CN101050117A - Method and equipment for preparing precursor body of poly carbon silane ceramics of containing zirconium - Google Patents
Method and equipment for preparing precursor body of poly carbon silane ceramics of containing zirconium Download PDFInfo
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Abstract
This invention discloses method and apparatus for preparing polycarbosilane ceramic precursor containing Zr. The method comprises: utilizing low molecular weight polymer with S-H bonds (polysilane, polycarbosilane or poly(dimethyl silane)) as the raw material, organic metallic compound containing Zr as the additive, and Ar, N2 or their mixture as the protective atmosphere, and pyrolyzing at high temperatures and normal pressure to obtain Zr-containing SiC ceramic precursor PZCS. The pyrolysis apparatus comprises a three-necked flask in the heater, a pyrolysis column in the electric heating jacket, a condensing tube, a separatory funnel, and a vacuum system seam. The method is simple, and can control the content and properties of Zr in the precursor and the ceramic. The product has such advantages as high purity, high remoldability, and high heat resistance.
Description
Technical field
The present invention relates to a kind of preparation method and device that contains the precursor body of poly carbon silane ceramics of heterogeneous element zirconium, especially relate to a kind of with the main chain silicon-containing polymer with contain preparation method and the device that the zirconium metal-organic compound is the precursor body of poly carbon silane ceramics that contains the heterogeneous element zirconium of main raw material.
Background technology
Along with science and technology development, fields such as national defence, aerospace, the energy have proposed more and more higher requirement to the lightweight of material, high-strength, Gao Mo, high temperature resistant, corrosion-resistant, anti-oxidant, performance such as resistance to wear.Development high-performance ceramic and matrix material replacement conventional high-temperature alloy thereof and refractory metal material have become main direction of studying from now on.High-performance ceramic is in fields such as high-temperature engine, turbine, atomic reactor wall, catalyzer heat exchanger and firing system, MEMS (Microelectromechanic system) pyrostats, in industrial aspect such as metallurgy, weapons, electronics, a lot of purposes are arranged also.
The SiC pottery has excellent properties such as high strength, high-modulus, high temperature resistant, anticorrosive, anti-oxidant, low density, intensity can remain to 1600 ℃, the pottery antioxidant property reaches 1300 ~ 1700 ℃, from use temperature and over-all properties such as anti-oxidant, the SiC pottery is the preferred material that is used for the ultrahigh-temperature working part, has purposes widely at high-technology field.
Infer that according to theory single-phase SiC pottery has splendid heatproof potentiality, pure β-SiC crystal can high temperature resistantly reach 2600 ℃.But the high thermal resistance of existing SiC pottery does not but far reach this theoretical temperatures, and its basic reason is that existing SiC pottery is not to be made up of pure β-SiC crystal.In SiC pottery temperature-rise period, when temperature reaches more than 1400 ℃, original β-SiC crystallite constantly obtains new replenishing from external phase, crystal grain is sharply grown up, diameter reaches more than the 7nm, and original vitreous state external phase becomes the sealing coat of megacryst intergranular, and big crystal grain and be full of and form very big interfacial stress between the sealing coat of defective causes SiC pottery mechanical properties decrease.After temperature surpassed 1800 ℃, β-SiC grain-size can surpass 1 μ m, and begins to separate out from ceramic surface, causes the SiC ceramic powderization, and the mechanical property of SiC pottery is sharply reduced.
Therefore, for preparation high-performance SiC pottery, maximum problem is to prevent that β under the ultrahigh-temperature-SiC crystal grain from too growing up.In order to improve the performance of SiC pottery, in preparation SiC ceramic precursor process, introduce high melting compound or heterogeneous element, synthesize and contain heterogeneous element SiC pottery, become the main flow of current high-performance SiC stupalith development.
The disclosed main preparation methods that contains the SiC pottery of heterogeneous element has that sintering process (comprising reaction sintering, normal pressure-sintered, liquid phase sintering and HIP sintering etc.), self-propagating high-temperature burning are synthetic, sol-gel method (Sol-gel), chemical vapor deposition (CVD) and organic precursor method conversion method etc.Method costs such as sintering process are higher, and the skewness of the heterogeneous element of introducing in product particularly is difficult to prepare complex construction SiC based composite ceramic material.The precursor conversion method is to be precursor with organic polymer (being generally organometallic polymer), utilize its characteristic moulding such as solvable after, through the elevated temperature heat disaggregating treatment, make it to change into the method for inorganic ceramic material from organism.This organometallic polymer is called organic precursor method or ceramic precursor (Preceramicpolymer, Precursor), the precursor conversion method have the preparation process temperature low, be easy to be shaped, product purity is higher, be easy to advantage such as industrialization, has become one of main method of preparation ceramic fiber, ceramic matric composite.
