CN101949073B - Preparation method of superfine zirconium oxide/silicon carbide fiber with radial and gradient distribution - Google Patents
Preparation method of superfine zirconium oxide/silicon carbide fiber with radial and gradient distribution Download PDFInfo
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- CN101949073B CN101949073B CN2010102502324A CN201010250232A CN101949073B CN 101949073 B CN101949073 B CN 101949073B CN 2010102502324 A CN2010102502324 A CN 2010102502324A CN 201010250232 A CN201010250232 A CN 201010250232A CN 101949073 B CN101949073 B CN 101949073B
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Abstract
The invention discloses a preparation method of superfine zirconium oxide/silicon carbide fiber with the radial and gradient distribution. The method comprises the following steps: using polycarbosilane and tetrabutyl zirconate, which weight ratio is 1:1-9:1 and solvent xylene to prepare a polycarbosilane/tetrabutyl zirconate solution, performing electrostatic spinning to prepare polycarbosilane/tetrabutyl zirconate protofiber; placing the protofiber in an oven, maintaining the temperature to 80-120 DEG C for 120-30 hours in the air to obtain polycarbosilane/tetrabutyl zirconate cured fiber; performing air pre-oxidation to the cured fiber, and firing at a high temperature to obtain the superfine zirconium oxide/silicon carbide fiber with the radial and gradient distribution finally. The method of the invention uses silicon carbide as matrix and zirconium oxide as the surface layer, the content of zirconium oxide is lowered along the radial direction, the product of the invention has small diameter and large specific area; and electrostatic spinning is performed at the room temperature, the preparation conditions are mild and the spinnability of the fiber is good.
Description
Technical field
The present invention relates to a kind of preparation method of superfine zirconia/silicon carbide gradient distributed fibers.
Background technology
T. Ishikawa; H. Yamaoka; Y. Harada; T. Fujii and T. Nagasawa. A general process in situ formation of functional surface layers on ceramics[J]. Nature; 2002; 416:64-67. disclose employing precursor converted in-situ method; with the Polycarbosilane is raw material; with the synthetic precursor of low molecule additive tetrabutyl zirconate; make continuous Polycarbosilane/tetrabutyl zirconate fiber through melt spinning again; melt processed obtains fusion-free fibre to place air to carry out not this fiber; fusion-free fibre placed carry out high temperature under the high temperature furnace inert atmosphere protection and burn till, make zirconia/silicon carbide gradient distributed fibers.This fiber has advantages such as high strength, high temperature tolerance, high antioxidant; But the fibre diameter of this melt spinning method preparation is still bigger, especially adopt melt spinning to prepare zirconia/silicon carbide gradient distributed fibers, need preparation Polycarbosilane/tetrabutyl zirconate precursor, its spinnability is restricted by factor affecting such as tetrabutyl zirconate content and dispersiveness thereof.In addition, be liquid down because Polycarbosilane (softening point is 200 ~ 220 ℃) normal temperature is down solid, tetrabutyl zirconate (boiling point is 310 ℃) normal temperature, still-process is also restive when the preparation precursor.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of superfine zirconia/silicon carbide gradient distributed fibers.The Gradient distribution fibre property is better, diameter reaches ultra-fine level to realize preparing, and has the far characteristic of absorption.
Technical scheme of the present invention is: be dissolved in Polycarbosilane and tetrabutyl zirconate in the dimethylbenzene altogether, obtain fibrillation by electrostatic spinning, burn till through overcuring heat treatment, air pre-oxidation, high temperature then, finally obtain superfine zirconia/silicon carbide gradient fiber.The fibre diameter size is controlled by the process conditions of electrostatic spinning.
