CN105624834A - Barium zirconate fiber and method for preparing same - Google Patents
Barium zirconate fiber and method for preparing same Download PDFInfo
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- CN105624834A CN105624834A CN201610065710.1A CN201610065710A CN105624834A CN 105624834 A CN105624834 A CN 105624834A CN 201610065710 A CN201610065710 A CN 201610065710A CN 105624834 A CN105624834 A CN 105624834A
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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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Abstract
The invention relates to a barium zirconate fiber and a method for preparing the same. The diameter of the barium zirconate fiber is 1-20 micrometers, and crystalline phases of the barium zirconate fiber are cubic phases and can keep stable under the condition of high temperatures of 1500 DEG C. The method includes proportionally sufficiently stirring basic zirconium carbonate, barium sources, acid sources and solvents under the condition of temperatures of 10-90 DEG C until solution is clear and transparent, and concentrating the solution under vacuum conditions to obtain barium zirconate precursor spinning solution; carrying out high-speed centrifugal thread throwing on the precursor spinning solution to obtain a diameter precursor fiber and carrying out high-temperature heat treatment on the diameter precursor fiber to obtain the barium zirconate fiber. The barium zirconate fiber and the method have the advantages of simple processes, low cost, high yield, environmental friendliness and the like. Besides, the barium zirconate fiber is reliable in quality, has the uniform diameter and has a broad application prospect in the field of high-temperature heat-insulation materials, high-temperature proton conductors, fuel batteries and the like.
Description
Technical field
The present invention relates to a kind of barium zirconate fiber and preparation method thereof, belong to field of inorganic nonmetallic material.
Background technology
Barium zirconate (BaZrO3) belong to cubic perovskite structure, solid density 6.23g/cm3. Fusing point is up to 2690 DEG C, and thermal coefficient of expansion is little, is about 7.9 �� 10-6K-1(30-1000 DEG C), low grade fever capacitance, sintering activity is low, does not have phase transformation, Heat stability is good from-269 DEG C to 1327 DEG C, is a kind of excellent heat coating material; The preparation of barium zirconate powder body is referring to CN101319383A. On the other hand, there is not chemical reaction in barium zirconate and Yt-Ba-Cu-O superconductor, is the desirable crucible material of growth Yt-Ba-Cu-O superconductor; Preparation method referring to a CN103979979A barium zirconate crucible. Additionally, barium zirconate thermal conductivity is low, mechanically and structurally good stability, heat shock resistance under extreme environmental conditions, thermal shock resistance is good, is the high temperature insulating material of a kind of excellence; At present, as high temperature insulating material, existing more report prepared by barium zirconate ceramic material, for instance the preparation method that CN103864419A discloses a kind of high fine and close barium zirconate pottery. But compared with ceramic fibre, ceramic block material density is big, thermal conductivity is high, and heat-resistant knocking stability can be poor. But there is not yet the report about barium zirconate fibre technology up to now.
In recent years, global environment and energy problem, cause the extensive concern of people. Energy-conserving and environment-protective have become as the inevitable requirement of social development. Ceramic fibre is lightweight, specific heat capacity is little, mechanical resistant is vibrated, service efficiency advantages of higher is paid close attention to widely, current ceramic fibre material is used widely at industrial departments such as metallurgy, machinery, oil, chemical industry, electronics, boats and ships, transportation and light industry, and is applied to the frontiers of science and technology such as aerospace and atomic energy. Give full play to the advantage of fibrous material itself, suitable environment uses suitable material, improve the service efficiency of material and the energy, reduce cost and energy waste, improve the important research and development task that environment is Material Field. In order to make up the deficiency of barium zirconate Material Field, it is proposed to the present invention.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of resistant to elevated temperatures barium zirconate fibrous material and preparation method thereof, provides a novel product for barium zirconate high temperature insulating material.
Terminological interpretation:
Described barium zirconate, molecular formula is BaZrO3;
Described high temperature refers to up to 1500 DEG C of hot conditionss.
Technical scheme is as follows:
A kind of barium zirconate fiber, diameter is 1-20 ��m, and the crystalline phase of described barium zirconate fiber is Emission in Cubic, and keeps crystalline phase stable under up to 1500 DEG C of hot conditionss. Described barium zirconate fiber is tested respectively the XRD figure spectrum of different temperatures in 1300 DEG C, 1400 DEG C and 1500 DEG C, and result is as shown in Figure 5, it was shown that barium zirconate is Emission in Cubic, and under hot conditions, crystalline phase is stable.
High spot reviews of the present invention be up under 1500 DEG C of hot conditionss the crystalline phase stability of barium zirconate fiber; Self-evident, under room temperature, the crystalline phase of barium zirconate fiber is also very stable.
