space flight, military affairs and other current high-tech and sophisticated technology field, just play increasingly heavier
The effect wanted.
Zirconium oxide fibre is divided into staple fiber and continuous fiber, due to the difficulty in Zirconium oxide fibre technology of preparing, in the world
Zirconium oxide fibre usually by length greater than 1 meter becomes continuous zirconia fiber.Carry out both at home and abroad mostly since 1964
Be zirconium oxide staple fiber technology of preparing in terms of research, Shandong University crystalline material National Key Laboratory Xu Dong professor grinds
Study carefully team to take the lead within 1998 obtaining important breakthrough in terms of the preparation of continuous zirconia fiber.Using the method for various presomas,
Specific method has been described in patent CN1206397C, and continuous zirconia fiber has been prepared in laboratory.In
Described in CN201410240102.0 a kind of continuous crystal fibre of km grade High-temperature-reszirconium zirconium oxide preparation method,
A kind of method that zirconium oxyacetate-methanol system prepares continuous oxidation zirconium crystal fibre is described in CN201410240079.5, all
The processes such as the synthesis of presoma, the preparation of spinning solution, dry spinning, pressure parsing, high temperature heat treatment are described in detail.But
Be, the above method to the concern of the intensity of continuous zirconia fiber and can prehensile it is inadequate, obtained continuous zirconia fiber
Intensity needs to be further increased, and winding performance is bad.The intensity size of continuous zirconia fiber directly affects its conduct
Mechanical structure enhancing and the effect that is played of functional composite material, and the important application form of continuous fiber material is for compiling
Knit body, thus its can prehensile be premise that it can weave.
Therefore, improve continuous zirconia fiber intensity and can prehensile, it is imperative.For this purpose, proposing the present invention.
Summary of the invention:
In view of the shortcomings of the prior art, the present invention is on the basis of the continuous zirconia fiber that original preparation method obtains, into
One step processing, improve continuous zirconia fiber mechanical strength and can prehensile, for fiber braiding and application carry out technology and
Materials for support.
Technical scheme is as follows:
A method of improve continuous zirconia fiber intensity and can prehensile, comprise the following steps that
By continuous zirconia fiber fast transfer to 1200-1500 DEG C of high-temperature area, stays for some time, then set rapidly
It is cooling under room temperature environment.
, according to the invention it is preferred to, residence time 2-200s；Further preferred 2-10s.
, according to the invention it is preferred to, by continuous zirconia fiber fast transfer to 1400 DEG C of high-temperature areas, 10s is stopped, so
After be immediately placed under room temperature environment it is cooling.
, according to the invention it is preferred to, when continuous zirconia fiber fast transfer to 1200-1500 DEG C of progress high-temperature residence,
Continuous zirconia fiber both ends apply Minimal Tension, the size 20-200cN of tension.Apply Minimal Tension processing, zirconium oxide can be made
Continuous fiber tow lousiness is less, and smooth without bending, corrugationless, fiber ordering degree is higher.After high-temperature process, fiber is formed
Zirconia grains it is tiny, the tensile strength of monfil is up to 3.0GPa.
, according to the invention it is preferred to, the cooling high-intensitive continuous zirconia fiber obtained of room temperature is subjected to identical tension or perseverance
Linear velocity orderly winds to get coiled continuous zirconia fiber.Can tens meters of coiling length to upper km.
, according to the invention it is preferred to, the Tensity size of winding is 50-300cN, linear velocity 200-2000mm/min.
, according to the invention it is preferred to, being placed in cooling procedure under room temperature environment is natural cooling.