The present invention includes following steps:
(1) preparation spinning solution: is 1: 1 ~ 9: 1 with Polycarbosilane and tetrabutyl zirconate by mass ratio, is solvent with dimethylbenzene, preparation Polycarbosilane/tetrabutyl zirconate solution, and with ultrasonic dispersion 30 minutes;
(2) electrostatic spinning: spinning condition is: the syringe needle internal diameter is 0.5 ~ 1.5mm, and voltage is 12 ~ 30kV, receives flight lead from being 15 ~ 25cm, and feeding rate is 10 ~ 50 μ l/min, and aluminium foil is received silk, makes Polycarbosilane/tetrabutyl zirconate fibrillation;
(3) slaking heat treatment: above-mentioned fibrillation is placed baking oven, under air,, obtain Polycarbosilane/tetrabutyl zirconate slaking fiber 80 ~ 120 ℃ of insulations 30 ~ 120 hours;
(4) air pre-oxidation: above-mentioned slaking fiber is placed oxidation furnace, in oxidizing atmosphere, heat up, and 190 ~ 220 ℃ of insulations 0.5 ~ 1.5 hour, do not melted Polycarbosilane/tetrabutyl zirconate fiber after being cooled to room temperature according to 15 ~ 25 ℃/h;
(5) high temperature burns till: above-mentioned fusion-free fibre is placed high-purity argon gas protection high temperature furnace down, be warming up to 1200 ~ 1450 ℃, and be incubated 1 hour under this temperature, obtain superfine zirconia/silicon carbide gradient distributed fibers.
Described Polycarbosilane is that softening point is 200 ~ 220 ℃ a solid.
Described tetrabutyl zirconate is that mass fraction is the butanol solution of 80 ~ 90% tetrabutyl zirconate.
Described Polycarbosilane is 1: 1 ~ 1.4 with the mixed solvent ratio of n-butanol and dimethylbenzene: 1g/ml.
The present invention adopts dimethylbenzene to make solvent, because Polycarbosilane and the dissolubility of tetrabutyl zirconate in dimethylbenzene are relatively good, the preparation of spinning solution is fairly simple, and the good spinnability of solution; Replaced traditional melt-spinning technology with electrostatic spinning, it has broken traditional coating idea, introduces low molecule additive in the precursor in early stage of fiber production, then in the pre-oxidation in later stage, burn till typing.Fiber with carborundum be matrix, superficial layer be zirconia and radially content successively decrease, diameter is little, specific area is big.
Description of drawings
Fig. 1 is the stereoscan photograph of the superfine zirconia/silicon carbide gradient distributed fibers of embodiment 1 preparation;
Fig. 2 is the power spectrum test position figure on the superfine zirconia/silicon carbide gradient distributed fibers surface of embodiment 1 preparation;
Fig. 3 is the power spectrum test position figure in the superfine zirconia/silicon carbide gradient distributed fibers cross section of embodiment 1 preparation.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) preparation spinning solution: is altogether to be dissolved in dimethylbenzene at 4: 1 with the butanol solution of Polycarbosilane solid (softening point is 200 ~ 220 ℃) and 85% tetrabutyl zirconate according to the mass ratio of Polycarbosilane and tetrabutyl zirconate, by Polycarbosilane and solvent (dimethylbenzene and n-butanol) than being 1.1: 1g/ml prepares Polycarbosilane/tetrabutyl zirconate solution, and with ultrasonic dispersion 30 minutes;
(2) electrostatic spinning: spinning condition is: the syringe needle internal diameter is 0.8mm, and voltage is 15kV, receives flight lead from being 20cm, and feeding rate is 20 μ l/min, and aluminium foil is received silk, makes Polycarbosilane/tetrabutyl zirconate fibrillation;
(3) slaking heat treatment: above-mentioned fibrillation is placed baking oven, and 80 ℃ are incubated 120 hours under air, obtain Polycarbosilane/tetrabutyl zirconate slaking fiber;
(4) air pre-oxidation: above-mentioned slaking fiber is placed oxidation furnace, in oxidizing atmosphere, heat up, and 210 ℃ of insulations 1 hour, do not melted Polycarbosilane/tetrabutyl zirconate fiber after being cooled to room temperature according to 20 ℃/h;
(5) high temperature burns till: above-mentioned fusion-free fibre is placed high-purity argon gas protection high temperature furnace down, be warming up to 1300 ℃, and be incubated 1 hour under this temperature, obtain superfine zirconia/silicon carbide gradient distributed fibers.
The stereoscan photograph of its superfine zirconia/silicon carbide gradient distributed fibers as shown in Figure 1.
As can be seen from Figure 1, fiber is nonwoven fabric distributions, surfacing.
