CN108505145B - Calcium zirconate fiber and preparation method thereof - Google Patents

Calcium zirconate fiber and preparation method thereof Download PDF

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CN108505145B
CN108505145B CN201810320370.1A CN201810320370A CN108505145B CN 108505145 B CN108505145 B CN 108505145B CN 201810320370 A CN201810320370 A CN 201810320370A CN 108505145 B CN108505145 B CN 108505145B
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calcium zirconate
calcium
fiber
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CN108505145A (en
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王新强
施淑颖
袁康康
许东
朱陆益
张光辉
刘雪松
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Shandong University
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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
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Inorganic Fibers (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention relates to a calcium zirconate fiber and a preparation method thereof. The calcium zirconate fiber has a diameter of 0.5 to 2 μm, belongs to an orthorhombic system, is single-phase calcium zirconate, and has no second phase. The preparation method comprises the following steps: fully stirring basic zirconium carbonate, glacial acetic acid, a calcium source and a solvent according to a proportion at the temperature of 25-90 ℃ until the solution is clear to form a precursor solution; adding a spinning aid into the precursor solution, stirring and dissolving at 25-60 ℃, and adjusting the obtained precursor solution to a certain viscosity by using a solvent to obtain a precursor spinning solution; and (3) performing electrostatic spinning on the obtained precursor spinning solution to obtain precursor fibers, and performing high-temperature heat treatment to obtain the calcium zirconate fibers. The invention has simple preparation process and low cost, and can reach the molecular level uniformity in the preparation process. The obtained fiber has uniform diameter and reliable quality, has excellent high-temperature stability and alkali resistance, and has wide application prospect in the fields of high-temperature heat insulation materials, thermal barrier coating materials, chrome-free bricks of cement rotary kilns and corrosion-resistant crucibles for titanium alloy smelting.

Description

Calcium zirconate fiber and preparation method thereof
Technical Field
The invention relates to the technical field of synthetic fibers, in particular to a calcium zirconate fiber and a preparation method thereof.
Background
Calcium zirconate (CaZrO)3) Is CaO-ZrO2The compound with the highest and most stable CaO content in the system belongs to perovskite type compounds. At 1750 deg.C, the structure is changed from orthogonal structure to cubic structure, its melting point is high (higher than 2300 deg.C), thermal expansion coefficient is small, thermal shock resistance is good, and it is widely used as structural ceramic and refractory material. Calcium zirconate has excellent alkali resistance and has been used to produce chrome-free cement kiln firebricks, see CN101759229A calcium zirconate and magnesia calcium zirconium bricks for cement kilns made using calcium zirconate. Calcium zirconate is chemically stable and is well suited for casting highly chemically active alloys such as titanium alloys, for example, CN103071764A discloses CaZrO for precision casting of titanium and titanium alloys3A shell and a method for preparing the same. In addition, calcium zirconate is a high-temperature structural material which is recognized at home and abroad at present and effectively solves the problem of alumina blockage of the continuous casting steel submerged nozzle, see CN 1420103A. Calcium zirconate ceramic having dielectric properties (dielectric constant) due to microwaver30, quality factor × frequency Q × f 16800GHz, resonant frequency temperature coefficient tauf(-26.5 ppm/° c) can be used for capacitors and dielectric resonators under microwave conditions, see CN103449810A low temperature co-fired calcium zirconate microwave dielectric ceramic material.
The conventional method for preparing calcium zirconate materials has many disadvantages, such as: the high-temperature solid-phase reaction method is difficult to uniformly mix the raw materials, so that a material with a uniform microstructure is difficult to obtain in a later process, and a mechanically ground mixture is often required to react at a higher temperature within a longer reaction time and is easy to cause uneven grain growth; the melting method has the defect of high energy consumption; the ball milling method has the defects of over-low purity of reaction products, incomplete reaction, low yield and the like.
At present, calcium zirconate materials are mostly in the form of powder, shell, ceramic and other materials, and the inventor of the invention prepares calcium zirconate fibers by a centrifugal wire spinning method in the earlier stage, but the diameter of the fibers prepared by the method is large, and the preparation process of precursor sol is complex. (see: Ceramics International, 2014, 40: 12525-.
Therefore, the invention is especially provided in order to give full play to the advantages of the fiber morphology and solve the defects in the preparation process of the calcium zirconate fiber at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the calcium zirconate fiber and the preparation method thereof, the method has simple process, energy conservation, uniform fiber diameter and crystal grain and high product purity, and provides a new product for the calcium zirconate refractory material.