According to the present invention, the continuous zirconia fiber can be obtained according to prior art preparation.It can refer to Chinese patent
File CN201410240102.0.Preferably, it obtains as follows:
(1) preparation of poly- acetyl acetone zirconium precursor body
1. in zirconium oxychloride: dehydrated alcohol=100g:640~800g ratio, weigh zirconium oxychloride raw material be dissolved in it is anhydrous
In ethyl alcohol, acetylacetone,2,4-pentanedione is added and stirs 1~2 hour；Triethylamine-alcohol mixed solution is added, is stirred to react 1~4 hour, obtains
Solution containing poly- acetylacetone,2,4-pentanedione zirconium；Wherein, it zirconium oxychloride: acetylacetone,2,4-pentanedione: rubs triethylamine=1:1.8~2.0:1.9~2.5
Your ratio, triethylamine in triethylamine-alcohol mixed solution: ethyl alcohol=35~45:100 volume ratio；
2. the solution containing poly- acetylacetone,2,4-pentanedione zirconium is removed etoh solvent through being concentrated under reduced pressure, powder is obtained, according to oxychlorination
Zirconium: acetone is added in acetone=100g:300~800mL ratio, dissolves soluble matter, and decompression, which filters, removes insoluble salt triethylenetetraminehexaacetic acid
Amine white precipitate, gained filtrate is by being concentrated under reduced pressure recycling acetone, until before obtaining dry powder to get poly- acetylacetone,2,4-pentanedione zirconium
Drive body；
(2) preparation of spinning solution
Poly- acetyl acetone zirconium precursor body is dissolved in anhydrous methanol, according to yttrium oxide: (zirconium oxide+yttrium oxide)=5.7
The ratio addition yttrium salt of~8mol%, stirring form solution, and the method by evaporating solvent is concentrated, until acquisition viscosity 10~
Transparent, the uniform and stable spinning liquid as precursor of 100Pas, the viscosity are measured at 20 DEG C；
(3) dry spinning
Spinning liquid as precursor is moved into the liquid tank in device for spinning, 5~10min of vacuum defoamation, in temperature 10~40
DEG C, under the conditions of relative humidity 20~80%, pressurizeed 0.5~2.5MPa, made to spinning solution with the mode of steel cylinder nitrogen or metering pump
Its spinneret orifice for being 0.03~0.20mm from aperture sprays, and through multistage drafting and receives silk, obtains 10~40 μm of diameter of poly- acetyl
Acetone zirconium presoma continuous fiber；
(4) pressure parses
Presoma continuous fiber is placed in the pressure vessel for being preheated to 90~130 DEG C, pressure control is 2 after being passed through atmosphere
~15 atmospheric pressure, heat temperature raising make 120~200 DEG C of temperature, carry out dissection process, and the processing time is 5min~4h, so that
Ligand acetylacetone,2,4-pentanedione in precursor fibre parses；After dissection process, the steam of discharge enrichment acetylacetone,2,4-pentanedione makes to press
Temperature in force container is down to 80~100 DEG C, and the fiber after pressure is parsed continues to be placed in dry 5~30min in container, so
It takes out and is heat-treated afterwards；
(5) it is heat-treated
By the parsing of step (4) pressure, treated that fiber is placed in sintering furnace is heat-treated, in the presence of steam, with
The heating rate of 0.5~3 DEG C/min is warming up to 500~800 DEG C, and poly- acetyl acetone zirconium precursor body generation is made sufficiently to parse and tie
Crystalline substance is converted into continuous oxidation zirconium crystal fibre.
According to the present invention, a kind of preferred embodiment, comprises the following steps that
Continuous zirconia fiber is rapidly entered into 1400 DEG C of high-temperature regions, the high-temperature region residence time is 10s, applies tension and is
Then continuous zirconia fiber is directly placed in and cools down at room temperature by 100cN.The stretch-proof for measuring continuous zirconia fiber monofilament is strong
Degree reaches as high as 3.0GPa in 2.0GPa or so.
