CN102351539B - Method for preparing electrostatic spinning liquid of zirconium boride nano ceramic fiber - Google Patents
Method for preparing electrostatic spinning liquid of zirconium boride nano ceramic fiber Download PDFInfo
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- CN102351539B CN102351539B CN 201110186104 CN201110186104A CN102351539B CN 102351539 B CN102351539 B CN 102351539B CN 201110186104 CN201110186104 CN 201110186104 CN 201110186104 A CN201110186104 A CN 201110186104A CN 102351539 B CN102351539 B CN 102351539B
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Abstract
The invention relates to a method for preparing electrostatic spinning liquid of zirconium boride nano ceramic fiber. The method comprises the following steps: (1) adding an aqueous solution of zirconium oxychloride octahydrate into a boric acid aqueous solution, adding a cane sugar aqueous solution, a citric acid aqueous solution and uniformly mixing, regulating the pH value of 4-5, stirring and reacting for 10-16 hours to obtain a precursor solution; (2) uniformly mixing the precursor solution and a spinning auxiliary agent under the room temperature, adding a surfactant to obtain the electrostatic spinning liquid of the zirconium boride ceramic fiber. The invention has the advantages of simple operation process, low cost and low equipment requirement; the nano fiber with good appearance form can be obtained under the high-voltage field by the prepared spinning liquid, further, zirconium boride nano ceramic fiber with good surface form can be obtained by the appropriate sintering process; the fiber has performances of high temperature resistance, low density and the like, and has wide application prospect.
Description
Technical field
The invention belongs to the preparation field of superhigh temperature ceramics fiber, particularly relate to the preparation method of electrostatic spinning liquid of zirconium boride nano ceramic fiber.
Background technology
Along with high-tech development, have higher requirement to high-strength, the Gao Mo of material, high temperature resistant, corrosion-resistant, anti-oxidant, the performance such as resistance to wear in the fields such as national defence, space flight and aviation, the energy.
Zirconium boride 99.5004323A8ure (ZrB
2) pottery has high-melting-point (＞3000 ℃), high rigidity, high-modulus, high heat conductance and specific conductivity, good heat-shock resistance, extremely strong chemical bond and the good overall characteristics such as chemical stability, therefore can be applicable to the ultrahigh-temperature extreme environment more than 2000 ℃, such as the leading edge parts of hypersonic reentry space vehicle, rocket propulsion system, refractory materials, plasma electrode etc.And, zirconium boride ceramic has minimum density in superhigh temperature ceramic material, therefore become the candidate material of the tool potentiality of ultrahigh-temperature Application Areas, can be applicable to the critical material of making space aircraft and launch vehicle heat-protection system thereof etc., thereby can adapt to the environmental requirement of hypersonic flying for long time, and can keep the aerodynamic configuration of aircraft near-complete.
Because zirconium boride 99.5004323A8ure has extremely strong covalent linkage, lower volume and crystal boundary rate of diffusion and product easily volatilize to wait and cause its sintering densification difficult.Zirconium boride 99.5004323A8ure anti-oxidant/ablative, the damage tolerance characteristic is relatively poor, be used for high-temperature structural material as monophase materials and will be subject to certain limitation, therefore preparing the zirconium boride 99.5004323A8ure based composite ceramic material can improve not only that it is anti-oxidant/and ablative, also can effectively improve its sintering densification process, mechanical property etc.As introduce SiC, and can improve zirconium boride ceramic oxidation-resistance at high temperature, its intensity can be brought up to more than the 1GPa, and Shanghai Silicate Inst., Chinese Academy of Sciences proposes and has realized that injection forming and the SPS sintering means under the high-intensity magnetic field have obtained textured ZrB
2-SiC pottery, this bill of material reveals obvious antioxidant property advantage.ZrSi
2Introducing then reduced below the sintering densification temperature to 1550 ℃ of ZrB2, and can further improve its thermal conductivity and specific conductivity; An amount of ZrO
2Introducing, but Effective Raise ZrB then
2Intensity and the toughness of pottery.
Though zirconium boride 99.5004323A8ure has a lot of superior characteristics, but its performance that shows at present can't satisfy the needs of practical application, the preparation, sintering densification process and the matrix material preparation thereof that both at home and abroad mainly concentrate on material powder for the research of zirconium boride 99.5004323A8ure improve the aspects such as its mechanical property, high temperature oxidation resistance, but there is no the relevant report about zirconium boride ceramic fiber and matrix material preparation thereof.
Ceramic fiber has incomparable high temperature resistant, the anti-oxidant function of organic fibre and unique electricity, optical property. and this fibrid is generally made by the direct melt-spinning of inorganic raw material, but can't make fiber for the zirconium boride ceramic material because of the melting difficulty, the application of so-gel technique then can remedy the deficiency of scorification.
In recent years, it is found that the solution that sol-gel method is mixed with is well positioned to meet the desired viscosity of electrostatic spinning as presoma, making inorganics carry out electrostatic spinning becomes possibility.For example, and the Xue Mei Cui of Taean, Korea university etc. (Materials Letters, 2008,62:1961-1964) obtained ultra-fine ZrC fiber by electrostatic spinning; The people such as the Changlu Shao of Northeast Normal University utilize electrostatic spinning technique to obtain high temperature resistant ZrO nanofiber.
