CN103993387B - A kind of preparation method of the superhigh temperature resistant continuous zirconia crystal fiber of km level - Google Patents
A kind of preparation method of the superhigh temperature resistant continuous zirconia crystal fiber of km level Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of superhigh temperature resistant continuous zirconia crystal fiber of km level.The method includes that the preparation of poly-acetyl acetone zirconium precursor body, the preparation of spinning liquid, dry spinning, pressure resolve and heat treatment, it is to prepare poly-acetyl acetone zirconium precursor body with zirconium oxychloride, acetylacetone,2,4-pentanedione, triethylamine for raw material, this presoma and stabilizer are dissolved in methanol in proportion, obtain the spinning liquid of 10～100Pa s through evaporation and concentration；This spinning liquid obtains poly-acetyl acetone zirconium precursor body continuous fiber through dry spinning；By this precursor fibre in pressure vessel, pressure, heat temperature raising dissection process is controlled after being passed through atmosphere, part acetylacetone,2,4-pentanedione in precursor fibre is parsed, take out after fiber drying, carry out middle high-temperature heat treatment, sintering obtains monofilament continuous length and reaches the continuous oxidation zirconium crystal fibre of thousands of meters, as superhigh temperature resistant heat-barrier material.
Description
Technical field
The present invention relates to the preparation method of a kind of high-performance superhigh temperature resistant continuous oxidation zirconium crystal fibre, particularly relate to a kind of poly-acetyl
The method that acetone zirconium system prepares continuous oxidation zirconium crystal fibre, belongs to Zirconium oxide fibre field of material technology.
Background technology
Continuous oxidation zirconium crystal fibre is a kind of 26S Proteasome Structure and Function material with very big application potential, space flight, military affairs and other
Current high-tech and sophisticated technology field, just playing the most important effect.
Zirconia crystal fiber is divided into chopped fiber and continuous fiber, due to the difficulty in Zirconium oxide fibre technology of preparing, leads in the world
The Zirconium oxide fibre that length is often more than 1 meter becomes continuous oxidation zirconium fiber.Crystalline material National Key Laboratory of Shandong University is permitted
The research team of east professor takes the lead in obtaining important breakthrough for 1998 in terms of the preparation of continuous zirconia fiber.Due to zirconium oxide itself
Fusing point high (2715 DEG C), and melt viscosity is less, and its fiber cannot use melted method to be prepared, and can only use each
The method planting presoma, concrete grammar has been described in patent CN1206397C.It is currently used for preparing continuous fiber
Still suffering from weak point in precursor synthesis method, such as make solvent with methanol, the water in reaction system only could be high finally
Temperature steams, and easily causes the hydrolysis of poly-zirconium precursor body, and then have impact on productivity and the degree of polymerization.
Summary of the invention
For the deficiencies in the prior art, it is to avoid the hydrolysis of poly-zirconium precursor body also improves productivity and the degree of polymerization, and the present invention provides one to adopt
The method preparing superhigh temperature resistant continuous oxidation zirconium crystal fibre by the newly synthesized system of poly-acetylacetone,2,4-pentanedione zirconium.
Technical scheme is as follows:
The preparation method of a kind of superhigh temperature resistant continuous zirconia crystal fiber of km level, comprises the steps:
1, the preparation of poly-acetyl acetone zirconium precursor body
(1) in zirconium oxychloride: the ratio of dehydrated alcohol=100g:640～800g, weigh zirconium oxychloride raw material and be dissolved in anhydrous second
In alcohol, add acetylacetone,2,4-pentanedione and stir 1～2 hour；Add triethylamine-alcohol mixed solution, stirring reaction 1～4 hour, obtain
Solution containing poly-acetylacetone,2,4-pentanedione zirconium；
Wherein, zirconium oxychloride: acetylacetone,2,4-pentanedione: triethylamine=1:1.8～2.0:1.9～2.5 mol ratios, in triethylamine-alcohol mixed solution
Triethylamine: ethanol=35～45:100 volume ratio.