According to the present invention, a kind of high intensity can wind the preparation method of continuous zirconia fiber, comprise the following steps that
(1) preparation of poly- acetyl acetone zirconium precursor body
1. in zirconium oxychloride: dehydrated alcohol=100g:640~800g ratio, weigh zirconium oxychloride raw material be dissolved in it is anhydrous
In ethyl alcohol, acetylacetone,2,4-pentanedione is added and stirs 1~2 hour；Triethylamine-alcohol mixed solution is added, is stirred to react 1~4 hour, obtains
Solution containing poly- acetylacetone,2,4-pentanedione zirconium；Wherein, it zirconium oxychloride: acetylacetone,2,4-pentanedione: rubs triethylamine=1:1.8~2.0:1.9~2.5
Your ratio, triethylamine in triethylamine-alcohol mixed solution: ethyl alcohol=35~45:100 volume ratio；
2. the solution containing poly- acetylacetone,2,4-pentanedione zirconium is removed etoh solvent through being concentrated under reduced pressure, powder is obtained, according to oxychlorination
Zirconium: acetone is added in acetone=100g:300~800mL ratio, dissolves soluble matter, it is white that filters pressing removes insoluble triethylamine hydrochloride
Color precipitating, gained filtrate is by being concentrated under reduced pressure recycling acetone, until obtaining dry powder to get poly- acetyl acetone zirconium precursor
Body；
(2) preparation of spinning solution
Poly- acetyl acetone zirconium precursor body is dissolved in anhydrous methanol, according to yttrium oxide: (zirconium oxide+yttrium oxide)=5.7
The ratio addition yttrium salt of~8mol%, stirring form solution, and the method by evaporating solvent is concentrated, until acquisition viscosity 10~
Transparent, the uniform and stable spinning liquid as precursor of 100Pas, the viscosity are measured at 20 DEG C；
(3) dry spinning
Spinning liquid as precursor is moved into the liquid tank in device for spinning, 5~10min of vacuum defoamation, in temperature 10~40
DEG C, under the conditions of relative humidity 20~80%, pressurizeed 0.5~2.5MPa, made to spinning solution with the mode of steel cylinder nitrogen or metering pump
Its spinneret orifice for being 0.03~0.20mm from aperture sprays, and through multistage drafting and receives silk, obtains 10~40 μm of diameter of poly- acetyl
Acetone zirconium presoma continuous fiber；
(4) pressure parses
Presoma continuous fiber is placed in the pressure vessel for being preheated to 90~130 DEG C, pressure control is 2 after being passed through atmosphere
~15 atmospheric pressure, heat temperature raising make 120~200 DEG C of temperature, carry out dissection process, and the processing time is 5min~4h, so that
Ligand acetylacetone,2,4-pentanedione in precursor fibre parses；After dissection process, the steam of discharge enrichment acetylacetone,2,4-pentanedione makes to press
Temperature in force container is down to 80~100 DEG C, and the fiber after pressure is parsed continues to be placed in dry 5~30min in container, so
It takes out and is heat-treated afterwards；
(5) it is heat-treated
By the parsing of step (4) pressure, treated that fiber is placed in sintering furnace is heat-treated, in the presence of steam, with
The heating rate of 0.5~3 DEG C/min is warming up to 500~800 DEG C, then by continuous zirconia fiber fast transfer to 1200-
1500 DEG C of high-temperature areas stop 2-200s, and zirconium oxide company can be wound to get high intensity by being then immediately placed under room temperature environment to cool down
Continuous fiber.
The principle of the present invention:
The continuous zirconia fiber handled by 500-800 DEG C forms crystal grain generally in 20-50nm, and crystal grain is relatively fine,
According to conventional heat treatment method, crystal grain can gradually grow up with the promotion of temperature, can grow when temperature is increased to 1500 DEG C
To 1 microns, the binding force between crystal grain is greatly reduced, and fibre strength also weakens therewith.The present invention is using at quick high-temp
The method of reason blocks the slow growth course of crystal grain, and the crystal grain for forming fiber still keeps lesser size, a large amount of grain boundary density
Fiber tensile strength with higher is also ensured with binding force.And high intensity is the premise that continuous fiber can be wound, and is otherwise held
Easily there is fracture, tow is torn or even can not winding phenomenon.
Beneficial effects of the present invention are as follows:
1, the continuous zirconia fiber that the prior art including the patent of seminar's early period of the invention obtains, is twining
It is not brilliant around property aspect.Inventors have found that continuous zirconia fiber is rapidly heated to 1200-1500 DEG C, high-temperature residence one
Then the section time is detached from rapidly hot environment, is cooled to room temperature.It not only can significantly improve winding performance, but also can be with
Significantly improve the mechanical property of continuous zirconia fiber.Such as: the method referring to disclosed in CN201410240102.0, with last
Based on 500-800 DEG C handles obtained continuous zirconia fiber, as early as possible after quick high-temp processing, the zirconium oxide for forming fiber is brilliant
Grain is still relatively fine, and does not occur phenomenon of obviously growing up, and winding performance significantly improves.
2, by the present invention treated continuous zirconia fiber, the stretch-proof of continuous zirconia fiber monofilament is strong after treatment
Degree is 2-3 times of intensity after slow temperature program processing, and mechanical property significantly improves.
