CN103951455A - Method for preparing dense carbon nanotube-fiber-precursor ceramic composite material with the assistance of freeze drying - Google Patents
Method for preparing dense carbon nanotube-fiber-precursor ceramic composite material with the assistance of freeze drying Download PDFInfo
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- CN103951455A CN103951455A CN201410140431.8A CN201410140431A CN103951455A CN 103951455 A CN103951455 A CN 103951455A CN 201410140431 A CN201410140431 A CN 201410140431A CN 103951455 A CN103951455 A CN 103951455A
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Abstract
The invention discloses a method for preparing dense carbon nanotube-fiber-precursor ceramic composite material with the assistance of freeze drying, which comprises the following steps: dipping fiber strips in a carbon nanotube aqueous solution, performing vacuum pumping; then performing freeze drying processing to obtain a fiber-carbon nanotube preform; fully dipping the preform in an organic precursor solution, curing; and finally performing pyrolyzation at a high temperature in Ar atmosphere to prepare the porous fiber-carbon nanotube-ceramic based composite material. The method of the invention not only improves the toughness and strength of the ceramic-based composite material by introduction of carbon nanotubes, but also has the advantages of simple process, low cost, and low requirement for the length-diameter ratio of the carbon nanotube raw material.
Description
Technical field
The invention belongs to the preparation field of ceramic composite, more specifically, a kind of particularly method that adopts the fine and close carbon nanotube/fiber/precursor ceramic composite material of the auxiliary preparation of lyophilize.
Background technology
Fiber/precursor ceramic is a type high temp structured material, compare with other material, it has the features such as low density, high strength, high tenacity, high temperature resistant, resistance to chemical attack, resistance to ablation, antiscour, high rigidity and high-wearing feature, not only overcome the shortcoming of one-component ceramic brittle rupture, also retained the excellent properties that pottery has.And by the introducing of carbon nanotube, can greatly improve electroconductibility and the mechanical property of material, be expected to further improve the performance of fiber/precursor ceramic composite material.Feature based on carbon nanotube/fiber/precursor ceramic, this material has broad application prospects in fields such as strategic weapon, space technology, energy technology, chemical industry, transportation industries.
Lyophilize, also can be referred to as drying bu sublimation, it is that the temperature through a certain amount of wet stock is reduced to below material eutectic temperature, make the moisture fully charge of material inside, form solid-state ice, then suitably extract the air in dryness storehouse, make it reach certain vacuum tightness, afterwards hot-plate is heated at the temperature that reaches suitable, ice is directly distilled as water vapour, recycle the water vessel of vacuum system or the condensation of moisture device of refrigeration system by water vapor condensation, thereby obtain dry products material.Its most significant advantage is: freezing dry process can make the particle in material be fixed up by original position, has kept the original microscopic pattern of material.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, for prior art, prepare carbon nanotube/fiber/precursor ceramic composite material technique comparatively complicated, and be difficult to make carbon nanotube can be dispersed in preferably on the interface between fiber/precursor ceramic and (play the effect that weakens interface bond strength), can be distributed in preferably the deficiency that (hinders dislocation moving and crack propagation in matrix) in precursor ceramic matrix again, there is technique simple, and can significantly optimize the distribution of carbon nanotube in matrix material so that it brings into play the advantage of self-acting better.
Technical purpose of the present invention is achieved by following technical proposals:
Adopt the method for the fine and close carbon nanotube-fiber-precursor ceramic composite material of the auxiliary preparation of lyophilize, according to following step, carry out:
Step 1, is impregnated into fabric in the suspension of carbon nanotube, and vacuumizes; Then the fabric after dipping is placed in to 0 ℃ and is frozen into below solid-state block, on lyophilizer, carry out subsequently lyophilize, obtain carbon nanotube-fiber preform;
Step 2, is impregnated into carbon nanotube-fiber preform in organic precursor-organic solvent, and vacuumizes; Then under 110-120 degree, solidify 6～10h, obtain carbon nanotube-fiber-organic precursor block;
Step 3, under atmosphere of inert gases, is warming up to 900～1200 ℃ from room temperature with 2～15 ℃/min speed by carbon nanotube-fiber-organic precursor block, and pyrolysis 1-2h obtains the fiber-carbon nanotube-precursor ceramic composite material of porous;
Step 4, repeats step 2 and step 3 by the fiber-carbon nanotube-precursor ceramic composite material obtaining through step 3, repeats dipping and pyrolysis, can obtain fine and close carbon nanotube-fiber-precursor ceramic composite material.
In wherein said step 1, in the suspension of carbon nanotube, carbon nanotube concentration is 0.1～5wt%; Described fiber is carbon fiber or silicon carbide fiber, and described fabric is that carbon cloth laminated material, two-dimentional carbon cloth laminated material, three-dimensional carbon fiber knit body, the Unidirectional SiClx fibrous bundle that unidirectional carbon fiber tow arrangement forms arranged the silicon carbide fiber cloth laminated material forming, two-dimentional silicon carbide fiber cloth laminated material, any one in the silicon carbide fiber knitted body of three-dimensional.
