CN107986797A - Solid union ceramic forerunner, composite fibre cotton and preparation method thereof - Google Patents
Solid union ceramic forerunner, composite fibre cotton and preparation method thereof Download PDFInfo
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- CN107986797A CN107986797A CN201711304618.7A CN201711304618A CN107986797A CN 107986797 A CN107986797 A CN 107986797A CN 201711304618 A CN201711304618 A CN 201711304618A CN 107986797 A CN107986797 A CN 107986797A
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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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/62236—Fibres based on aluminium oxide
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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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/6225—Fibres based on zirconium oxide, e.g. zirconates such as PZT
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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
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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
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
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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
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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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- Inorganic Fibers (AREA)
Abstract
The present invention relates to a kind of solid union ceramic forerunner, composite fibre cotton and preparation method thereof, poly- aikyiaiurnirsoxan beta and poly- zirconium oxygen alkane are first prepared as solid union ceramic forerunner by high temperature bunching, then cellucotton precursor is prepared into fibre by centrifugal drying silk or injection, further by curing, cracking, the technique such as sintering and prepare composite fibre cotton.The solid union ceramic forerunner softening point and rheological characteristic being prepared are adjustable, and cost is relatively low, solvent-free, environmentally protective in follow-up spinning operations, and fiber precursor is insensitive to humidity in air, easy to large-scale production.And preparation-obtained composite fibre cotton pliability is splendid, mechanical behavior under high temperature is excellent, and can be widely used in the fields such as vehicle exhaust insulation blanket, high temperature filtration core carrier, Industrial Stoves heat-preservation cotton.
Description
Technical field
The present invention relates to a kind of solid union ceramic forerunner, composite fibre cotton and preparation method thereof.
Background technology
Pure phase alumina fibre has good performance at a temperature of less than 1200 DEG C, but when temperature is after of continuing rising
Height, the crystallite dimension in simple alumina fibre can increased dramatically, so as to influence its applied at elevated temperature performance.Therefore it is usually added into certain
The heterogeneous element of amount such as SiO2、ZrO2Etc. preparing phase containing mullite, ZrO2The composite fibre of Tetragonal.
Viscosity is low after the fusing point height of aluminium oxide-zirconium oxide composite ceramics and thawing, traditional melt drawing technique can not be used
Production.Chemical method is to prepare the main production line of ceramic fibre, more at present to prepare alumina-silica using sol-gal process
Zirconium composite fibre cotton.
Chinese patent CN102465357A discloses a kind of polycrystal zirconia fiber and zirconium oxide/alumina composite fiber
Preparation method, its prepare colloidal sol contain Cl elements, the discharge of HCl pernicious gases is had in sintering process, thus to environment,
Equipment and personnel safety have adverse effect on；Spinning-aid agent is introduced in another aspect spinning system, adds cost of spinning
And during Post isothermal treatment, leaving away for spinning-aid agent can adversely affect the structure of fiber.
Chinese patent CN103408292A discloses a kind of preparation method of alumina-zirconia ceramic fiber, it is prepared
The process of colloidal sol is complicated, it is necessary to the viscosity of gel be controlled by aging technique, to adapt to spinning to colloid rheological property
It is required that；And fiber precursor is more sensitive to the humidity in air in spinning process, and condition is harsher, precursor is easily adhered simultaneously
Silk, or even in the pasty state.
For these reasons, it is special to propose the present invention.
The content of the invention
, should it is an object of the invention to provide a kind of solid union ceramic forerunner, composite fibre cotton and preparation method thereof
Preparation method technique is simple, cost is relatively low, environmentally friendly, and the Zirconium oxide fibre cotton being prepared has superior function, tool
There is larger application prospect.
To reach above-mentioned purpose, the present invention provides following technical solution：A kind of preparation side of solid union ceramic forerunner
Method, comprises the following steps：
Poly- aikyiaiurnirsoxan beta and poly- zirconium oxygen alkane are provided, the poly- aikyiaiurnirsoxan beta and poly- zirconium oxygen alkane are mixed, and is obtained by high temperature bunching
To the solid union ceramic forerunner.
Further, in the solid union ceramic forerunner, the quality proportioning of zr element and aluminium element is converted into
ZrO2:Al2O3, it is preferably X：(10-X), wherein 1≤X≤9.
Further, during the high temperature bunching, temperature is preferably 120-200 DEG C.