3, by the present invention treated continuous zirconia fiber, identical tension can be carried out or constant linear velocity is orderly wound, it is fine
The length and weight of dimension can accurate measurement, be advantageous to classification, storage and transport.
Detailed description of the invention
Fig. 1 is to be handled in embodiment 1 to the SEM photograph of 600 DEG C of continuous zirconia fibers；
Fig. 2 is the SEM photograph of the continuous zirconia fiber after 1300 DEG C quickly processing in embodiment 1；
Fig. 3 is the crystal grain distribution of the continuous zirconia fiber after 1300 DEG C quickly processing in embodiment 1；
Fig. 4 is to be handled in comparative example 1 to the SEM photograph of 1300 DEG C of continuous zirconia fibers；
Fig. 5 is the photo that high-intensitive continuous zirconia fiber is orderly wound obtained in embodiment 1.
Specific embodiment
Below by specific embodiment, the present invention will be further described, but not limited to this.
Continuous zirconia fiber as described in the examples is prepared as follows to obtain:
(1) preparation of poly- acetyl acetone zirconium precursor body
1. weighing 100g zirconium oxychloride ZrOCl2·8H2O, according to zirconium oxychloride: dehydrated alcohol=100g:640g ratio
It is dissolved in dehydrated alcohol, be zirconium oxychloride: acetylacetone,2,4-pentanedione according to molar ratio: triethylamine=1:2.0:2.0 ratio measures acetyl
Acetylacetone,2,4-pentanedione, is first slowly added into the ethanol solution of zirconium oxychloride by acetone 31.1g and triethylamine 60.9g, is sufficiently stirred
Even formation mixed solution；Then the mixed solution (mixed proportion is 60.9g triethylamine: 160g ethyl alcohol) of triethylamine and ethyl alcohol is slow
Slow to be added into above-mentioned mixed solution, sufficiently reaction stirring 2 hours obtains golden yellow reaction solution, that is, contains poly- acetyl acetone
The solution of zirconium.
2. etoh solvent and water are removed through being concentrated under reduced pressure at 40~45 DEG C of temperature, vacuum degree 0.09MPa, until obtaining
Pale yellow powder, according to zirconium oxychloride: acetone is added in acetone=100g:300ml ratio, dissolves soluble matter, and filters pressing removes not
Molten triethylamine hydrochloride white precipitate obtains golden yellow filtrate, recycles acetone, until obtaining dry and hard faint yellow solid object, i.e.,
Poly- acetyl acetone zirconium precursor body.
(2) preparation of spinning solution
The poly- acetyl acetone zirconium precursor body of 100g is dissolved in 160g anhydrous methanol, according to yttrium oxide: (zirconium oxide+oxidation
Yttrium) yttrium nitrate hexahydrate 19.1g is added in=5.7% ratio, and stirring forms golden solution, passes through the method concentration of evaporation solvent
Solution, until obtaining transparent, the uniform and stable spinning solution that viscosity reaches 100Pas at 20 DEG C of room temperature.
(3) dry spinning
Spinning solution is moved into the liquid tank in device for spinning, vacuum defoamation 10min, is 20 DEG C and relative humidity in temperature
Under the conditions of 80%, applies the pressure of 1.8MPa to spinning solution with the mode of steel cylinder nitrogen or metering pump, make it from 30 holes, hole
The niobium tantalum alloy spinning plate that diameter is 0.05mm sprays, and through drawing-off and receives silk, obtains 30 μm of diameter, transparent, ordered arrangement, continuous
Precursor fibre.
(4) pressure parses
The poly- continuous precursor fibre of acetylacetone,2,4-pentanedione zirconium of above-mentioned acquisition is placed in the pressure vessel having been warmed up to 120 DEG C
In, in water vapour atmosphere, progress pressure dissection process under conditions of 2.2 atmospheric pressure of pressure and 134 DEG C is controlled, the time is handled
For 30min, then the gas in pressure vessel is discharged, will be further taken out after fiber placement 5min again after opening container door, according to
Ligand acetylacetone,2,4-pentanedione has 50% to be resolved out in weight difference calculating precursor fibre before and after the processing.
(5) high temperature is heat-treated
By pressure parsing, treated that fiber is placed in program-controlled sintering furnace, in the presence of water vapor, with the liter of 0.5 DEG C/min
Warm rate is warming up to 600 DEG C and keeps the temperature 1h, obtains continuous zirconia fiber.Tensile strength is in 0.2-0.5MPa.SEM photograph is as schemed
Shown in 1.