(2) etoh solvent will be removed containing the solution of poly-acetylacetone,2,4-pentanedione zirconium through concentrating under reduced pressure, obtains powder, according to zirconium oxychloride:
The ratio of acetone=100g:300～800ml adds acetone, dissolves soluble substance, and filter pressing removes insoluble N,N-Diethylethanamine hydrochloride white precipitate,
Gained filtrate reclaims acetone by concentrating under reduced pressure, until obtaining dry powder, obtains poly-acetyl acetone zirconium precursor body.
2, the preparation of spinning liquid
Poly-acetyl acetone zirconium precursor body is dissolved in absolute methanol, according to yittrium oxide: (zirconium oxide+yittrium oxide)=5.7～8mol%
Ratio add yttrium salt, stirring formed solution, by evaporation solvent method concentrate, until obtain viscosity 10～100Pa s saturating
Bright, uniform, stable spinning liquid as precursor, described viscosity is measured when 20 DEG C.
3, dry spinning
Being moved into by spinning liquid as precursor in the liquid tank in device for spinning, vacuum defoamation 5～10min, in temperature 10～40 DEG C, phase
Under the conditions of humidity 20～80%, by the mode of steel cylinder nitrogen or dosing pump to spinning liquid pressurization 0.5～2.5MPa so that it is from aperture
It is the spinneret orifice ejection of 0.03～0.20mm, through multistage drafting and receipts silk, obtains the poly-acetylacetone,2,4-pentanedione zirconium of diameter 10～40 μm
Presoma continuous fiber.
4, pressure resolves
Being placed in by presoma continuous fiber in the pressure vessel being preheated to 90～130 DEG C, after being passed through atmosphere, Stress control is 2～15
Individual atmospheric pressure, heat temperature raising, making temperature is 120～200 DEG C, carries out dissection process, and the process time is 5min～4h so that front
The part acetylacetone,2,4-pentanedione driven in body fiber parses；After dissection process terminates, the steam of discharge enrichment acetylacetone,2,4-pentanedione makes pressure
Temperature in container is down to 80～100 DEG C, and the fiber after being resolved by pressure is dried 5～30min in continuing to be positioned over container, then
Taking-up carries out heat treatment.
5, heat treatment
Heat treatment is carried out in fiber after step 4 pressure dissection process is placed in sintering furnace, in the presence of steam, with
The heating rate of 0.5～3 DEG C/min is warming up to 500～800 DEG C, makes poly-acetyl acetone zirconium precursor body occur fully resolve and crystallize
It is converted into continuous oxidation zirconium crystal fibre；It is warming up to 1800～2200 DEG C with the heating rate of 3～6 DEG C/min, and is incubated 1～3h
It is sintered, it is thus achieved that the continuous oxidation zirconium crystal fibre of a diameter of 5～20 μm.
The monofilament continuous length of gained continuous oxidation zirconium crystal fibre of the present invention is more than km, long up to thousands of rice, is for list
The silk continuous length continuous zirconia crystal fiber of km level.The crystalline phase of gained continuous oxidation zirconium crystal fibre is complete stable cubic phase
Or Tetragonal and Emission in Cubic coexist.
According to currently preferred, the zirconium oxychloride raw material described in step 1 is eight hydration zirconium oxychlorides, molecular formula
ZrOCl2·8H2O。
According to currently preferred, described in step 2, yttrium salt is Yttrium trinitrate or Yttrium chloride(Y2Cl6), as stabilizer.Conventional yttrium salt is
Six water Yttrium trinitrates or six water Yttrium chloride(Y2Cl6)s.
According to currently preferred, spinning plate described in step 3 is niobium tantalum alloy spinning plate or platinum spinning plate.Spinning plate hole count
It is 1～1000, preferably 20～200, further preferred 30～100.Spinning plate aperture is preferably 0.05～0.1mm.