Test position among Fig. 21 and 2 is carried out energy spectrum analysis, and its element set becomes to list in respectively table 1 and table 2.
Show that through energy spectrum analysis the Zr content specific surface on the fibre section is low.
(1) preparation spinning solution: is altogether to be dissolved in dimethylbenzene at 9: 1 with the butanol solution of Polycarbosilane solid (softening point is 200 ~ 220 ℃) and 85% tetrabutyl zirconate according to the mass ratio of Polycarbosilane and tetrabutyl zirconate, press Polycarbosilane and solvent (dimethylbenzene and n-butanol) than preparing Polycarbosilane/tetrabutyl zirconate solution for 1.3:1g/ml, and with ultrasonic dispersion 30 minutes;
(2) electrostatic spinning: spinning condition is: the syringe needle internal diameter is 1.2mm, and voltage 20kV receives flight lead from be 15cm, and feeding rate 30 μ l/min, aluminium foil receive thread, make Polycarbosilane/tetrabutyl zirconate fibrillation;
(3) slaking heat treatment: above-mentioned fibrillation is placed baking oven, and 80 ℃ are incubated 120 hours under air, obtain Polycarbosilane/tetrabutyl zirconate slaking fiber;
(4) air pre-oxidation: above-mentioned slaking fiber is placed oxidation furnace, in oxidizing atmosphere, heat up, and 210 ℃ of insulations 1 hour, do not melted Polycarbosilane/tetrabutyl zirconate fiber after being cooled to room temperature according to 20 ℃/h;
(5) high temperature burns till: above-mentioned fusion-free fibre is placed high-purity argon gas protection high temperature furnace down, be warming up to 1300 ℃, and be incubated 1 hour under this temperature, obtain superfine zirconia/silicon carbide gradient distributed fibers.
Embodiment 3
(1) preparation spinning solution: is that 1.5:1 is dissolved in the dimethylbenzene altogether with the butanol solution of Polycarbosilane solid (softening point is 200 ~ 220 ℃) and 85% tetrabutyl zirconate according to the mass ratio of Polycarbosilane and tetrabutyl zirconate, by Polycarbosilane and solvent (dimethylbenzene and n-butanol) than being 1.1: 1g/ml prepares Polycarbosilane/tetrabutyl zirconate solution, and with ultrasonic dispersion 30 minutes;
(2) electrostatic spinning: spinning condition is: the syringe needle internal diameter is 0.8mm, and voltage 25kV receives flight lead from 25cm, feeding rate 40 μ l/min, and aluminium foil is received silk, makes Polycarbosilane/tetrabutyl zirconate fibrillation;
(3) slaking heat treatment: above-mentioned fibrillation is placed baking oven, and 120 ℃ are incubated 80 hours under air, obtain Polycarbosilane/tetrabutyl zirconate slaking fiber;
(4) air pre-oxidation: above-mentioned slaking fiber is placed oxidation furnace, in oxidizing atmosphere, heat up, and 200 ℃ of insulations 1.5 hours, do not melted Polycarbosilane/tetrabutyl zirconate fiber after being cooled to room temperature according to 15 ℃/h;
(5) high temperature burns till: above-mentioned fusion-free fibre is placed high-purity argon gas protection high temperature furnace down, be warming up to 1400 ℃, and be incubated 1 hour under this temperature, obtain superfine zirconia/silicon carbide gradient distributed fibers.