Further, it is carried out at the same time vacuum distillation during the high temperature bunching.
To reach above-mentioned purpose, the present invention provides also following technical solution：One kind is by the solid union ceramic forerunner
Preparation method obtained by solid union ceramic forerunner, the softening point of the solid union ceramic forerunner is located at 50-125
℃。
To reach above-mentioned purpose, the present invention provides and and for example descends technical solution：A kind of preparation method of composite fibre cotton, including
Following steps：
S1, provide spinning material, and the spinning material includes the solid union ceramic forerunner, by the spinning material
Cellucotton precursor is obtained by spinning technique；
S2, by the cellucotton precursor cured and cracked, to obtain fiber cotton fabric；
S3, by the fiber cotton fabric after cracking be sintered with superhigh temperature processing, to obtain the composite fibre cotton.
Further, in step S1, the spinning technique includes centrifugal drying silk, the specific steps bag of the centrifugal drying silk
Include：
The spinning material is placed in centrifugation tumbling machine, heat up heating in nitrogen atmosphere, treats that the spinning material melts
After melting as uniform melt and removing residual bubbles, the wire hole high speed of getting rid of of the melt from the centrifugation tumbling machine is thrown away,
To obtain cellucotton precursor.
Further, the condition of the centrifugal drying silk includes：The temperature of the heating heating is preferably 110-180 DEG C, institute
State centrifugation tumbling machine rotating speed be preferably 4000-20000r/min, it is described centrifugation tumbling machine wire tray aperture of getting rid of be preferably 0.1-
0.5mm。
Further, in step S1, the spinning technique includes injection into fibre, specific steps bag of the injection into fibre
Include：
The spinning material is placed in blowing device, heating is heated to the spinning material and melts completely, in the spray
Blow and be blown in equipment into fibre to obtain cellucotton precursor.
Further, the injection includes into fine condition：Temperature is preferably 100-220 DEG C, air pressure is preferably 0.05-
0.6MPa, hydraulic pressure are preferably that the angle of 0.05-0.15Mpa, spinneret liquid direction and airflow direction are preferably 20-70 °.
Further, in step S2, the cured specific steps include：
The cellucotton precursor is placed in climatic chamber, is first warming up to 30-40 DEG C, in the relative humidity of 30-45%
Lower insulation 20min-2h, then 60-95 DEG C is warming up to, 10min-2h is kept the temperature under the humidity of 60-95%, is cooled to room temperature and is consolidated
The fiber cotton fabric of change.
Further, in step S2, the specific steps of the cracking include：
Cellucotton fabric after curing is placed in high temperature furnace and is warming up to 500-800 DEG C with 0.5-30 DEG C/min, and is being split
Insulation 30min-2h is cracked in solution atmosphere.
Further, one kind in nitrogen, argon gas, helium and air is included for forming the gas of the cracking atmosphere
Or more than one gases.
Further, in step S3, the specific steps of the sintering include：
Fiber cotton fabric after cracking is warming up to 1000- in air atmosphere with the heating rate of 0.15-100 DEG C/min
1800 DEG C, sintering processes 1min-10h.
Further, the composite fibre cotton is Zirconia-alumina composite fibre cotton, and the zirconium oxide is preferably t-
ZrO2, the aluminium oxide is preferably γ-Al2O3Or α-Al2O3。
To reach above-mentioned purpose, the present invention provides technical solution as follows：A kind of preparation by the composite fibre cotton
Composite fibre cotton obtained by method.
Compared with prior art, the beneficial effects of the present invention are：
(1) preparation method of solid union ceramic forerunner of the invention passes through after mixing poly- aikyiaiurnirsoxan beta and poly- zirconium oxygen alkane
High temperature bunching obtains solid union ceramic forerunner, and the solid union ceramic forerunner is cheap as spinning material, and its
Softening point and rheological characteristic are adjustable, and two component compatibility of Zr, Al is good, and ratio is adjustable.Meanwhile spinning material of the present invention
In be free of spin finish aid, avoid spin finish aid under high temperature leave away cause fiber volume shrink and mechanical property loss it is unfavorable
Influence.
(2) composite fibre cotton Preparation Method of the invention prepares cellucotton using centrifugal drying silk or injection fiber-forming process,
The spinning technique stable system, fiber precursor are insensitive to the humidity of spinning environment, avoid solution and get rid of fibre prepared by a technique
Dimension precursor is easily adhered and the problem of silk even in the pasty state.