According to currently preferred, the atmosphere described in step 4 is the mixed gas of water vapour and alcohol vapour.Preferred volume ratio
Water vapour: alcohol vapour=1～the mixed atmosphere of 3:1.
According in step 4 of the present invention preferably, after being passed through atmosphere, Stress control is at 15 atmospheric pressure, and heat temperature raising makes the temperature be
200 DEG C, carrying out dissection process, the process time is 20min～1h；Or, after being passed through atmosphere, Stress control is at 2～4 air
Pressure, heat temperature raising makes temperature be 120～145 DEG C, carries out dissection process, and the process time is 30min～2h.
Y in step 2 of the present invention2O3: (Y2O3+ZrO2) mol ratio 5.7～8mol% be by disclosure satisfy that crystal of zirconium oxide is brilliant
The composition requirement coexisted for complete stable cubic phase or Tetragonal and Emission in Cubic mutually determines.When needing complete stable cubic phase
During zirconia crystal fiber, preferably Y2O3: (Y2O3+ZrO2) mol ratio be 6～8mol%；When needs Tetragonal is with vertical
Side coexist mutually zirconia crystal fiber time, preferably Y2O3: (Y2O3+ZrO2) mol ratio be more than or equal to 5.7mol%
Less than 6mol%.
According to currently preferred, the steam described in step 5 is water vapour.The sintering furnace used is program control sintering furnace, journey
Control sintering furnace is this area conventional equipment；Carry out middle high-temperature heat treatment.
Present invention advantage compared with prior art is as follows:
1, the method reaction system of the present invention uses dehydrated alcohol to make solvent, can be with ethanol-water azeotropic thing band during concentrating
Go out the water in reaction system, it is to avoid because of the hydrolysis of the poly-acetyl acetone zirconium precursor body that the residual of water causes, improving productivity
Meanwhile, the degree of polymerization and the stability of poly-acetylacetone,2,4-pentanedione zirconium are substantially increased.
2, the present invention use acetone as poly-acetylacetone,2,4-pentanedione zirconium and the separating medium of triethylamine hydrochloride, compared with oxolane,
Acetone is more stable, can repeatedly recycle, greatly reduce production cost.
3. the continuous precursor fibre that the present invention obtains through dry spinning resolves through high temperature pressure, can be by precursor fibre
Major part organic ligand is removed, and beneficially post processing and the nucleus of fiber is formed, and improves quality and the transparency of fiber.
4, the continuous oxidation zirconium crystal fibre that prepared by the present invention after 1800-2200 DEG C of superhigh temperature processes, excellent in mechanical performance,
Grain development is abundant, and composition is single, free from admixture, and purity is high, and monofilament continuous length reaches thousands of rice, is a kind of rare resistance to super
High temperature insulating material.
Accompanying drawing explanation
Fig. 1 is the precursor fibre that embodiment 1 step (3) dry spinning obtains；
Fig. 2 is the continuous oxidation zirconium crystal fibre after embodiment 1 step (5) heat treatment.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, but is not limited to this.
Embodiment 1:
(1) preparation of poly-acetyl acetone zirconium precursor body
1. 100g zirconium oxychloride ZrOCl is weighed2·8H2O, according to zirconium oxychloride: the ratio of dehydrated alcohol=100g:640g is molten
In dehydrated alcohol, it is zirconium oxychloride according to mol ratio: acetylacetone,2,4-pentanedione: the ratio of triethylamine=1:2.0:2.0 measures acetylacetone,2,4-pentanedione
31.1g and triethylamine 60.9g, is first slowly added to acetylacetone,2,4-pentanedione to the ethanol solution of zirconium oxychloride, stirs shape
Become mixed solution；Then the mixed solution (mixed proportion is 60.9g triethylamine: 160g ethanol) of triethylamine with ethanol is delayed
In slow addition extremely above-mentioned mixed solution, fully reaction stirring 2 hours, obtain golden yellow reactant liquor, i.e. contain poly-acetylacetone,2,4-pentanedione
The solution of zirconium.