Summary of The Invention
The invention adopts the electrostatic spinning technology to prepare the calcium zirconate material with the fiber morphology. Compared with the traditional preparation method of the calcium zirconate material, the method has the advantages of simple process, energy conservation, high purity of the prepared calcium zirconate, uniform crystal grains and nanoscale. Meanwhile, the appearance of the fiber has the advantages of small diameter, large length-diameter ratio, large specific surface area, fluffiness and the like, so that the material has lower thermal conductivity, better mechanical property and better temperature resistance. The fiber is soaked in high-concentration alkali solution for a long time, and the shape, structure and composition of the fiber are not changed, so that the fiber has excellent alkali resistance.
Detailed Description
The technical scheme of the invention is as follows:
the calcium zirconate fiber is pure-phase calcium zirconate, belongs to an orthorhombic system, has the diameter of 0.5-2 mu m, and keeps stable crystalline phase at the temperature of 1200 ℃.
According to the invention, preferably, the calcium zirconate fiber is soaked in 2mol/L NaOH solution at 80 ℃ for 24 hours, and the fiber morphology and the composition are not changed.
According to the present invention, it is preferable that the calcium zirconate fiber maintains a good fiber morphology at a high temperature of 1200 c without occurrence of sintering adhesion between fibers.
According to the invention, the preparation method of the calcium zirconate fiber comprises the following steps:
(1) according to the molar ratio of basic zirconium carbonate: a calcium source: glacial acetic acid 1: (1-1.5): 2.55, respectively weighing basic zirconium carbonate, a calcium source and glacial acetic acid, adding the basic zirconium carbonate, the calcium source and the glacial acetic acid into a solvent at the temperature of 25-90 ℃, stirring for reaction and dissolution, and stirring for 1-12 h to obtain a calcium zirconate precursor solution;
(2) adding a spinning aid into the calcium zirconate precursor solution obtained in the step (1), and stirring and dissolving at the temperature of 25-60 ℃ for 1-6 h; after the spinning aid is completely dissolved, adjusting the viscosity by using the solvent in the step (1), and continuously stirring for 0.25-2 h to prepare a calcium zirconate precursor spinning solution;
(3) performing electrostatic spinning on the calcium zirconate precursor spinning solution prepared in the step (2) to obtain calcium zirconate precursor fibers;
(4) and (3) heating the calcium zirconate precursor fiber obtained in the step (3) to 600-800 ℃ at a heating rate of 0.5-2 ℃/min under the air condition, then heating to 800-1200 ℃ at a heating rate of 2-3 ℃/min, and preserving heat for 1-2h to obtain the calcium zirconate fiber.
According to the invention, the calcium source in the step (1) is one of or the combination of calcium nitrate tetrahydrate, anhydrous calcium chloride, calcium acetate monohydrate and calcium propionate;
preferably, the calcium source is calcium nitrate tetrahydrate.
According to the present invention, the solvent in step (1) is preferably water, absolute methanol, absolute ethanol or a combination thereof.
According to the invention, the reaction temperature of the solution in the step (1) is preferably 40-60 ℃.
Preferably, the spinning aid in step (2) is polyethylene oxide (PEO), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), or a combination thereof, wherein the PEO has an average molecular weight of 100 ten thousand, the PVP has an average molecular weight of 130 ten thousand, and the PVA has an average molecular weight of 8.8 ten thousand;
preferably, the mass ratio of the spinning aid to the basic zirconium carbonate in the step (1) is (0.05-0.3): 10.
according to the invention, the dissolving temperature of the spinning aid in the step (2) is preferably 25-45 ℃.
According to the invention, the viscosity of the solvent in the step (2) is preferably adjusted to 10-50 Pa · s, and the stirring time is preferably 0.5-1h after the viscosity is adjusted.
According to the invention, the electrostatic spinning process conditions in the step (3) are preferably as follows: the spinning voltage is 12-16 kV, the propelling speed is 1.0-2.0 mL/h, the receiving distance is 18-25 cm, the spinning humidity is 20-45%, and the spinning temperature is 20-40 ℃.
The diameter of the calcium zirconate fiber prepared by the method is 0.5-2 mu m, the calcium zirconate fiber belongs to an orthorhombic system, the crystal grains are uniform, and the fiber quality is reliable.