(3) whole technique is environmentally protective, can quickly accomplish scale production, and the cellucotton sample finally prepared is flexible
Property is splendid, and mechanical behavior under high temperature is excellent.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate attached drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the process step figure of the preparation method of the composite fibre cotton of the present invention；
Fig. 2 is the SEM figures of the composite fibre cotton shown in the embodiment of the present invention one；
Fig. 3 is the XRD diagram of the composite fibre cotton shown in the embodiment of the present invention one；
Fig. 4 is the XRD diagram of the composite fibre cotton shown in the embodiment of the present invention two.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
The preparation method of the solid union ceramic forerunner of the present invention, comprises the following steps：
Poly- aikyiaiurnirsoxan beta and poly- zirconium oxygen alkane are provided, are 120-200 in temperature after the poly- aikyiaiurnirsoxan beta and poly- zirconium oxygen alkane are mixed
The solid union ceramic forerunner is obtained by high temperature bunching under conditions of DEG C, and during the high temperature bunching at the same time
It is evaporated under reduced pressure.
Pass through the solid union ceramic forerunner obtained by the preparation method of the solid union ceramic forerunner, its softening point
Positioned at 70-125 DEG C, and the quality proportioning of zr element and aluminium element is converted into ZrO2:Al2O3, it is preferably X：(10-X), wherein 1≤
X≤9。
Fig. 1 is referred to, the preparation method of composite fibre cotton of the invention, comprises the following steps：
S1, provide spinning material, and the spinning material includes the solid union ceramic forerunner, and the spinning is former
Material is placed in centrifugation tumbling machine, and the wire tray aperture of getting rid of of the centrifugation tumbling machine is preferably 0.1-0.5mm, by spinning material in nitrogen gas
Heating is heated to 110-180 DEG C of preferable temperature in atmosphere, treats the spinning material melting as uniform melt and removes residual bubbles
Afterwards, the melt is thrown away at a high speed from the getting rid of in wire hole for centrifugation tumbling machine with the preferred rotating speed of 4000-20000r/min, with
Obtain cellucotton precursor；
Alternatively,
Spinning material is provided, the spinning material includes the solid union ceramic forerunner, by the spinning material
It is placed in blowing device, heating is heated to 100-220 DEG C of preferable temperature, excellent in air pressure after the spinning material completely melting
Elect 0.05-0.6MPa as, hydraulic pressure is preferably 0.05-0.15MPa, and spinneret liquid flow path direction and airflow direction angle are preferably 20-70 °
Under conditions of, fibre is blown into, obtains cellucotton precursor.
The cellucotton precursor, be placed in climatic chamber by S2,30-40 DEG C is first warming up to, in the relatively wet of 30-45%
The lower insulation 20min-2h of degree, then 60-95 DEG C is warming up to, 10min-2h is kept the temperature under the humidity of 60-95%, is cooled to room temperature to obtain
Cured fiber cotton fabric；
Cellucotton fabric after curing, be placed in high temperature furnace and be warming up to 500-800 DEG C with 0.5-30 DEG C/min by S3, and
Cracking atmosphere in insulation 30min-2h cracked, for formed it is described cracking atmosphere gas include nitrogen, argon gas, helium with
And one or more mixed gas in air；
Fiber cotton fabric after cracking, be warming up to by S4 in air atmosphere with the heating rate of 0.15-100 DEG C/min
1000-1800 DEG C, sintering processes 1min-10h, to obtain the composite fibre cotton.
Below in conjunction with specific embodiments come to the present invention illustrated in further detail.
Embodiment one
1. the preparation of solid union ceramic forerunner：
By the poly- aikyiaiurnirsoxan betas of 500g (Poly aluminoxane, PAO) and the poly- zirconium oxygen alkane of 40g (Polyzirconoxane,
PNZ) it is mixed and stirred for that uniformly, mixed liquor is placed in reaction kettle, 100 DEG C is heated under stirring, 1h is evaporated under reduced pressure, continues to heat up
To 120 DEG C and 1h is kept the temperature, then stops heating, room temperature is down under nitrogen protection and obtains solid-state zirconium-aluminium that softening point is 85 DEG C
Composite ceramics presoma, and the quality proportioning of zr element and aluminium element is converted into ZrO2:Al2O3For 1:9.