Embodiment 1:
A method of improve continuous zirconia fiber intensity and can prehensile, comprise the following steps that
Continuous zirconia fiber is rapidly entered into 1300 DEG C of high-temperature regions, the high-temperature region residence time is 2s, applies tension and is
Then fiber is directly placed in and cools down at room temperature by 50cN.The tensile strength of monfil is measured in 1.5GPa or so.SEM photograph
As shown in Fig. 2, crystal grain distribution figure is as shown in Figure 3.By Fig. 2,3 it is found that after the present embodiment is handled fiber dense uniform, fiber
Crystallite dimension is smaller, is mainly distributed on 80-100nm.
The continuous zirconia fiber that will be cooled to room temperature is orderly wound, and control winding linear velocity is 1000mm/min,
Tensity size is 150cN, and fiber roll is orderly and with certain fluffy degree.
Embodiment 2:
As described in Example 1, except that continuous zirconia fiber is rapidly entered 1400 DEG C of high-temperature regions, high-temperature region is stopped
Staying the time is 10s, and application tension is 100cN, is then directly placed in fiber and cools down at room temperature.Measure the stretch-proof of monfil
Intensity reaches as high as 3.0GPa in 2.0GPa or so.
The continuous zirconia fiber that will be cooled to room temperature is orderly wound, and control winding linear velocity is 2000mm/min,
Tensity size is 250cN, and fiber roll is orderly and arrangement is closer.
Embodiment 3:
As described in Example 1, except that continuous zirconia fiber is rapidly entered 1500 DEG C of high-temperature regions, high-temperature region is stopped
Staying the time is 30s, is then directly placed in fiber and cools down at room temperature, measures the tensile strength of monfil on the left side 1.6GPa
It is right.
The continuous zirconia fiber that will be cooled to room temperature is orderly wound, and control winding linear velocity is 1500mm/min,
Tensity size is 300cN, and fiber roll is orderly and arrangement is closer.
Embodiment 4:
As described in Example 1, except that continuous zirconia fiber is rapidly entered 1300 DEG C of high-temperature regions, high-temperature region is past
Again by 30 times, each residence time is 2s, and application tension is 150cN, is then directly placed in fiber and cools down at room temperature, measures
The tensile strength of monfil is in 1.5GPa or so.
The continuous zirconia fiber that will be cooled to room temperature is orderly wound, and control winding linear velocity is 1500mm/min,
Tensity size is 200cN, and fiber roll is orderly and arrangement is closer.
Embodiment 5:
As described in Example 1, except that continuous zirconia fiber is rapidly entered 1400 DEG C of high-temperature regions, high-temperature region is stopped
Staying the time is 30s, and application tension is 200cN, is then directly placed in fiber and cools down at room temperature, measures the stretch-proof of monfil
Intensity is in 1.8GPa or so.
The continuous zirconia fiber that will be cooled to room temperature is orderly wound, and control winding linear velocity is 2000mm/min,
Tensity size is 300cN, and fiber roll is orderly and arrangement is closer.
Comparative example 1:
As described in Example 1, except that continuous zirconia fiber is warming up to 1300 DEG C according to 3 DEG C/min, heat preservation
2s.The tensile strength of monfil is measured in 0.5-1.0GPa or so.Composition fiber crystal grain start to grow up, fibre strength compared with
1000 degree of declines are obvious, can prehensile it is poor.The SEM photograph of fiber grain size is as shown in figure 4, as shown in Figure 4, fiber crystal grain
It is larger.As it can be seen that crystal grain can gradually grow up with the promotion of temperature, between crystal grain by the fiber of slow temperature program processing
Binding force is greatly reduced, and fibre strength also weakens therewith.
Comparative example 2:
As described in Example 1, except that continuous zirconia fiber is rapidly entered 1000 DEG C of high-temperature regions.Measure monofilament
The tensile strength of fiber is smaller with the intensity difference of the continuous zirconia fiber obtained according to normal procedure in 1.0GPa or so.
It can be wound, but the use temperature spread apart from fiber is larger, fiber will appear biggish contraction in use.