The calcium zirconate fibers are prepared by an electrostatic spinning method, and the spinning solution is formed by reaction in the solution, so that the uniformity of molecular level can be achieved; the formed fiber has fine diameter, large length-diameter ratio and specific surface area, uniform crystal grains and nano-scale; the product has high purity and low crystallization temperature, does not need high temperature heat treatment and long-time heat preservation, and saves energy. The calcium zirconate fiber has the advantages of light weight, uniform crystal grains, small diameter, large specific surface area, fluffy appearance and the like, and the small diameter and the large specific surface area ensure that the material has lower heat conductivity, better mechanical property and better temperature resistance.
The invention has the following excellent effects:
1. the invention takes alkali zirconium carbonate, calcium source and glacial acetic acid as reactants, water, methanol, ethanol or mixture thereof as solvent, and the reactants are stirred and dissolved under certain temperature condition, and then spinning aid is added and the viscosity is adjusted to prepare calcium zirconate precursor spinning solution; preparing calcium zirconate precursor fibers by an electrostatic spinning method; and sintering at high temperature to obtain the calcium zirconate fiber. The preparation process is simple, energy-saving and low in cost.
In addition, through a large number of experimental researches, the optimal ratio of the basic zirconium carbonate to the calcium nitrate tetrahydrate is obtained, so that the obtained calcium zirconate fiber is a pure phase and has no other impurity phases; the precursor spinning solution has the advantages of molecular level uniformity, high product purity, uniform crystal grains and stable and reliable quality.
2. The calcium zirconate fiber has the advantages of good crystallization property, uniform crystal grains, small diameter, fluffy appearance, lower thermal conductivity than other appearance materials, better mechanical property and better temperature resistance, and can still keep good fiber appearance under the high temperature condition of 1200 ℃. The calcium zirconate fiber has wide application prospect in the fields of high-temperature heat insulation materials, thermal barrier coating materials and the like.
3. The calcium zirconate fiber provided by the invention is soaked in a high-concentration alkali solution for a long time, and has the advantages of no change in appearance, structure and composition and excellent alkali resistance. The method has wide application prospect in the fields of cement rotary kiln chromium-free bricks, titanium alloy smelting, submerged nozzle alumina deposition blockage prevention and the like.
Drawings
FIG. 1 is a photograph of a calcium zirconate precursor fiber obtained in example 1 of the present invention.
FIG. 2 is a photograph of a calcium zirconate fiber obtained after heat treatment at 900 ℃ in example 1 of the present invention.
FIG. 3 is an SEM photograph of calcium zirconate fibers obtained after heat treatment at 900 ℃ in example 1 of the present invention.
FIG. 4 is an SEM photograph of calcium zirconate fibers obtained after heat treatment at 1200 ℃ in example 3 of the present invention.
FIG. 5 is an XRD photograph of calcium zirconate fibers obtained in example 2 of the present invention and comparative examples 1 to 4. Wherein (a)1:1, (b)1:1.05, (c)1:1.15, (d) 1:1.2, (e)1:1.25 represent molar ratios of zirconium basic carbonate to calcium nitrate tetrahydrate of 1:1 (comparative example 1), 1:1.05 (comparative example 2), 1:1.15 (comparative example 3), 1:1.2 (comparative example 4), 1:1.25 (example 2), respectively.
FIG. 6 is an SEM photograph of calcium zirconate fibers after alkali etching in Experimental example 1 of the present invention.
FIG. 7 is an SEM photograph of calcium zirconate fibers after alkali etching in Experimental examples 2 and 3 of the present invention. Wherein a and c represent soaking in 1mol/L NaOH solution for 12 and 24 hours (Experimental example 2), and b and d represent soaking in 2mol/L NaOH solution for 12 and 24 hours (Experimental example 3).
Detailed Description
The present invention will be further described by way of examples, but not limited thereto, with reference to the accompanying drawings.
The raw materials used in the examples are conventional raw materials, and the equipment used is conventional equipment, commercially available products.
Example 1:
a preparation method of calcium zirconate fibers comprises the following steps:
(1) according to the molar ratio of basic zirconium carbonate to calcium nitrate tetrahydrate of 1:1.25, weighing 10.0000g of basic zirconium carbonate and 9.5693g of calcium nitrate tetrahydrate in a beaker, adding 5.0000g of glacial acetic acid and a proper amount of methanol, and heating and stirring at 60 ℃ until the basic zirconium carbonate and the calcium nitrate are dissolved to form a clear calcium zirconate precursor solution.
(2) 0.116g of polyethylene oxide (PEO, average molecular weight 100 ten thousand) is added into the calcium zirconate precursor solution obtained in the step (1), the mixture is heated and stirred at the temperature of 40 ℃ until the mixture is dissolved, the mixture is prepared into 54.0000g by using methanol, and the stirring is continued for 0.5h without heating, so that the calcium zirconate precursor spinning solution with the viscosity of 15Pa & s is prepared.