On the other hand, the present inventor it has been unexpectedly discovered that, described barium zirconate fiber remains in that fibre morphology well and sintering adhesion does not occur between fiber under up to 1500 DEG C of hot conditionss. As shown in Figure 4. This point key very can be accomplished, only under high temperature, fibre morphology is good and do not stick together between fiber its application of guarantee time convenience and excellent machinability.
Currently preferred, the diameter of described barium zirconate fiber is 2-15 ��m; It is preferred that, the diameter of described barium zirconate fiber is 4-8 ��m.
According to the present invention, the preparation method of a kind of barium zirconate fiber, comprise the following steps that
(1) it is zirconium oxycarbonate according to mol ratio: barium source: acid source=1:(1��1.5): the ratio of (2��6), weigh zirconium oxycarbonate, barium source and acid source respectively, join in solvent at 10��90 DEG C of temperature and stirring condition, carry out solution reaction, reaction 1��12h, obtains barium zirconate precursor solution;
(2) by step (1) gained barium zirconate precursor solution concentrating under reduced pressure at 30��70 DEG C of temperature, until obtain water white transparency, uniformly, viscosity be the barium zirconate precursor fibre spinning liquid of 10��50Pa s;
(3) it is centrifuged getting rid of silk by the barium zirconate precursor fibre spinning liquid that step (2) prepares, obtains barium zirconate precursor fibre;
(4) the barium zirconate precursor fibre that step (3) obtains is warming up to 600��800 DEG C with the heating rate of 1��3 DEG C/min under air conditions, is incubated 10-50min; Then being warming up to 1200��1500 DEG C with the heating rate of 3��5 DEG C/min again, insulation 1-2h obtains barium zirconate fiber.
According to currently preferred, step (1) described solvent load is acid source by volume: solvent=100:100��1000; Solvent described in step (1) is methanol, ethanol or its combination.
According to currently preferred, the barium source described in step (1) is brium carbonate, barium acetate one or a combination set of. When barium source is brium carbonate, feed molar proportioning is preferably zirconium oxycarbonate: brium carbonate: acid source=1:1:(4��6); When barium source is barium acetate, feed molar proportioning is preferably zirconium oxycarbonate: barium acetate: acid source=1:1:(2��4).
According to currently preferred, the acid source described in step (1) is glacial acetic acid, trifluoroacetic acid or its combination. When using the mixed acid of glacial acetic acid and trifluoroacetic acid, the mass ratio of glacial acetic acid and trifluoroacetic acid is 3:5-6.5.
According to currently preferred, the solution reaction temperature described in step (1) is 20��60 DEG C.
According to currently preferred, the concentrating under reduced pressure temperature described in step (2) is 40��60 DEG C;
According to currently preferred, the described centrifugal drying silk process conditions of step (3) are: getting rid of a temperature 10��35 DEG C, humidity 15��45%, centrifuge speed is 12000��30000r/min, getting rid of a hole linear velocity is 30��50m/s, and getting rid of an aperture is 0.2mm��0.5mm.
Barium zirconate fiberoptic fiber diameter prepared by the present invention is 1-20 ��m, it is preferable that 2-15 ��m, it is most preferred that 4-8 ��m; The crystalline phase of described barium zirconate fiber is Emission in Cubic, and keeps crystalline phase stable under up to 1500 DEG C of hot conditionss, and fibre morphology well and sintering adhesion does not occur between fiber.
The excellent results of the present invention is as follows:
1, the barium zirconate fibre crystallinity of the present invention can be good, uniform diameter, remains in that crystalline phase is stable, fibre morphology is good and sintering adhesion does not occur between fiber have good high temperature insulating performance under up to 1500 DEG C of hot conditionss. The barium zirconate fiber of the present invention at high temperature insulating material, high-temperature proton-conductor or/and there is wide application in the fields such as fuel cell.
2, the present invention selects zirconium oxycarbonate to be zirconium source, brium carbonate or barium acetate are barium source, glacial acetic acid or trifluoroacetic acid are acid source (part), methanol or ethanol are as solvent, barium zirconate precursor fibre spinning liquid is prepared when specific temperature, stirring, concentrating under reduced pressure, obtaining barium zirconate fiber again through centrifugal drying silk and high temperature sintering, preparation technology is simple, cost is low, productivity is high, environmental protection. Meanwhile, precursor sol is uniform and stable, and gained fiber quality is reliable and stable.
3, the barium zirconate fibre diameter that prepared by the present invention is 1-20 ��m, compared with pottery barium zirconate block materials, lightweight, specific heat capacity is little, mechanical resistant vibration, service efficiency are high, it may be achieved the energy-conserving and environment-protective requirement of high temperature insulating material.