In described step 2, described organic precursor is any one in Polycarbosilane, polysiloxane, polysilazane, poly-borosilicate azane; Described organic solvent is any one in divinylbenzene, dimethylbenzene, normal hexane; In organic precursor-organic solvent, organosilane precursor body burden is 30～70wt%.
Wherein the number-average molecular weight 1000-1400(of Polycarbosilane is for example purchased from Suzhou Cerafil Ceramic Fiber Co., Ltd.); Polysiloxane is hydrogen containing siloxane, and number-average molecular weight 500-800(is for example purchased from spark chemical plant, Jiangxi); Polysilazane number-average molecular weight 450-600(is for example purchased from the National University of Defense technology); Poly-borosilicate azane number-average molecular weight 800-1000(is for example purchased from University Of Tianjin's Materials Academy).
In described step 3, described atmosphere of inert gases is nitrogen, helium or argon gas.
The invention has the beneficial effects as follows, with respect to: (1), then is introduced and is speculated presoma high temperature pyrolysis to prepare matrix material at carbon fiber surface deposition of carbon nanotubes or adopt chemical gaseous phase depositing process carbon nano-tube on carbon fiber by electrophoretic; (2) by high-energy ultrasonic method or melting, stir carbon nanotube is evenly mixed with organic precursor, be introduced into again in carbon fiber knit body high temperature pyrolysis to prepare two kinds of common technologies of matrix material, technical process of the present invention is comparatively simple, energy consumption is lower, and can introduce the CNTs of higher volume fraction, make carbon nanotube in interface and ceramic matrix, all have good distribution simultaneously, reach the effect of optimizing carbon nanotube distribution in matrix material, be conducive to obtain the material that performance is more excellent.
Accompanying drawing explanation
Fig. 1 is the SEM image of carbon fiber/carbon nanotube precast body that in the embodiment of the present invention 1, lyophilize obtains.
Fig. 2 is the carbon fiber/carbon nanotube/composite silicon carbide ceramic material fracture surface SEM photo finally obtaining in the embodiment of the present invention 1.
Embodiment
Below in conjunction with specific embodiment, the present invention is done more specifically bright.
The carbon nanotube aqueous slurry (massfraction of carbon nanotube is 5%, and the dispersion agent of use is PVP) that the carbon nanotube water system suspension using in following examples is produced for Nanometer Port Co., Ltd., Shenzhen.
Embodiment 1
(1) weigh 10g carbon nanotube aqueous slurry, and add wherein in 40g deionized water, stir and obtain carbon nanotube suspension;
(2) the two-dimension laminate carbon fiber batten with regular shape of having sheared is immersed in above-mentioned suspension liquid, and vacuumize 30min;
(3) exhaust after vacuum, by the carbon fiber batten that is soaked with carbon nanotube suspension in refrigerator-freezer, freezing 8h at-197 ℃; By its lyophilize 48h on lyophilizer, obtain carbon fiber/carbon nanotube precast body subsequently;
(4) weigh 30g Polycarbosilane (Suzhou Cerafil Ceramic Fiber Co., Ltd.), be dissolved in 22g diethylbenzene, stir and obtain organosilane precursor liquid solution;
(5) carbon nanotube/fiber preform is impregnated in organosilane precursor liquid solution, and vacuumizes 30min; Then at 120 ℃, solidify 6h, obtain carbon nanotube/carbon fiber/organic precursor block;
(6) by carbon nanotube/fiber/organic precursor block under Ar gas, with 10 ℃/min and at 1000 ℃ pyrolysis 2h, obtain the carbon nanotube/carbon fiber/composite silicon carbide ceramic material of porous;
(7) by the carbon nanotube/carbon fiber of the porous obtaining/composite silicon carbide ceramic material repeating step (4) (5) (6), obtain fine and close carbon nanotube/carbon fiber/composite silicon carbide ceramic material.
Carbon fiber/carbon nanotube precast body that in the present embodiment, lyophilize obtains and the carbon fiber/carbon nanotube/composite silicon carbide ceramic material fracture surface SEM photo finally obtaining are distinguished as shown in Figure 1 and Figure 2.As can be seen from Figure 1, in carbon fiber/carbon nanotube precast body that lyophilize obtains, carbon nanotube lamella is wrapped in carbon fiber surface uniformly, and forms and build bridge between carbon fiber.This structure not only can effectively be improved the interface combination of carbon fiber and ceramic matrix, and can improve intensity and the toughness of matrix.Fig. 2 can find out, the introducing of organic precursor and high temperature pyrolysis process do not affect carbon nanotube in the distribution of carbon fiber surface, also finds simultaneously, and have extracting of obvious carbon nanotube, this can effectively improve intensity and the toughness of ceramic matrix.