2., under temperature 40～45 DEG C, vacuum 0.09MPa, etoh solvent and water are removed through concentrating under reduced pressure, until obtaining yellowish
Color powder, according to zirconium oxychloride: the ratio of acetone=100g:300ml adds acetone, dissolves soluble substance, and filter pressing removes insoluble
N,N-Diethylethanamine hydrochloride white precipitate, it is thus achieved that golden yellow filtrate, reclaim acetone, until obtaining dry and hard faint yellow solid thing, i.e.
Poly-acetyl acetone zirconium precursor body.
(2) preparation of spinning liquid
Poly-for 100g acetyl acetone zirconium precursor body is dissolved in 160g absolute methanol, according to yittrium oxide: (zirconium oxide+yittrium oxide)
The ratio of=5.7% adds six water Yttrium trinitrate 19.1g, and stirring forms golden solution, concentrates solution by the method for evaporation solvent,
Until obtaining viscosity at room temperature 20 DEG C to reach transparent, uniform, the stable spinning liquid of 100Pa s.
(3) dry spinning
Being moved into by spinning liquid in the liquid tank in device for spinning, vacuum defoamation 10min, is 20 DEG C and relative humidity 80% in temperature
Under the conditions of, spinning liquid is applied the pressure of 1.8MPa by the mode of steel cylinder nitrogen or dosing pump so that it is from 30 holes, hole
Footpath is the niobium tantalum alloy spinning plate ejection of 0.05mm, through drawing-off with receive silk, it is thus achieved that diameter 30 μm, transparent, ordered arrangement,
Continuous print precursor fibre, as shown in Figure 1.
(4) pressure resolves
The poly-continuous precursor fibre of acetylacetone,2,4-pentanedione zirconium of above-mentioned acquisition is placed in and has been warmed up to the pressure vessel of 120 DEG C,
In water vapour atmosphere, under conditions of controlling 2.2 atmospheric pressure of pressure and 134 DEG C, carry out pressure dissection process, process the time
For 30min, then the gas in pressure vessel is discharged, further take out after again fiber being placed 5min after opening container door, root
According to the weight difference before and after processing calculate part acetylacetone,2,4-pentanedione in precursor fibre have 50% resolved out.
(5) high-temperature heat treatment in: the fiber after pressure dissection process is placed in program control sintering furnace, in the presence of water vapor,
It is warming up to 500 DEG C with the heating rate of 0.5 DEG C/min, is warming up to 1600 DEG C with the heating rate of 3 DEG C/min, and is incubated 1h,
High-purity, grain development Tetragonal completely can be obtained and zirconia crystal fiber that Emission in Cubic coexists, ZrO2+Y2O3Content
Up to more than 99.95%, diameter 15 μm, transparent, orderly, continuous oxidation zirconium crystal fibre, as shown in Figure 2.
Embodiment 2:
As described in step (1) in embodiment 1,100g zirconium oxychloride is dissolved in 800g dehydrated alcohol, forms clear solution,
It is zirconium oxychloride according to mol ratio: acetylacetone,2,4-pentanedione: the ratio of triethylamine=1:2.2:1.8 measures acetylacetone,2,4-pentanedione 35g and triethylamine
55.1g, is now slowly added to acetylacetone,2,4-pentanedione to the ethanol solution of zirconium oxychloride, stirs 2 hours；Triethylamine is pressed with ethanol
Ratio according to 55.1g:160g forms mixed liquor, is slowly added to above-mentioned solution by this mixed liquor, fully reaction stirring 4
Hour, obtain golden yellow reactant liquor, i.e. contain the solution of poly-acetylacetone,2,4-pentanedione zirconium.
Embodiment 3:
As described in step (3) dry spinning in embodiment 1, being moved into by spinning liquid in the liquid tank in device for spinning, vacuum takes off
Bubble 10min, under the conditions of ambient temperature is 25 DEG C and relative humidity 40%, applies 2.0MPa with steel cylinder nitrogen to spinning liquid
Pressure so that it is from hole count be 100, aperture be 0.06mm niobium tantalum alloy spinning plate ejection, through multistage drafting and receive silk,
Obtain diameter 20 μm, transparent, ordered arrangement, continuous print precursor fibre.