Accompanying drawing explanation
Fig. 1 is the photo of the barium zirconate precursor fibre obtained in the embodiment of the present invention 1.
Fig. 2 is the photo of the barium zirconate fiber obtained in the embodiment of the present invention 1.
Fig. 3 is the SEM photograph of the barium zirconate fiber obtained in the embodiment of the present invention 1.
Fig. 4 is the SEM photograph of the barium zirconate fiber obtained in the embodiment of the present invention 2.
Fig. 5 is the XRD figure of the barium zirconate fiber different temperatures obtained in the embodiment of the present invention 1.
Detailed description of the invention
The present invention will be further described by the examples below and in conjunction with accompanying drawing, but is not limited to this.
The raw materials used convenient source that is in embodiment, device therefor is conventional equipment, commercial products.
Embodiment 1: prepare barium zirconate fiber as acid source with acetic acid
(1) weighing 31.80g zirconium oxycarbonate, 19.74g brium carbonate, in beaker, is subsequently adding 24g glacial acetic acid, 24g methanol, and heated and stirred under 60 DEG C of conditions, until dissolving, prepares barium zirconate precursor solution.
(2) the barium zirconate fiber solution of gained concentrating under reduced pressure under 40 DEG C of conditions is removed solvent, obtain the barium zirconate precursor sol that viscosity is 60Pa s, stand aging 1h and obtain spinning liquid.
(3) being 25 DEG C in temperature, humidity is 30%, and rotating speed controls at 18000r/min, and spinneret orifice diameter is 0.2mm, is injected by the spinning liquid obtained and gets rid of in wire tray at a high speed, drawing-off filamentation under high speed centrifugation effect, it is thus achieved that barium zirconate precursor fibre. The barium zirconate precursor fibre photo that centrifugal drying silk obtains is as shown in Figure 1.
(4) the barium zirconate precursor fibre obtained is warming up to 600 DEG C with the heating rate of 1 DEG C/min, is incubated 30min; Then it is warmed up to 1200 DEG C with 3 DEG C/min, is incubated 2h, Temperature fall, barium zirconate fiber can be obtained. Barium zirconate fibre picture is as in figure 2 it is shown, SEM photograph is as it is shown on figure 3, the diameter of fiber is at 4��8 ��m.
Crystalline phase stability experiment:
With 4 DEG C/min, the barium zirconate fiber in embodiment 1 is warmed up to 1300 DEG C, 1400 DEG C and the 1500 DEG C XRD figure spectrums then testing different temperatures respectively respectively, and result is as shown in Figure 5, it was shown that barium zirconate is Emission in Cubic, and under hot conditions, crystalline phase is stable.
Embodiment 2:
As described in Example 1, the difference is that step (4): the barium zirconate precursor fibre obtained is warming up to 600 DEG C with the heating rate of 1 DEG C/min, be incubated 30min; Then being warmed up to 1500 DEG C with 3 DEG C/min, be incubated 2h, Temperature fall, can obtain barium zirconate fiber, its SEM photograph is as shown in Figure 4. Barium zirconate fiber still can keep sintering adhesion between good form and fiber.
Embodiment 3: prepare barium zirconate fiber as acid source with trifluoroacetic acid:
As described in Example 1, institute is the difference is that being changed acid source into trifluoroacetic acid by glacial acetic acid, and weighing quality is that 45.6g trifluoroacetic acid is dissolved in solvent, is then added in zirconium oxycarbonate and brium carbonate. Prepared by spinning liquid, centrifugal drying silk and sintering process be with embodiment 1.
Embodiment 4: prepare barium zirconate fiber as acid source with the mixed acid of trifluoroacetic acid and acetic acid:
As described in Example 1, institute is the difference is that weighing 12g glacial acetic acid and 12g methanol is dissolved in 31.80 zirconium oxycarbonates, weigh 22.8g trifluoroacetic acid and 22.8g methanol is dissolved in the brium carbonate of 19.74g, two kinds of solution mixing systems, until dissolving respectively, are then obtained barium zirconate precursor solution by heated and stirred under 60 DEG C of conditions. Prepared by spinning liquid, centrifugal drying silk and sintering process be with embodiment 1. Gained barium zirconate fiber remains in that crystalline phase is stable, fibre morphology is good and sintering adhesion does not occur between fiber under up to 1500 DEG C of hot conditionss.