Claims (10)
1. it is a kind of improve continuous zirconia fiber intensity and can prehensile method, comprise the following steps that
By continuous zirconia fiber fast transfer to 1200-1500 DEG C of high-temperature area, stays for some time, be then immediately placed in room
It is cooling under warm environment.
2. it is according to claim 1 improve continuous zirconia fiber intensity and can prehensile method, which is characterized in that
Residence time is 2-200s.
3. it is according to claim 2 improve continuous zirconia fiber intensity and can prehensile method, which is characterized in that
Residence time is 2-10s.
4. it is according to claim 1 improve continuous zirconia fiber intensity and can prehensile method, which is characterized in that
By continuous zirconia fiber fast transfer to 1400 DEG C of high-temperature areas, 10s is stopped, is then immediately placed under room temperature environment cooling.
5. it is according to claim 1 improve continuous zirconia fiber intensity and can prehensile method, which is characterized in that
When continuous zirconia fiber fast transfer to 1200-1500 DEG C of progress high-temperature residence, continuous zirconia fiber both ends, which apply, to be parted a little
Power, the size 20-200cN of tension.
6. it is according to claim 1 improve continuous zirconia fiber intensity and can prehensile method, which is characterized in that
The cooling high-intensitive continuous zirconia fiber obtained of room temperature is subjected to identical tension or constant linear velocity orderly winds to get coiled oxidation
Zirconium continuous fiber.
7. it is according to claim 6 improve continuous zirconia fiber intensity and can prehensile method, which is characterized in that
The Tensity size of winding is 50-300cN, linear velocity 200-2000mm/min.
8. it is according to claim 1 improve continuous zirconia fiber intensity and can prehensile method, which is characterized in that
Being placed in cooling procedure under room temperature environment is natural cooling.
9. it is according to claim 1 improve continuous zirconia fiber intensity and can prehensile method, which is characterized in that
Continuous zirconia fiber obtains as follows:
(1) preparation of poly- acetyl acetone zirconium precursor body
1. in zirconium oxychloride: dehydrated alcohol=100g:640~800g ratio weighs zirconium oxychloride raw material and is dissolved in dehydrated alcohol
In, acetylacetone,2,4-pentanedione is added and stirs 1~2 hour；Triethylamine-alcohol mixed solution is added, is stirred to react 1~4 hour, must contain
The solution of poly- acetylacetone,2,4-pentanedione zirconium；Wherein, zirconium oxychloride: acetylacetone,2,4-pentanedione: triethylamine=1:1.8~2.0:1.9~2.5 mole
Than triethylamine in triethylamine-alcohol mixed solution: ethyl alcohol=35~45:100 volume ratio；
2. the solution containing poly- acetylacetone,2,4-pentanedione zirconium is removed etoh solvent through being concentrated under reduced pressure, powder is obtained, according to zirconium oxychloride: third
Acetone is added in ketone=100g:300~800mL ratio, dissolves soluble matter, and decompression, which filters, removes insoluble triethylamine hydrochloride white
Precipitating, gained filtrate is by being concentrated under reduced pressure recycling acetone, until obtaining dry powder to get poly- acetyl acetone zirconium precursor body；
(2) preparation of spinning solution
Poly- acetyl acetone zirconium precursor body is dissolved in anhydrous methanol, according to yttrium oxide: (zirconium oxide+yttrium oxide)=5.7~
The ratio addition yttrium salt of 8mol%, stirring form solution, and the method by evaporating solvent is concentrated, until acquisition viscosity 10~
Transparent, the uniform and stable spinning liquid as precursor of 100Pas, the viscosity are measured at 20 DEG C；
(3) dry spinning
Spinning liquid as precursor is moved into the liquid tank in device for spinning, 5~10min of vacuum defoamation, in 10~40 DEG C of temperature, phase
Under the conditions of humidity 20~80%, with the mode of steel cylinder nitrogen or metering pump to spinning solution 0.5~2.5MPa of pressurization, make it from hole
The spinneret orifice that diameter is 0.03~0.20mm sprays, and through multistage drafting and receives silk, obtains 10~40 μm of diameter of poly- acetyl acetone
Zirconium precursor body continuous fiber；
(4) pressure parses
Presoma continuous fiber is placed in the pressure vessel for being preheated to 90~130 DEG C, pressure control is 2~15 after being passed through atmosphere
A atmospheric pressure, heat temperature raising make 120~200 DEG C of temperature, carry out dissection process, the processing time is 5min~4h, so that forerunner
Ligand acetylacetone,2,4-pentanedione in body fiber parses；After dissection process, the steam of discharge enrichment acetylacetone,2,4-pentanedione holds pressure
Temperature in device is down to 80~100 DEG C, and the fiber after pressure is parsed continues to be placed in dry 5~30min in container, then takes
It is heat-treated out；
(5) it is heat-treated
By the parsing of step (4) pressure, treated that fiber is placed in sintering furnace is heat-treated, in the presence of steam, with 0.5~3
DEG C/heating rate of min is warming up to 500~800 DEG C, make poly- acetyl acetone zirconium precursor body that sufficiently parsing and crystallization conversion occur
For continuous oxidation zirconium crystal fibre.