2. the preparation of composite fibre cotton：
Spinning material comprising the solid-state zirconium-aluminium composite ceramics presoma, be placed in there-necked flask by S1, is protected in nitrogen
Lower heating is heated to 110 DEG C, and after its melting for uniform melt and after removing residual bubbles, quickly and evenly pouring into rotating speed is
5000r/min, gets rid of the tumbling machine that wire tray aperture is 0.4mm, and melt spinning raw material is thrown away from wire hole high speed is got rid of, and it is fine to obtain presoma
Tie up precursor；
S2, by S1 gained precursor fibre precursor be placed in climatic chamber, be first warming up to 40 DEG C, 30% it is opposite
30min is kept the temperature under humidity, then is warming up to 90 DEG C, 20min is kept the temperature under 80% humidity, is cooled to room temperature to obtain cured fiber；
Gained cured fiber in S2, be placed in high temperature furnace and be warming up to 700 DEG C with 1 DEG C/min by S3, keeps the temperature 1h, cracks atmosphere
For air；
S4, by S3 gained cracking after fiber cotton fabric 1200 DEG C of processing are warming up to the heating rate of 30 DEG C/min
20min, sintering atmosphere are air, you can obtain-the Al containing γ2O3With t-ZrO2The Zirconia-alumina composite fibre cotton of crystalline phase.
Fig. 2 and Fig. 3 are referred to, the SEM of the composite fibre cotton according to obtained by the preparation method of the composite fibre cotton shines
Piece and XRD spectra are as shown in the figure.As can be seen from Figure, fiber surface is smooth, size uniform, and fibre diameter is 2-4 μm；XRD results
Show, the crystalline phase composition of fiber is γ-Al2O3With t-ZrO2。
Embodiment two
1. the preparation of solid union ceramic forerunner：
500g PAO and 40g PNZ are mixed and stirred for that uniformly, mixed liquor is placed in reaction kettle, are heated under stirring
100 DEG C, 1h is evaporated under reduced pressure, 120 DEG C is continuously heating to and keeps the temperature 1h, then stopped heating, be down to room temperature under nitrogen protection and obtain
To solid-state zirconium-aluminium composite ceramics presoma that softening point is 85 DEG C, and the quality proportioning of zr element and aluminium element is converted into ZrO2:
Al2O3For 1:9.
2. the preparation of composite fibre cotton：
Spinning material comprising the solid-state zirconium-aluminium composite ceramics presoma, is poured into the liquid material for being blown device for spinning by S1
Guan Zhong, adjusts the temperature of liquid material pipe to 135 DEG C, and melting spinning is carried out for uniform melt and after removing residual bubbles after its melting
Silk, control pressure 0.45MPa, hydraulic pressure 0.08MPa, it is in about 60 ° of angles to keep liquid flow path direction and airflow direction, is blown out forerunner
Body fiber precursor, fibre length about 15cm, size uniform and without slag ball；
S2, by S1 gained precursor fibre precursor be placed in climatic chamber, be first warming up to 40 DEG C, 30% it is opposite
20min is kept the temperature under humidity, then is warming up to 90 DEG C, 20min is kept the temperature under 80% humidity, is cooled to room temperature to obtain cured fiber；
Gained cured fiber in S2, be placed in high temperature furnace and be warming up to 600 DEG C with 1 DEG C/min by S3, keeps the temperature 1h, cracks atmosphere
For air；
S4, by S3 gained cracking after fiber cotton fabric 1400 DEG C of processing are warming up to the heating rate of 30 DEG C/min
10min, sintering atmosphere are air, you can obtain-the Al containing γ2O3With t-ZrO2The Zirconia-alumina composite fibre cotton of crystalline phase,
Refer to Fig. 4.
Embodiment three
1. the preparation of solid union ceramic forerunner：
500g PAO and 320g PNZ are mixed and stirred for that uniformly, mixed liquor is placed in reaction kettle, are heated under stirring
180 DEG C, it is evaporated under reduced pressure and keeps the temperature 1h, then stop heating, is down to room temperature under nitrogen protection and obtains softening point and be 97 DEG C consolidating
State zirconium-aluminium composite ceramics presoma, and the quality proportioning of zr element and aluminium element is converted into ZrO2:Al2O3For 1:1.