(3) And (3) performing electrostatic spinning on the calcium zirconate precursor spinning solution obtained in the step (2) at the temperature of 25 ℃ and the humidity of 30% to prepare the calcium zirconate precursor fiber. The spinning voltage of the electrostatic spinning is 13kV, the advancing speed is 1.5mL/h, and the receiving distance is 20 cm.
(4) And heating the obtained calcium zirconate precursor fiber to 600 ℃ at the heating rate of 1 ℃/min, then heating to 900 ℃ at the heating rate of 2 ℃/min, preserving the heat for 1h, and naturally cooling to obtain the calcium zirconate fiber.
The photo of the calcium zirconate precursor fiber is shown in figure 1; the photograph of the calcium zirconate fiber after the 900 ℃ heat treatment is shown in FIG. 2, and the SEM photograph is shown in FIG. 3.
Example 2:
as described in example 1, except that the obtained calcium zirconate precursor fiber is heated to 600 ℃ at a heating rate of 1 ℃/min in the step (4), then heated to 1000 ℃ at a heating rate of 2 ℃/min, and is kept warm for 1h, and then is naturally cooled.
Example 3:
as described in example 1, except that the obtained calcium zirconate precursor fiber is heated to 600 ℃ at a heating rate of 1 ℃/min in the step (4), then heated to 1200 ℃ at a heating rate of 2 ℃/min, and the temperature is maintained for 1h, and then the temperature is naturally reduced. The SEM photograph is shown in FIG. 4.
Comparative example 1:
as described in example 2, except that in step (1) the molar ratio of zirconium basic carbonate to calcium nitrate tetrahydrate is 1:1, weighing 10.0000g of basic zirconium carbonate and 7.6554g of calcium nitrate tetrahydrate.
Comparative example 2:
as described in example 2, except that in step (1) the molar ratio of zirconium basic carbonate to calcium nitrate tetrahydrate is 1:1.05, weigh 10.0000g zirconium basic carbonate, 8.0382g calcium nitrate tetrahydrate.
Comparative example 3:
as described in example 2, except that in step (1) the molar ratio of zirconium basic carbonate to calcium nitrate tetrahydrate is 1:1.15, weighing 10.0000g of basic zirconium carbonate and 8.8037g of calcium nitrate tetrahydrate.
Comparative example 4:
as described in example 2, except that in step (1) the molar ratio of zirconium basic carbonate to calcium nitrate tetrahydrate is 1:1.2, weighing 10.0000g of basic zirconium carbonate and 9.1865g of calcium nitrate tetrahydrate.
The XRD patterns of the fibers obtained by the different molar ratios of the zirconium basic carbonate and the calcium nitrate tetrahydrate in the example 2 and the comparative examples 1 to 4 are tested, and the results are shown in figure 5. As can be seen from fig. 5, when the molar ratio of the basic zirconium carbonate to the calcium nitrate tetrahydrate is 1: the material prepared at 1.25 is pure phase calcium zirconate without generating a second phase.
Experimental example 1
The calcium zirconate fiber obtained in example 1 was washed and dried in acetone, followed by alkali resistance test, as follows:
weighing 50mg of calcium zirconate fibers, putting the calcium zirconate fibers into 20mL of NaOH solution with the concentration of 1mol/L and the temperature kept at 80 ℃, sampling for 1 hour, 2 hours and 3 hours respectively, centrifugally cleaning the fibers to be neutral by using deionized water, and drying. SEM photographs of calcium zirconate fibers at different corrosion times are shown in fig. 6. As can be seen from FIG. 6, after the fiber is corroded in 1mol/L NaOH solution for 1-3 h, neither the morphology nor the surface of the fiber is changed.
Experimental example 2:
as described in Experimental example 1, except that the time for immersing the calcium zirconate fibers in the NaOH solution maintained at a temperature of 80 ℃ of 1mol/L was extended to 12 hours and 24 hours. SEM photographs after fiber etching are shown in FIGS. 7a and c. As can be seen from FIG. 7, after the fiber is corroded in 1mol/L NaOH solution for 12 hours and 24 hours, the shape and the surface of the fiber are not changed.
Experimental example 3:
as described in experimental example 1, except that the concentration of the NaOH solution was increased to 2mol/L and the soaking time of the calcium zirconate fibers in the alkali solution was extended to 12 hours and 24 hours. SEM pictures after fiber corrosion are shown in FIGS. 7b and d. As can be seen from FIG. 7, after the fiber is corroded in 2mol/L NaOH solution for 12 hours and 24 hours, the shape and the surface of the fiber are not changed.