But also do not find relevant ultrahigh-temperature zirconium boride 99.5004323A8ure (ZrB both at home and abroad
2) research of nano ceramic fibers.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of electrostatic spinning liquid of zirconium boride nano ceramic fiber, and the method operating procedure is simple, and is with low cost, and is lower to the requirement of equipment; Made spinning solution can obtain preferably zirconium boride ceramic rice fiber of configuration of surface, and this fiber has the performances such as high temperature resistant, low density, has a extensive future.
The preparation method of a kind of electrostatic spinning liquid of zirconium boride nano ceramic fiber of the present invention comprises:
(1) preparation of precursor solution
The aqueous solution of eight hydration zirconium oxychlorides is joined in the boric acid aqueous solution, add aqueous sucrose solution again, aqueous citric acid solution mixes, and regulating at last the pH value is 4～5, and stirring reaction 10～16h gets precursor solution;
(2) zirconium boride ceramic fiber electrostatic spinning solution is synthetic
Under the room temperature, above-mentioned precursor solution with after spin finish aid evenly mixes, is added tensio-active agent, namely get zirconium boride ceramic fiber electrostatic spinning solution.
The mol ratio of eight hydration zirconium oxychlorides described in the step (1) and boric acid is 1: 1～1: 10.
The mol ratio of the sucrose described in the step (1) and eight hydration zirconium oxychlorides is 1: 1～1: 15.
The mol ratio of citric acid and eight hydration zirconium oxychlorides is 0.1: 1～10: 1 in the aqueous citric acid solution described in the step (1).
Spin finish aid described in the step (2) is a kind of in polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylene glycol, polyoxyethylene and the hydroxypropylcellulose.
Spin finish aid described in the step (2) accounts for 10～40% of eight hydration zirconium oxychlorides, boric acid, sucrose, citric acid and spin finish aid total mass.
Tensio-active agent described in the step (2) is a kind of in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Potassium dodecyl phosphate and the sorbitol anhydride mono-laurate.
Tensio-active agent described in the step (2) accounts for 0.5% of eight hydration zirconium oxychlorides, boric acid, sucrose, citric acid and spin finish aid total mass.
Know-why of the present invention: Yi Shui, eight hydration zirconium oxychlorides, boric acid, sucrose are main raw material, and improve the spinnability of spinning solution by adding the polymer spin finish aid, obtain stable electrostatic spinning liquid.
Beneficial effect:
(1) operating procedure of the present invention is simple, and is with low cost, lower to the requirement of equipment;
(2) the made spinning solution of the present invention can obtain preferably nanofiber of mode of appearance under high-voltage electric field, can obtain preferably zirconium boride ceramic rice fiber of configuration of surface by suitable sintering process again, and high temperature resistant, the performances such as low density have a extensive future.
Description of drawings
Fig. 1 amplifies 1000 times schematic diagram for the spun fiber of the electrostatic spinning liquid of zirconium boride nano ceramic fiber of preparation.
Fig. 2 amplifies 7000 times schematic diagram for the spun fiber of the electrostatic spinning liquid of zirconium boride nano ceramic fiber of preparation.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
To contain 0.6445g eight hydration zirconium oxychloride aqueous solutions, dropwise join and stirring in the aqueous solution that contains 0.2473g boric acid, add respectively again and contain the 0.2853g aqueous sucrose solution and contain the 1.6811g aqueous citric acid solution, mix, regulation system pH value to 4～5 form solution, reaction 10h, add the 0.7146g polyvinyl alcohol, fully dissolving obtains uniform spinning solution, add at last and account for eight hydration zirconium oxychlorides, boric acid, sucrose, 0.5% sodium lauryl sulphate of citric acid and spin finish aid total mass also mixes, and obtains the electrostatic spinning liquid of zirconium boride nano ceramic fiber.
Embodiment 2
To contain 0.6445g eight hydration zirconium oxychloride aqueous solutions, dropwise join and stirring in the aqueous solution that contains 0.2647g boric acid, add respectively again and contain the 0.2853g aqueous sucrose solution and contain the 1.2232g aqueous citric acid solution, mix, regulation system pH value to 4～5 form solution, reaction 14h, add the 0.4799g polyvinyl alcohol, fully dissolving obtains uniform spinning solution, add at last and account for eight hydration zirconium oxychlorides, boric acid, sucrose, 0.5% Sodium dodecylbenzene sulfonate of citric acid and spin finish aid total mass also mixes, and obtains the electrostatic spinning liquid of zirconium boride nano ceramic fiber.
Embodiment 3
To contain 0.6445g eight hydration zirconium oxychloride aqueous solutions, dropwise join and stirring in the aqueous solution that contains 0.3081g boric acid, add respectively again and contain the 0.2853g aqueous sucrose solution and contain the 0.8262g aqueous citric acid solution, mix, regulation system pH value to 4～5 form solution, reaction 12h, add the 0.6192g polyvinylpyrrolidone, fully dissolving obtains uniform spinning solution, add at last and account for eight hydration zirconium oxychlorides, boric acid, sucrose, 0.5% Sodium dodecylbenzene sulfonate of citric acid and spin finish aid total mass also mixes, and obtains the electrostatic spinning liquid of zirconium boride nano ceramic fiber.