Embodiment 2
(1) weigh 20g carbon nanotube aqueous slurry, and add wherein in 30g deionized water, stir and obtain carbon nanotube suspension;
(2) the two-dimension laminate carbon fiber batten with regular shape of having sheared is immersed in above-mentioned suspension liquid, and vacuumize 30min;
(3) exhaust after vacuum, by the carbon fiber batten that is soaked with carbon nano-tube aqueous solutions in refrigerator-freezer, freezing 8h at-197 ℃; By its lyophilize 48h on lyophilizer, obtain carbon fiber/carbon nanotube precast body subsequently;
(4) weigh 30g Polycarbosilane, be dissolved in 22g diethylbenzene, stir and obtain organosilane precursor liquid solution;
(5) carbon nanotube/fiber preform is impregnated in organosilane precursor liquid solution, and vacuumizes 30min; Then at 120 ℃, solidify 6h, obtain carbon nanotube/carbon fiber/organic precursor block;
(6) by carbon nanotube/fiber/organic precursor block under Ar gas, with 10 ℃/min and at 1000 ℃ pyrolysis 2h, obtain the carbon nanotube/carbon fiber/composite silicon carbide ceramic material of porous;
(7) by the carbon nanotube/carbon fiber of the porous obtaining/composite silicon carbide ceramic material repeating step (4) (5) (6), obtain fine and close carbon nanotube/carbon fiber/composite silicon carbide ceramic material.
The raising of content of carbon nanotubes in carbon nanotube suspension, can cause content of carbon nanotubes in final material to rise.The size of fiber surface carbon nanotube layer and bridge formation all improves simultaneously.
Embodiment 3
(1) weigh 10g carbon nanotube aqueous slurry, and add wherein in 40g deionized water, stir and obtain carbon nanotube suspension;
(2) the two-dimension laminate carbon fiber batten with regular shape of having sheared is immersed in above-mentioned suspension liquid, and vacuumize 30min;
(3) exhaust after vacuum, by the carbon fiber batten that is soaked with carbon nano-tube aqueous solutions in refrigerator-freezer, freezing 8h at-18 ℃; By its lyophilize 48h on lyophilizer, obtain carbon fiber/carbon nanotube precast body subsequently;
(4) weigh 30g Polycarbosilane, be dissolved in 22g diethylbenzene, stir and obtain organosilane precursor liquid solution;
(5) carbon nanotube/fiber preform is impregnated in organosilane precursor liquid solution, and vacuumizes 30min; Then at 120 ℃, solidify 6h, obtain carbon nanotube/carbon fiber/organic precursor block;
(6) by carbon nanotube/fiber/organic precursor block under Ar gas, with 10 ℃/min and at 1000 ℃ pyrolysis 2h, obtain the carbon nanotube/carbon fiber/composite silicon carbide ceramic material of porous;
(7) by the carbon nanotube/carbon fiber of the porous obtaining/composite silicon carbide ceramic material repeating step (4) (5) (6), obtain fine and close carbon nanotube/carbon fiber/composite silicon carbide ceramic material.
Freezing temp is very large for the distribution influence of carbon nanotube in final material.Improve freezing temp, can form relatively large ice crystal, thereby cause more carbon nanotube to be wrapped in carbon fiber surface, and build bridge seldom.
Embodiment 4
(1) weigh 10g carbon nanotube aqueous slurry, and add wherein in 40g deionized water, stir and obtain carbon nanotube suspension;
(2) the two-dimension laminate carbon fiber batten with regular shape of having sheared is immersed in above-mentioned suspension liquid, and vacuumize 30min;
(3) exhaust after vacuum, by the carbon fiber batten that is soaked with carbon nano-tube aqueous solutions in refrigerator-freezer, freezing 8h at-197 ℃; By its lyophilize 48h on lyophilizer, obtain carbon fiber/carbon nanotube precast body subsequently;
(4) weigh 30 hydrogen containing siloxanes (spark chemical plant, Jiangxi), be dissolved into 15g divinylbenzene, and drip 0.02g cypress Jinsui River as catalyzer, stir and obtain organosilane precursor liquid solution;
(5) carbon nanotube/fiber preform is impregnated in organosilane precursor liquid solution, and vacuumizes 30min; Then at 120 ℃, solidify 6h, obtain carbon nanotube/carbon fiber/organic precursor block;
(6) by carbon nanotube/fiber/organic precursor block under Ar gas, with 10 ℃/min and at 1000 ℃ pyrolysis 2h, obtain carbon nanotube/carbon fiber/silicon-oxygen-carbon ceramic matrix material of porous;
(7), by the carbon nanotube/carbon fiber of the porous obtaining/silicon-oxygen-carbon ceramic matrix material repeating step (4) (5) (6), obtain fine and close carbon nanotube/carbon fiber/silicon-oxygen-carbon ceramic matrix material.