Embodiment 4:
As described in embodiment 1, step (4) pressure resolves, the continuous precursor fibre that step (3) obtains is placed in
It is preheated in the pressure vessel of 120 DEG C, in water vapour atmosphere, under conditions of controlling 15 atmospheric pressure of pressure and 200 DEG C
Carrying out pressure dissection process, the process time is 1h, is then discharged by the gas in pressure vessel, opens after container door again by fibre
Dimension is placed after 5min and is further taken out, and has 90% according to what the weight difference before and after processing calculated part acetylacetone,2,4-pentanedione in precursor fibre
It is resolved out.
Embodiment 5:
As described in step (2) in embodiment 1, except that according to yittrium oxide: the ratio of (zirconium oxide+yittrium oxide)=8.0%
Example adds six water Yttrium trinitrates, and the amount of six water Yttrium trinitrates is adjusted to 27.6g by 19.1g.
Embodiment 6:
As described in step (2) in embodiment 1, except that according to yittrium oxide: the ratio of (zirconium oxide+yittrium oxide)=6.0%
Example adds six water Yttrium trinitrates, and the amount of six water Yttrium trinitrates is adjusted to 20.2g by 19.1g.
Embodiment 7:
As described in step (2) in embodiment 1, except that according to yittrium oxide: the ratio of (zirconium oxide+yittrium oxide)=5.7%
Example adds six water Yttrium chloride(Y2Cl6)s, and the amount of six water Yttrium trinitrates is adjusted to 15.1g by 19.1g.
Claims (4)
1. a preparation method for the continuous zirconia crystal fiber of superhigh temperature resistant km level, comprises the steps:
(1), the preparation of poly-acetyl acetone zirconium precursor body
1. in zirconium oxychloride: the ratio of dehydrated alcohol=100g:640～800g, weigh zirconium oxychloride raw material and be dissolved in dehydrated alcohol,
Add acetylacetone,2,4-pentanedione to stir 1～2 hour；Add triethylamine-alcohol mixed solution, stirring reaction 1～4 hour, poly-second must be contained
The solution of acyl acetone zirconium；
Wherein, zirconium oxychloride: acetylacetone,2,4-pentanedione: triethylamine=1:1.8～2.0:1.9～2.5 mol ratios, in triethylamine-alcohol mixed solution
Triethylamine: ethanol=35～45:100 volume ratio；
Described zirconium oxychloride raw material is eight hydration zirconium oxychlorides；
2. by removing etoh solvent containing the solution of poly-acetylacetone,2,4-pentanedione zirconium through concentrating under reduced pressure, powder is obtained, according to zirconium oxychloride: acetone
The ratio of=100g:300～800mL adds acetone, dissolves soluble substance, and filter pressing removes insoluble N,N-Diethylethanamine hydrochloride white precipitate, gained
Filtrate reclaims acetone by concentrating under reduced pressure, until obtaining dry powder, obtains poly-acetyl acetone zirconium precursor body；
(2), the preparation of spinning liquid
Poly-acetyl acetone zirconium precursor body is dissolved in absolute methanol, according to yittrium oxide: (zirconium oxide+yittrium oxide)=5.7～8mol%
Ratio add yttrium salt, stirring formed solution, by evaporation solvent method concentrate, until obtain viscosity 10～100Pa s saturating
Bright, uniform, stable spinning liquid as precursor, described viscosity is measured when 20 DEG C；
(3), dry spinning
Being moved into by spinning liquid as precursor in the liquid tank in device for spinning, vacuum defoamation 5～10min, at temperature 10～40 DEG C, relatively
Under the conditions of humidity 20～80%, by the mode of steel cylinder nitrogen or dosing pump to spinning liquid pressurization 0.5～2.5MPa so that it is from aperture be