Embodiment 4
To contain 0.6445g eight hydration zirconium oxychloride aqueous solutions, dropwise join and stirring in the aqueous solution that contains 0.3436g boric acid, add respectively again and contain the 0.2853g aqueous sucrose solution and contain the 1.6811g aqueous citric acid solution, mix, regulation system pH value to 4～5 form solution, reaction 11h, add the 0.998g hydroxypropylcellulose, fully dissolving obtains uniform spinning solution, add at last and account for eight hydration zirconium oxychlorides, boric acid, sucrose, 0.5% Sodium dodecylbenzene sulfonate of citric acid and spin finish aid total mass also mixes, and obtains the electrostatic spinning liquid of zirconium boride nano ceramic fiber.
Embodiment 5
To contain 0.6445g eight hydration zirconium oxychloride aqueous solutions, dropwise join and stirring in the aqueous solution that contains 0.5422g boric acid, add respectively again and contain the 0.2853g aqueous sucrose solution and contain the 1.9832g aqueous citric acid solution, mix, regulation system pH value to 4～5 form solution, reaction 10h, add the 0.7146g polyoxyethylene, fully dissolving obtains uniform spinning solution, add at last and account for eight hydration zirconium oxychlorides, boric acid, sucrose, 0.5% sorbitol anhydride mono-laurate of citric acid and spin finish aid total mass also mixes, and obtains the electrostatic spinning liquid of zirconium boride nano ceramic fiber.
Claims (3)
1. the preparation method of an electrostatic spinning liquid of zirconium boride nano ceramic fiber comprises:
(1) aqueous solution with eight hydration zirconium oxychlorides joins in the boric acid aqueous solution, adds aqueous sucrose solution again, and aqueous citric acid solution mixes, and regulating at last the pH value is 4～5, and stirring reaction 10～16h gets precursor solution;
(2) under the room temperature, above-mentioned precursor solution with after spin finish aid evenly mixes, is added tensio-active agent, namely get zirconium boride ceramic fiber electrostatic spinning solution;
The mol ratio of eight hydration zirconium oxychlorides described in the step (1) and boric acid is 1:1～1:10;
The mol ratio of the sucrose described in the step (1) and eight hydration zirconium oxychlorides is 1:1～1:15;
The mol ratio of citric acid and eight hydration zirconium oxychlorides is 0.1:1～10:1 in the aqueous citric acid solution described in the step (1);
Spin finish aid described in the step (2) is a kind of in polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylene glycol, polyoxyethylene and the hydroxypropylcellulose;
Tensio-active agent described in the step (2) is a kind of in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Potassium dodecyl phosphate and the sorbitol anhydride mono-laurate.
2. the preparation method of a kind of electrostatic spinning liquid of zirconium boride nano ceramic fiber according to claim 1, it is characterized in that: the spin finish aid described in the step (2) accounts for 10～40% of eight hydration zirconium oxychlorides, boric acid, sucrose, citric acid and spin finish aid total mass.
3. the preparation method of a kind of electrostatic spinning liquid of zirconium boride nano ceramic fiber according to claim 1, it is characterized in that: the tensio-active agent described in the step (2) accounts for 0.5% of eight hydration zirconium oxychlorides, boric acid, sucrose, citric acid and spin finish aid total mass.
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| CN102584243A (en) * | 2012-03-08 | 2012-07-18 | 东华大学 | Preparation method of zirconium boride ceramic fibre |
| CN102775148A (en) * | 2012-07-12 | 2012-11-14 | 东华大学 | Preparation method of magnesium diboride ceramic fiber precursor electrostatic spinning solution |
| CN102786305B (en) * | 2012-07-20 | 2014-07-23 | 东华大学 | Method for preparing continuous zirconium boride ceramic precursor fiber |
| CN104109912A (en) * | 2014-06-25 | 2014-10-22 | 东华大学 | Preparation method of zirconium boride-silicon composite ceramic fiber |
| CN104988604B (en) * | 2015-07-31 | 2018-01-30 | 安徽恒硕纺织品有限公司 | A kind of preparation method of zirconium carbide micro nanometer fiber |
| CN105314915A (en) * | 2015-12-01 | 2016-02-10 | 仇颖超 | Preparation method of ceramic fiber composite sulfonated polystyrene water reducing agent |
| CN105368257A (en) * | 2015-12-03 | 2016-03-02 | 丁玉琴 | Preparation method for low-expansion-coefficient ceramic fiber modified epoxy resin |
| CN111253161A (en) * | 2020-01-20 | 2020-06-09 | 陕西科技大学 | SiCf-ZrC-ZrB2Ceramic composite powder and preparation method thereof |
| CN111501132B (en) * | 2020-06-01 | 2022-07-29 | 山东省科学院新材料研究所 | Method for preparing nano zirconium boride ceramic fiber by using organic zirconium source, ceramic fiber and application |
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