2. the preparation of composite fibre cotton：
Spinning material comprising the solid-state zirconium-aluminium composite ceramics presoma, be placed in there-necked flask by S1, is protected in nitrogen
Lower heating is heated to 145 DEG C, and after its melting for uniform melt and after removing residual bubbles, quickly and evenly pouring into rotating speed is
5000r/min, gets rid of the tumbling machine that wire tray aperture is 0.4mm, and melt spinning raw material is thrown away from wire hole high speed is got rid of, and it is fine to obtain presoma
Tie up precursor；
S2, by S1 gained precursor fibre precursor be placed in climatic chamber, 80 DEG C are warming up to, under 80% humidity
20min is kept the temperature, is cooled to room temperature to obtain cured fiber；
Gained cured fiber in S2, be placed in high temperature furnace and be warming up to 600 DEG C with 5 DEG C/min by S3, keeps the temperature 2h, cracks atmosphere
For air；
S4, by S3 gained cracking after fiber cotton fabric with the heating rate of 30 DEG C/min be warming up to 1450 DEG C processing 1h,
Sintering atmosphere is air, you can obtains Zirconia-alumina composite fibre cotton.
Example IV
1. the preparation of solid union ceramic forerunner：
500g PAO and 320g PNZ are mixed and stirred for that uniformly, mixed liquor is placed in reaction kettle, are heated under stirring
180 DEG C, it is evaporated under reduced pressure and keeps the temperature 1h, then stop heating, is down to room temperature under nitrogen protection and obtains softening point and be 97 DEG C consolidating
State zirconium-aluminium composite ceramics presoma, and the quality proportioning of zr element and aluminium element is converted into ZrO2:Al2O3For 1:1.
2. the preparation of composite fibre cotton：
Spinning material comprising the solid-state zirconium-aluminium composite ceramics presoma, is poured into the liquid material for being blown device for spinning by S1
Guan Zhong, adjusts the temperature of liquid material pipe to 150 DEG C, and melting spinning is carried out for uniform melt and after removing residual bubbles after its melting
Silk, control pressure 0.45MPa, hydraulic pressure 0.08MPa, it is in about 55 ° of angles to keep liquid flow path direction and airflow direction, is blown out forerunner
Body fiber precursor, fibre length about 15cm, size uniform and without slag ball；
S2, by S1 gained precursor fibre precursor be placed in climatic chamber, 75 DEG C are warming up to, under 80% humidity
30min is kept the temperature, is cooled to room temperature to obtain cured fiber；
Gained cured fiber in S2, be placed in high temperature furnace and be warming up to 800 DEG C with 1 DEG C/min by S3, keeps the temperature 1h, cracks atmosphere
For air；
S4, by S3 gained cracking after fiber with the heating rate of 30 DEG C/min be warming up to 1400 DEG C processing 150min, burn
Knot atmosphere is air, you can obtains Zirconia-alumina composite fibre cotton.
Embodiment five
1. the preparation of solid union ceramic forerunner：
56g PAO and 320g PNZ are mixed and stirred for that uniformly, mixed liquor is placed in reaction kettle, are heated under stirring
170 DEG C, it is evaporated under reduced pressure and keeps the temperature 1h, then stop heating, is down to room temperature under nitrogen protection and obtains softening point and be 107 DEG C consolidating
State zirconium-aluminium composite ceramics presoma, and the quality proportioning of zr element and aluminium element is converted into ZrO2:Al2O3For 9:1.
2. the preparation of composite fibre cotton：
Spinning material comprising the solid-state zirconium-aluminium composite ceramics presoma, be placed in there-necked flask by S1, is protected in nitrogen
Lower heating is heated to 160 DEG C, and after its melting for uniform melt and after removing residual bubbles, quickly and evenly pouring into rotating speed is
4000r/min, gets rid of the tumbling machine that wire tray aperture is 0.4mm, and melt spinning raw material is thrown away from wire hole high speed is got rid of, and it is fine to obtain presoma
Tie up precursor；
S2, by S1 gained precursor fibre precursor be placed in climatic chamber, 80 DEG C are warming up to, under 80% humidity
20min is kept the temperature, is cooled to room temperature to obtain cured fiber；
Gained cured fiber in S2, be placed in high temperature furnace and be warming up to 600 DEG C with 5 DEG C/min by S3, keeps the temperature 2h, cracks atmosphere
For air；
S4, by S3 gained cracking after fiber with the heating rate of 10 DEG C/min be warming up to 1200 DEG C processing 2h, sinter gas
Atmosphere is air, you can obtains Zirconia-alumina composite fibre cotton.