10. a kind of high intensity can wind the preparation method of continuous zirconia fiber, comprise the following steps that
(1) preparation of poly- acetyl acetone zirconium precursor body
1. in zirconium oxychloride: dehydrated alcohol=100g:640~800g ratio weighs zirconium oxychloride raw material and is dissolved in dehydrated alcohol
In, acetylacetone,2,4-pentanedione is added and stirs 1~2 hour；Triethylamine-alcohol mixed solution is added, is stirred to react 1~4 hour, must contain
The solution of poly- acetylacetone,2,4-pentanedione zirconium；Wherein, zirconium oxychloride: acetylacetone,2,4-pentanedione: triethylamine=1:1.8~2.0:1.9~2.5 mole
Than triethylamine in triethylamine-alcohol mixed solution: ethyl alcohol=35~45:100 volume ratio；
2. the solution containing poly- acetylacetone,2,4-pentanedione zirconium is removed etoh solvent through being concentrated under reduced pressure, powder is obtained, according to zirconium oxychloride: third
Acetone is added in ketone=100g:300~800mL ratio, dissolves soluble matter, it is heavy that filters pressing removes insoluble triethylamine hydrochloride white
It forms sediment, gained filtrate is by being concentrated under reduced pressure recycling acetone, until obtaining dry powder to get poly- acetyl acetone zirconium precursor body；
(2) preparation of spinning solution
Poly- acetyl acetone zirconium precursor body is dissolved in anhydrous methanol, according to yttrium oxide: (zirconium oxide+yttrium oxide)=5.7~
The ratio addition yttrium salt of 8mol%, stirring form solution, and the method by evaporating solvent is concentrated, until acquisition viscosity 10~
Transparent, the uniform and stable spinning liquid as precursor of 100Pas, the viscosity are measured at 20 DEG C；
(3) dry spinning
Spinning liquid as precursor is moved into the liquid tank in device for spinning, 5~10min of vacuum defoamation, in 10~40 DEG C of temperature, phase
Under the conditions of humidity 20~80%, with the mode of steel cylinder nitrogen or metering pump to spinning solution 0.5~2.5MPa of pressurization, make it from hole
The spinneret orifice that diameter is 0.03~0.20mm sprays, and through multistage drafting and receives silk, obtains 10~40 μm of diameter of poly- acetyl acetone
Zirconium precursor body continuous fiber；
(4) pressure parses
Presoma continuous fiber is placed in the pressure vessel for being preheated to 90~130 DEG C, pressure control is 2~15 after being passed through atmosphere
A atmospheric pressure, heat temperature raising make 120~200 DEG C of temperature, carry out dissection process, the processing time is 5min~4h, so that forerunner
Ligand acetylacetone,2,4-pentanedione in body fiber parses；After dissection process, the steam of discharge enrichment acetylacetone,2,4-pentanedione holds pressure
Temperature in device is down to 80~100 DEG C, and the fiber after pressure is parsed continues to be placed in dry 5~30min in container, then takes
It is heat-treated out；
(5) it is heat-treated
By the parsing of step (4) pressure, treated that fiber is placed in sintering furnace is heat-treated, in the presence of steam, with 0.5~3
DEG C/heating rate of min is warming up to 500~800 DEG C, then by continuous zirconia fiber fast transfer to 1200-1500 DEG C of height
Temperature area stops 2-200s, and continuous zirconia fiber can be wound to get high intensity by being then immediately placed in cool down under room temperature environment.
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