The precursor conversion method of preparation high-performance SiC pottery is introduced heterogeneous element in the SiC ceramic precursor at present, improves the over-all properties of SiC pottery, makes the SiC pottery keep higher intensity, and its key problem in technology is to contain the synthetic of heterogeneous element SiC ceramic precursor.
Mostly the method for introducing heterogeneous element at present in precursor is to add metal simple-substance, reaction process is restive, processing unit is complicated, heterogeneous element distributivity in precursor and pottery thereof is inhomogeneous, do not reach the homogenize of molecule rank far away, be difficult to the effect that the performance heterogeneous element improves SiC ceramic precursor and ceramic performance thereof, and product purity is still lower, realizes that the difficulty of large-scale industrial production is still bigger.
Summary of the invention
The objective of the invention is to overcome existing Stainless Steel via Precursor Pyrolysis SiC pottery and fiber superhigh temperature resistant poor performance thereof, function singleness, processing unit than shortcomings such as complexity, a kind of SiC of raising pottery superhigh temperature resistant performance is provided, make SiC pottery functional diversities, preparation technology's equipment simply contains the SiC ceramic setter preparation and the device of heterogeneous element zirconium.
Further purpose of the present invention is to provide the SiC ceramic setter preparation of a kind of adjustable SiC ceramic precursor rheological property and reshaping.
For realizing first purpose of the invention described above, preparation method of the present invention adopts following technical proposals: with for example poly-silicon-carbon silane (PSCS) of the siliceous lower molecular weight organic polymer of main chain, the organic compound that polysilane (PS), Polycarbosilane (PCS), polydimethyl silane (PDMS) etc. contain the Si-H key is a raw material, the organometallic compound of zirconium such as the acetylacetonate compound of zirconium, carbonyl compound, keto compounds and dis-cyclopentadiene compounds are reaction additives, with Ar, N
2Or its mixture is protective atmosphere, utilizes the preparation of constant-pressure and high-temperature cracking process to contain the SiC ceramic precursor PZCS (Polyzirconocarbosilane) of heterogeneous element zirconium.The constant-pressure and high-temperature cracker of preparation facilities of the present invention comprises the reactor there-necked flask that places well heater, and described there-necked flask is provided with thermopair, N
2Inlet mouth and from the phegma of separating funnel inlet, there-necked flask is communicated with the material inlet of the cracking post that places electric mantle, the material outlet of described cracking post is communicated with prolong, described prolong is communicated with vapor pipe, vacuum system interface and separating funnel by transfer tube, the lower part outlet of described separating funnel is communicated with there-necked flask, also is provided with thermopair between electric mantle and the cracking post.
For realizing second purpose of the invention described above, on the basis of aforementioned schemes, the present invention passes through control and reacts factors such as the proportioning of main raw material and additive, temperature of reaction, reaction times, cracking temperature, reach the purpose that control contains the character such as softening temperature, molecular weight distribution of zirconium SiC ceramic precursor, to improve the physics rheological property of SiC ceramic precursor, help the reshaping processing of SiC ceramic precursor, contain zirconium SiC ceramic fiber etc. as spinning.
The present invention specifically may further comprise the steps: low-molecular weight polymer that (1) is siliceous with main chain such as liquid state are gathered silicon-carbon silane (PSCS), polydimethyl silane (PDMS), Polycarbosilane (PCS) (softening temperature is 80-450 ℃) or polysilane (PS) and are placed the reactor there-necked flask, and add the zirconium organometallics of 0.5wt%-20wt% (preferred 1wt%-10wt%); (2) the constant-pressure and high-temperature cracker that utilizes the present inventor to develop is at Ar or N
2Under the protection, reactor there-necked flask temperature rises to 350-480 ℃ (preferred 390-450 ℃) according to 0.1-1 ℃/min temperature rise rate, the cracking column temperature is controlled at 450-550 ℃, carry out the thermolysis rearrangement reaction, reaction times 0.5-20h (preferred 4-15h) gets the thick product of PZCS after the cooling; (3) should thick product through xylene soluble, filtration, filtrate is carried out underpressure distillation at 300-390 ℃, promptly gets the translucent PZCS of light yellow resin shape after the cooling.