Calcium zirconate fibers obtained in example 1 (not subjected to alkali etching) and fibers obtained in experimental example 3 immersed in a 2mol/L NaOH solution for 24 hours were subjected to EDS test, and the results are shown in table 1.
TABLE 1
Figure BDA0001625122230000061
From SEM photographs of experimental examples 1-3, it is clear that the shape and structure of the calcium zirconate fiber cannot be damaged after the calcium zirconate fiber is soaked in a high-concentration NaOH solution at 80 ℃ for a long time. EDS results show that the element content on the surface of the fiber is not changed, and the calcium zirconate fiber has excellent alkali resistance.

Claims (10)

1. The preparation method of the calcium zirconate fiber is characterized in that the calcium zirconate fiber is pure-phase calcium zirconate, belongs to an orthorhombic system, has the diameter of 0.5-2 mu m, and keeps stable crystalline phase at the temperature of 1000 ℃;
the method comprises the following steps:
(1) according to the molar ratio of basic zirconium carbonate: a calcium source: glacial acetic acid = 1: (1.25-1.5): 2.55, respectively weighing basic zirconium carbonate, a calcium source and glacial acetic acid, adding the basic zirconium carbonate, the calcium source and the glacial acetic acid into a solvent at the temperature of 25-90 ℃, stirring for reaction and dissolution, and stirring for 1-12 h to obtain a calcium zirconate precursor solution; the calcium source is one of or the combination of calcium nitrate tetrahydrate, calcium acetate monohydrate and calcium propionate;
(2) adding a spinning aid into the calcium zirconate precursor solution obtained in the step (1), and stirring and dissolving at the temperature of 25-60 ℃ for 1-6 h; after the spinning aid is completely dissolved, adjusting the viscosity by using the solvent in the step (1), and continuously stirring for 0.25-2 h to prepare a calcium zirconate precursor spinning solution;
(3) performing electrostatic spinning on the calcium zirconate precursor spinning solution prepared in the step (2) to obtain calcium zirconate precursor fibers;
(4) and (3) heating the calcium zirconate precursor fiber obtained in the step (3) to 600-800 ℃ at a heating rate of 0.5-2 ℃/min under the air condition, then heating to 800-1000 ℃ at a heating rate of 2-3 ℃/min, and preserving heat for 1-2h to obtain the calcium zirconate fiber.
2. The method of preparing calcium zirconate fiber according to claim 1, wherein the calcium zirconate fiber is soaked in 2mol/l aoh solution at 80 ℃ for 24 hours without change in fiber morphology and composition.
3. The method of producing calcium zirconate fibers according to claim 1, wherein the calcium zirconate fibers maintain a good fiber morphology at a high temperature of 1200 ℃ without causing sintering adhesion between the fibers.
4. The method of preparing calcium zirconate fibers according to claim 1, wherein the solvent used in step (1) is water, anhydrous methanol, anhydrous ethanol or a combination thereof.
5. The method of preparing calcium zirconate fibers according to claim 1, wherein the reaction and dissolution temperature in the step (1) is 40 to 60 ℃.
6. The method of preparing calcium zirconate fiber as claimed in claim 1, wherein the spin agent in step (2) is polyethylene oxide PEO, polyvinylpyrrolidone PVP, polyvinyl alcohol PVA or a combination thereof, wherein the average molecular weight of PEO is 100 ten thousand, the average molecular weight of PVP is 130 ten thousand, and the average molecular weight of PVA is 8.8 ten thousand.
7. The method for preparing calcium zirconate fibers according to claim 1, wherein the mass ratio of the spinning aid in the step (2) to the basic zirconium carbonate in the step (1) is (0.05-0.3): 10.
8. the method of preparing calcium zirconate fibers according to claim 1, wherein the solution temperature of the spinning aid in the step (2) is 25 to 45 ℃.
9. The method of preparing calcium zirconate fiber according to claim 1, wherein the viscosity of the solvent in the step (2) is adjusted to 10 to 50 Pa-s, and the stirring is continued for 0.5 to 1 hour after the viscosity is adjusted.
10. The method for preparing calcium zirconate fibers according to claim 1, wherein the electrospinning process conditions in the step (3) are as follows: the spinning voltage is 12-16 kV, the propelling speed is 1.0-2.0 mL/h, the receiving distance is 18-25 cm, the spinning humidity is 20-45%, and the spinning temperature is 20-40 ℃.
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