Embodiment 5:
As described in Example 1, the difference is that the barium acetate that in step (1), the brium carbonate of 19.74g is replaced by 25.54g, the quality of glacial acetic acid is 18g, and the amount of solvent methanol is 18g. Prepared by spinning liquid, centrifugal drying silk and sintering process be with embodiment 1. Gained barium zirconate fiber remains in that crystalline phase is stable, fibre morphology is good and sintering adhesion does not occur between fiber under up to 1500 DEG C of hot conditionss.
Claims (10)
1. a barium zirconate fiber, it is characterised in that fibre diameter is 1-20 ��m, the crystalline phase of described barium zirconate fiber is Emission in Cubic, and keeps crystalline phase stable under up to 1500 DEG C of hot conditionss.
2. barium zirconate fiber as claimed in claim 1, it is characterised in that described barium zirconate fiber remains in that fibre morphology well and sintering adhesion does not occur between fiber under up to 1500 DEG C of hot conditionss.
3. barium zirconate fiber as claimed in claim 1, it is characterised in that the diameter of described barium zirconate fiber is 2-15 ��m; The diameter of preferred described barium zirconate fiber is 4-8 ��m.
4. a preparation method for barium zirconate fiber described in any one of claim 1-3, comprises the following steps that
(1) it is zirconium oxycarbonate according to mol ratio: barium source: acid source=1:(1��1.5): the ratio of (2��6), weigh zirconium oxycarbonate, barium source and acid source respectively, join in solvent at 10��90 DEG C of temperature and stirring condition, carry out solution reaction, reaction 1��12h, obtains barium zirconate precursor solution;
(2) by step (1) gained barium zirconate precursor solution concentrating under reduced pressure at 30��70 DEG C of temperature, until obtain water white transparency, uniformly, viscosity be the barium zirconate precursor fibre spinning liquid of 10��50Pa s;
(3) it is centrifuged getting rid of silk by the barium zirconate precursor fibre spinning liquid that step (2) prepares, obtains barium zirconate precursor fibre;
(4) the barium zirconate precursor fibre that step (3) obtains is warming up to 600��800 DEG C with the heating rate of 1��3 DEG C/min under air conditions, is incubated 10-50min; Then it is warming up to 1200��1500 DEG C with the heating rate of 3��5 DEG C/min again, is incubated 1-2h, obtains barium zirconate fiber.
5. the preparation method of barium zirconate fiber as claimed in claim 4, it is characterised in that step (1) described solvent load is acid source by volume: solvent=100:100��1000.
6. the preparation method of barium zirconate fiber as claimed in claim 4, it is characterised in that the solvent described in step (1) is methanol, ethanol or its combination; Barium source described in step (1) is brium carbonate, barium acetate one or a combination set of.
7. the preparation method of barium zirconate fiber as claimed in claim 6, it is characterised in that when barium source is brium carbonate, feed molar proportioning is zirconium oxycarbonate: brium carbonate: acid source=1:1:(4��6); When barium source is barium acetate, material molar ratio is zirconium oxycarbonate: barium acetate: acid source=1:1:(2��4).
8. the preparation method of barium zirconate fiber as claimed in claim 4, it is characterised in that the acid source described in step (1) is glacial acetic acid, trifluoroacetic acid or its combination.
9. the preparation method of barium zirconate fiber as claimed in claim 4, it is characterised in that the solution reaction temperature described in step (1) is 20��60 DEG C; Preferably, the concentrating under reduced pressure temperature described in step (2) is 40��60 DEG C.
10. the preparation method of barium zirconate fiber as claimed in claim 4, it is characterized in that, the described centrifugal drying silk process conditions of step (3) are: get rid of a temperature 10��35 DEG C, humidity 15��45%, centrifuge speed is 12000��30000r/min, getting rid of a hole linear velocity is 30��50m/s, and getting rid of an aperture is 0.2mm��0.5mm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108505145A (en) * | 2018-04-11 | 2018-09-07 | 山东大学 | A kind of calcium zirconate fiber and preparation method thereof |
| CN112374884A (en) * | 2020-12-15 | 2021-02-19 | 湖南仁海科技材料发展有限公司 | High-specific-gravity tungsten alloy sintering setter plate and preparation method thereof |
| CN113089135A (en) * | 2021-04-08 | 2021-07-09 | 齐鲁工业大学 | High-entropy zirconate inorganic fiber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108505145A (en) * | 2018-04-11 | 2018-09-07 | 山东大学 | A kind of calcium zirconate fiber and preparation method thereof |
| CN112374884A (en) * | 2020-12-15 | 2021-02-19 | 湖南仁海科技材料发展有限公司 | High-specific-gravity tungsten alloy sintering setter plate and preparation method thereof |
| CN113089135A (en) * | 2021-04-08 | 2021-07-09 | 齐鲁工业大学 | High-entropy zirconate inorganic fiber and preparation method thereof |
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