Embodiment 4
(1) preparation spinning solution: is altogether to be dissolved in dimethylbenzene at 1: 1 with the butanol solution of Polycarbosilane solid (softening point is 200 ~ 220 ℃) and 85% tetrabutyl zirconate according to the mass ratio of Polycarbosilane and tetrabutyl zirconate, by Polycarbosilane and solvent (dimethylbenzene and n-butanol) than being 1.4: 1g/ml prepares Polycarbosilane/tetrabutyl zirconate solution, and with ultrasonic dispersion 30 minutes;
(2) electrostatic spinning: spinning condition is: the syringe needle internal diameter is 1.0mm, and voltage 25kV receives flight lead from 25cm, feeding rate 35 μ l/min, and aluminium foil is received silk, makes Polycarbosilane/tetrabutyl zirconate fibrillation;
(3) slaking heat treatment: above-mentioned fibrillation is placed baking oven, and 100 ℃ are incubated 100 hours under air, obtain Polycarbosilane/tetrabutyl zirconate slaking fiber;
(4) air pre-oxidation: above-mentioned slaking fiber is placed oxidation furnace, in oxidizing atmosphere, heat up, and 210 ℃ of insulations 1.5 hours, do not melted Polycarbosilane/tetrabutyl zirconate fiber after being cooled to room temperature according to 15 ℃/h;
(5) high temperature burns till: above-mentioned fusion-free fibre is placed high-purity argon gas protection high temperature furnace down, be warming up to 1400 ℃, and be incubated 1 hour under this temperature, obtain superfine zirconia/silicon carbide gradient distributed fibers.
Claims (2)
1. the preparation method of a superfine zirconia/silicon carbide gradient distributed fibers is characterized in that, may further comprise the steps:
(1) preparation spinning solution: with softening point is that 200 ~ 220 ℃ solid Polycarbosilane and mass fraction are that the butanol solution of 80 ~ 90% tetrabutyl zirconate is 1: 1 ~ 9: 1 by mass ratio, with dimethylbenzene is solvent, preparation Polycarbosilane/tetrabutyl zirconate solution, and with ultrasonic dispersion 30 minutes;
(2) electrostatic spinning: spinning condition is: the syringe needle internal diameter is 0.5 ~ 1.5mm, and voltage is 12 ~ 30kV, receives flight lead from being 15 ~ 25cm, and feeding rate is 10 ~ 50 μ l/min, and aluminium foil is received silk, makes Polycarbosilane/tetrabutyl zirconate fibrillation;
(3) slaking heat treatment: above-mentioned fibrillation is placed baking oven, under air,, obtain Polycarbosilane/tetrabutyl zirconate slaking fiber 80 ~ 120 ℃ of insulations 30 ~ 120 hours;
(4) air pre-oxidation: above-mentioned slaking fiber is placed oxidation furnace, in oxidizing atmosphere, heat up, and 190 ~ 220 ℃ of insulations 0.5 ~ 1.5 hour, do not melted Polycarbosilane/tetrabutyl zirconate fiber after being cooled to room temperature according to 15 ~ 25 ℃/h;
(5) high temperature burns till: above-mentioned fusion-free fibre is placed high-purity argon gas protection high temperature furnace down, be warming up to 1200 ~ 1450 ℃, and be incubated 1 hour under this temperature, obtain superfine zirconia/silicon carbide gradient distributed fibers.
2. the preparation method of superfine zirconia/silicon carbide gradient distributed fibers according to claim 1 is characterized in that, described Polycarbosilane is 1: 1 ~ 1.4 with the mixed solvent ratio of n-butanol and dimethylbenzene: 1g/ml; Described n-butanol is the n-butanol in the butanol solution of 80 ~ 90% tetrabutyl zirconate.
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| CN102392326B (en) * | 2011-10-10 | 2013-07-31 | 中国人民解放军国防科学技术大学 | Axial gradient silicon carbide fibers and preparation method and device thereof |
| CN105544013B (en) * | 2016-01-29 | 2017-11-24 | 东南大学 | Different silicon carbide fibre of a kind of zirconium content and preparation method thereof |
| CN110436935B (en) * | 2019-08-06 | 2022-03-04 | 江西嘉捷信达新材料科技有限公司 | Superfine zirconium dioxide/SiC composite long fiber and preparation method and application thereof |
| CN112210848B (en) * | 2020-10-12 | 2023-04-28 | 中国人民解放军国防科技大学 | Preparation method of multiphase SiZrOC micro-nano heat insulation fiber |
| CN114751761B (en) * | 2022-04-26 | 2023-04-18 | 天津城建大学 | Light-weight load-bearing nano ceramic aerogel based on electrospinning method and preparation method thereof |
| CN114753025B (en) * | 2022-05-10 | 2024-06-25 | 中国人民解放军国防科技大学 | High-strength high-toughness silicon-oxygen carbon fiber and preparation method and application thereof |
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