Presoma is changed to silica carbon matrix precursor, by similar processing step, also successfully prepared fine and close carbon fiber/carbon nanometer tube/silicon oxygen carbon ceramic composite materials.
Above-mentioned example adopts three-point bending strength and the fracture toughness property of the Materials Academy SJ-1A of University Of Tianjin type triaxial shear equipment test material.Test sample is of a size of 40mm * 4mm * 2mm, test span 32mm, loading rate 0.5mm/min.
Known by upper table, the appropriate carbon nanotube (as example 1) of introducing, can effectively improve intensity and the fracture toughness property of material, but excessive carbon nanotube makes the degradation (as example 2) of material on the contrary, freezing temp also can obviously affect the distribution of carbon nanotube in material, too high improve (as the example 3) that is unfavorable for material property of freezing temp simultaneously.Example 4 is performances of material after change presoma, although performance performance declines to some extent, because raw material is relatively cheap, also has certain application prospect.
The above-mentioned description to embodiment is to be convenient to those skilled in the art can understand and apply the invention.Person skilled in the art easily makes various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement of making for the present invention and modification all should be within protection scope of the present invention.
Each cited raw material of the present invention can be realized the present invention, and the bound value of raw material, interval value can realize the present invention, then this is not illustrated one by one.
Claims (6)
1. the method that adopts the fine and close carbon nanotube-fiber-precursor ceramic composite material of the auxiliary preparation of lyophilize, is characterized in that, according to following step, carries out:
Step 1, is impregnated into fabric in the suspension of carbon nanotube, and vacuumizes; Then the fabric after dipping is placed in to 0 ℃ and is frozen into below solid-state block, on lyophilizer, carry out subsequently lyophilize, obtain carbon nanotube-fiber preform;
Step 2, is impregnated into carbon nanotube-fiber preform in organic precursor-organic solvent, and vacuumizes; Then under 110-120 degree, solidify 6～10h, obtain carbon nanotube-fiber-organic precursor block;
Step 3, under atmosphere of inert gases, is warming up to 900～1200 ℃ from room temperature with 2～15 ℃/min speed by carbon nanotube-fiber-organic precursor block, and pyrolysis 1-2h obtains the fiber-carbon nanotube-precursor ceramic composite material of porous;
Step 4, repeats step 2 and step 3 by the fiber-carbon nanotube-precursor ceramic composite material obtaining through step 3, repeats dipping and pyrolysis, can obtain fine and close carbon nanotube-fiber-precursor ceramic composite material.
2. the auxiliary method of preparing fine and close carbon nanotube-fiber-precursor ceramic composite material of employing lyophilize according to claim 1, is characterized in that, in described step 1, in the suspension of carbon nanotube, carbon nanotube concentration is 0.1～5wt%.
3. the method for the fine and close carbon nanotube-fiber-precursor ceramic composite material of preparation is assisted in employing lyophilize according to claim 1, it is characterized in that, in described step 1, described fiber is carbon fiber or silicon carbide fiber, described fabric is that unidirectional carbon fiber tow is arranged the carbon cloth laminated material forming, the carbon cloth laminated material of two dimension, three-dimensional carbon fiber knit body, Unidirectional SiClx fibrous bundle is arranged the silicon carbide fiber cloth laminated material forming, the silicon carbide fiber cloth laminated material of two dimension, any one in three-dimensional silicon carbide fiber knitted body.
4. the method for the fine and close carbon nanotube-fiber-precursor ceramic composite material of preparation is assisted in employing lyophilize according to claim 1, it is characterized in that, in described step 2, described organic precursor is any one in Polycarbosilane, polysiloxane, polysilazane, poly-borosilicate azane; Described organic solvent is any one in divinylbenzene, dimethylbenzene, normal hexane; In organic precursor-organic solvent, organosilane precursor body burden is 30～70wt%.
5. the auxiliary method of preparing fine and close carbon nanotube-fiber-precursor ceramic composite material of employing lyophilize according to claim 1, is characterized in that the number-average molecular weight 1000-1400 of described Polycarbosilane; Polysiloxane is hydrogen containing siloxane, number-average molecular weight 500-800; Polysilazane number-average molecular weight 450-600; Poly-borosilicate azane number-average molecular weight 800-1000.
6. the auxiliary method of preparing fine and close carbon nanotube-fiber-precursor ceramic composite material of employing lyophilize according to claim 1, is characterized in that, in described step 3, described atmosphere of inert gases is nitrogen, helium or argon gas.
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| CN109534816A (en) * | 2017-09-21 | 2019-03-29 | 中南大学 | A method of preparing porous silicon carbide ceramic with high strength |
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