The spinneret orifice ejection of 0.03～0.20mm, through multistage drafting and receipts silk, obtains the poly-acetyl acetone zirconium precursor of diameter 10～40 μm
Body continuous fiber；
(4), pressure resolves
Being placed in by presoma continuous fiber in the pressure vessel being preheated to 90～130 DEG C, after being passed through atmosphere, Stress control is at 15 air
Pressure, heat temperature raising makes temperature be 200 DEG C, carries out dissection process, and the process time is 20min～1h；Make in precursor fibre
Part acetylacetone,2,4-pentanedione parses；After dissection process terminates, the steam of discharge enrichment acetylacetone,2,4-pentanedione makes the temperature fall in pressure vessel
To 80～100 DEG C, the fiber after being resolved by pressure is dried 5～30min in continuing to be positioned over container, then takes out and carries out heat treatment；
(5), heat treatment
Heat treatment, in the presence of steam, described steaming is carried out in fiber after step (4) pressure dissection process is placed in sintering furnace
Vapour is water vapour, is warming up to 500～800 DEG C with the heating rate of 0.5～3 DEG C/min, makes poly-acetyl acetone zirconium precursor body fill
Decompose analysis and crystallization conversion is continuous oxidation zirconium crystal fibre；It is warming up to 1800～2200 DEG C with the heating rate of 3～6 DEG C/min,
And be incubated 1～3h and be sintered, it is thus achieved that the continuous oxidation zirconium crystal fibre of a diameter of 5～20 μm, monofilament continuous length km with
On.
2. the preparation method of the superhigh temperature resistant continuous zirconia crystal fiber of km level as claimed in claim 1, it is characterised in that step
Suddenly (3) described spinning plate is niobium tantalum alloy spinning plate or platinum spinning plate；Spinning plate hole count is 20～200.
3. the preparation method of the superhigh temperature resistant continuous zirconia crystal fiber of km level as claimed in claim 1, it is characterised in that step
(2) Y in2O3: (Y2O3+ZrO2) mol ratio be 6～8mol%, obtain the zirconia crystal fiber of complete stable cubic phase.
4. the preparation method of the superhigh temperature resistant continuous zirconia crystal fiber of km level as claimed in claim 1, it is characterised in that step
(2) Y in2O3: (Y2O3+ZrO2) mol ratio be less than 6mol% more than 5.7, obtain Tetragonal and oxidation that Emission in Cubic coexists
Zirconium crystal fibre.
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| CN106929927B (en) * | 2015-12-30 | 2020-03-24 | 山东大学 | Preparation method of polyacetylacetonatozirconium precursor sol spinning solution and submicron zirconia crystal fiber |
| CN105839227B (en) * | 2016-06-06 | 2018-05-04 | 山东大学 | A kind of method that electrostatic spinning prepares mesoporous zircite fiber |
| CN106757525A (en) * | 2016-12-12 | 2017-05-31 | 浙江嘉华晶体纤维有限公司 | A kind of production method of crystal fibre |
| CN107686351A (en) * | 2017-07-18 | 2018-02-13 | 中国科学院上海硅酸盐研究所 | A kind of zirconium carbide ceramics fiber and preparation method thereof |
| CN110483099B (en) * | 2019-08-23 | 2021-09-17 | 山东大学 | Method for improving strength and winding ability of zirconia continuous fiber |
| CN110911672A (en) * | 2019-11-06 | 2020-03-24 | 三峡大学 | Ga2O3Preparation method of/C nanowire lithium ion battery cathode material |
| CN112876244B (en) * | 2021-04-08 | 2022-06-24 | 齐鲁工业大学 | Strontium zirconate inorganic fiber and preparation method thereof |
| CN113023775A (en) * | 2021-04-08 | 2021-06-25 | 齐鲁工业大学 | Preparation method of ligand-modified zirconia sol and zirconia polycrystalline fiber |
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