Embodiment six
1. the preparation of solid union ceramic forerunner：
56g PAO and 320g PNZ are mixed and stirred for that uniformly, mixed liquor is placed in reaction kettle, are heated under stirring
170 DEG C, it is evaporated under reduced pressure and keeps the temperature 1h, then stop heating, is down to room temperature under nitrogen protection and obtains softening point and be 107 DEG C consolidating
State zirconium-aluminium composite ceramics presoma, and the quality proportioning of zr element and aluminium element is converted into ZrO2:Al2O3For 9:1.
2. the preparation of composite fibre cotton：
Spinning material comprising the solid-state zirconium-aluminium composite ceramics presoma, is poured into the liquid material for being blown device for spinning by S1
Guan Zhong, adjusts the temperature of liquid material pipe to 170 DEG C, and melting spinning is carried out for uniform melt and after removing residual bubbles after its melting
Silk, control pressure 0.45MPa, hydraulic pressure 0.08MPa, it is in about 55 ° of angles to keep liquid flow path direction and airflow direction, is blown out forerunner
Body fiber precursor, fibre length about 15cm, size uniform and without slag ball；
S2, by S1 gained precursor fibre precursor be placed in climatic chamber, 75 DEG C are warming up to, under 80% humidity
30min is kept the temperature, is cooled to room temperature to obtain cured fiber；
Gained cured fiber in S2, be placed in high temperature furnace and be warming up to 800 DEG C with 1 DEG C/min by S3, keeps the temperature 1h, cracks atmosphere
For air；
S4, by S3 gained cracking after fiber cotton fabric with the heating rate of 30 DEG C/min be warming up to 1450 DEG C processing 1h,
Sintering atmosphere is air, you can obtains Zirconia-alumina composite fibre cotton.
Comparative example
In summary：The preparation method of the solid union ceramic forerunner of the present invention mixes poly- aikyiaiurnirsoxan beta and poly- zirconium oxygen alkane
Solid union ceramic forerunner is obtained by high temperature bunching afterwards, the solid union ceramic forerunner is low as spinning material, price
It is honest and clean, and its softening point and rheological characteristic are adjustable, two component compatibility of Zr, Al is good, and ratio is adjustable.It is meanwhile of the present invention
Spin finish aid is free of in spinning material, avoiding leaving away for spin finish aid under high temperature causes fiber volume to shrink and mechanical property energy loss
The adverse effect of mistake.
Also, the composite fibre cotton Preparation Method of the present invention prepares fiber using centrifugal drying silk or injection fiber-forming process
Cotton, the spinning technique stable system, fiber precursor is insensitive to the humidity of spinning environment, avoids solution and gets rid of prepared by a technique
Fiber precursor is easily adhered and the problem of silk even in the pasty state.
Meanwhile in preparation method of the invention, whole technique is environmentally protective, can quickly accomplish scale production, and most
The cellucotton sample pliability prepared eventually is splendid, and mechanical behavior under high temperature is excellent.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, its description is more specific and detailed, but simultaneously
Cannot therefore it be construed as limiting the scope of the patent.It should be pointed out that come for those of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (15)
1. a kind of preparation method of solid union ceramic forerunner, it is characterised in that comprise the following steps：
Poly- aikyiaiurnirsoxan beta and poly- zirconium oxygen alkane are provided, the poly- aikyiaiurnirsoxan beta and poly- zirconium oxygen alkane are mixed, and institute is obtained by high temperature bunching
State solid union ceramic forerunner.
2. solid union ceramic forerunner as claimed in claim 1, it is characterised in that in the solid union ceramic forerunner
In, the quality proportioning of zr element and aluminium element is converted into ZrO2:Al2O3, it is preferably X：(10-X), wherein 1≤X≤9.
3. the preparation method of solid union ceramic forerunner as claimed in claim 1, it is characterised in that in the high temperature bunching
During, temperature is preferably 120-200 DEG C.
4. the preparation method of solid union ceramic forerunner as claimed in claim 1, it is characterised in that in the high temperature bunching
During be carried out at the same time vacuum distillation.
It is 5. a kind of as consolidating obtained by the preparation method of the solid union ceramic forerunner described in any one of claims 1 to 4
State composite ceramics presoma, it is characterised in that the softening point of the solid union ceramic forerunner is located at 50-125 DEG C.
6. a kind of preparation method of composite fibre cotton, it is characterised in that comprise the following steps：
S1, provide spinning material, and the spinning material includes solid union ceramic forerunner as claimed in claim 5, by institute
State spinning material and cellucotton precursor is obtained by spinning technique；
S2, by the cellucotton precursor cured and cracked, to obtain fiber cotton fabric；
S3, by the fiber cotton fabric after cracking be sintered with superhigh temperature processing, to obtain the composite fibre cotton.
7. the preparation method of composite fibre cotton as claimed in claim 6, it is characterised in that in step S1, the spinning technique
Including centrifugal drying silk, the specific steps of the centrifugal drying silk include：
The spinning material is placed in centrifugation tumbling machine, heat up heating in nitrogen atmosphere, treats that the spinning material melting is
Uniform melt and after removing residual bubbles, the wire hole high speed of getting rid of of the melt from the centrifugation tumbling machine is thrown away, with
To cellucotton precursor.
8. the preparation method of composite fibre cotton as claimed in claim 7, it is characterised in that the condition bag of the centrifugal drying silk
Include：The temperature of the heating heating is preferably 110-180 DEG C, the rotating speed of the centrifugation tumbling machine is preferably 4000-20000r/
Min, the wire tray aperture of getting rid of of the centrifugation tumbling machine are preferably 0.1-0.5mm.
9. the preparation method of composite fibre cotton as claimed in claim 6, it is characterised in that in step S1, the spinning technique
Include including injection into fibre, the injection into fine specific steps：
The spinning material is placed in blowing device, heating is heated to the spinning material and melts completely, is set in the injection
It is blown for middle into fibre to obtain cellucotton precursor.
10. the preparation method of composite fibre cotton as claimed in claim 9, it is characterised in that condition bag of the injection into fibre
Include：Temperature is preferably 100-220 DEG C, air pressure is preferably that 0.05-0.6MPa, hydraulic pressure are preferably 0.05-0.15Mpa, spinneret liquid side
It it is preferably 20-70 ° to the angle with airflow direction.
11. the preparation method of composite fibre cotton as claimed in claim 6, it is characterised in that in step S2, the cured tool
Body step includes：
The cellucotton precursor is placed in climatic chamber, is first warming up to 30-40 DEG C, is protected under the relative humidity of 30-45%
Warm 20min-2h, then 60-95 DEG C is warming up to, 10min-2h is kept the temperature under the humidity of 60-95%, is cooled to room temperature to obtain cured
Fiber cotton fabric.
12. the preparation method of composite fibre cotton as claimed in claim 6, it is characterised in that in step S2, the tool of the cracking
Body step includes：
Cellucotton fabric after curing is placed in high temperature furnace and is warming up to 500-800 DEG C with 0.5-30 DEG C/min, and in cracking gas
30min-2h is kept the temperature in atmosphere to be cracked.
13. the preparation method of composite fibre cotton as claimed in claim 12, it is characterised in that for forming the cracking atmosphere
Gas include nitrogen, argon gas, helium and air in one or more kinds of gases.
14. the preparation method of composite fibre cotton as claimed in claim 6, it is characterised in that in step S3, the tool of the sintering
Body step includes：
Fiber cotton fabric after cracking is warming up to 1000-1800 in air atmosphere with the heating rate of 0.15-100 DEG C/min
DEG C, sintering processes 1min-10h.
A kind of 15. composite fibre as obtained by the preparation method of the composite fibre cotton any one of claim 6 to 14
Cotton.
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| CN111074426A (en) * | 2019-12-26 | 2020-04-28 | 山东鲁阳浩特高技术纤维有限公司 | Alumina-zirconia composite fiber blanket and preparation method thereof |
| CN113968725A (en) * | 2020-07-22 | 2022-01-25 | 中国科学院化学研究所 | Al-Zr complex phase oxide continuous ceramic fiber and preparation method thereof |
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| CN113968725A (en) * | 2020-07-22 | 2022-01-25 | 中国科学院化学研究所 | Al-Zr complex phase oxide continuous ceramic fiber and preparation method thereof |
| CN113968725B (en) * | 2020-07-22 | 2022-09-16 | 中国科学院化学研究所 | Al-Zr complex phase oxide continuous ceramic fiber and preparation method thereof |
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