Afterwards, can carry out follow-up reshaping, prepare matrix material as the spinning ceramic fiber or as steeping fluid.
Show that through IR, GPC, ultimate analysis the Si-H key of the SiC ceramic precursor PZCS that the present invention prepares is abundant, help reshaping processing, infrared spectrum and PCS are more or less the same, the molecular weight distribution broad.
Zirconium can reach the homogenize of molecule rank in precursor and pottery thereof, β-SiC crystal grain has more significantly effect in the growth under the ultrahigh-temperature in the SiC pottery to suppressing to introduce the heterogeneous element zirconium, and can improve ceramic densification degree, improved the superhigh temperature resistant performance of SiC pottery greatly, and the resistivity that contains zirconium SiC pottery of preparation is adjustable continuously, having good microwave absorbing property, is excellent absorbing material material standed for.
Periodic table of chemical element IVB (the Ti of family, Zr, Hf) and VB family (Nb, Ta) carbide of element and nitride all have high melt point (3000-4000 ℃), excellent high temperature toughness, resistance to fouling and good hardness, all should be the good additives of SiC ceramic precursor.The present inventor selects the additive of zirconium as the SiC ceramic precursor, and the synthetic SiC ceramic precursor that contains the heterogeneous element zirconium mainly is based on combined factors such as preparation cost and temperature tolerance and considers.
As seen, the present invention has following advantage: starting compound is various, wide material sources, the heterogeneous element zirconium is (according to the reasoning from logic analysis in the precursor, should be not only zirconium) content and performance index thereof controllable, compare with traditional metal simple-substance that in precursor, adds merely, this law preparation contain zirconium SiC ceramic precursor, zirconium can reach the homogenize of molecule rank in precursor and pottery thereof, reaction process is easy to control, processing unit is simple, output is high, and the product purity height, reshaping is good, the superhigh temperature resistant excellent performance; Realize large-scale industrial production easily.
Description of drawings
Fig. 1 is the structural representation that constant-pressure and high-temperature cracking process of the present invention prepares the PZCS device.
Fig. 2 is the infrared spectrogram of embodiment 1 synthetic PZCS.
Fig. 3 is the GPC spectrogram of embodiment 1 synthetic PZCS.
Fig. 4 is the TG spectrogram of embodiment 1 synthetic PZCS.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
With reference to Fig. 1, this device comprises: place the reactor there-necked flask 1 of well heater 5, be connected with thermopair 6-1, N on the there-necked flask 1
2 Inlet mouth 10 and from the phegma of separating funnel 9 inlet, there-necked flask 1 is communicated with the material inlet of the cracking post 2 that places electric mantle 3, the material outlet of cracking post 2 is communicated with prolong 4, prolong 4 is communicated with vapor pipe 8, vacuum system interface 7 and separating funnel 9 by transfer tube, the lower part outlet of separating funnel 9 is communicated with there-necked flask 1, is provided with thermopair 6-2 between electric mantle 3 and the cracking post 2.The following stated PZCS preparation method of the present invention embodiment all uses said apparatus.
The operation steps of each embodiment of the following stated PZCS preparation method of the present invention is: (1) with the poly-silicon-carbon silane (PSCS) of liquid state, polydimethyl silane (PDMS), Polycarbosilane (softening temperature is 80 ~ 450 ℃) (PCS) or polysilane (PS) place there-necked flask 1, and add the zirconium organometallics of 1wt% ~ 20wt%; (2) close venting port 8, system is vacuumized by vacuum system 7, and with Ar or N
2Feed there-necked flask 1, displacement is opened venting port 8, control Ar or N after falling air three times in the device
2Feeding speed and keep, utilize well heater 5 to make the material in the there-necked flask 1 be warming up to 350 ~ 480 ℃, carry out the polyreaction of zirconium organometallics and silicon-containing polymer, meanwhile, the gasification of partial reaction product enters row and separates post 2, utilizes electric mantle 3 to make row separate post 2 and is warming up to 450 ~ 550 ℃, gasification materiel is separated at row and is carried out the thermolysis rearrangement reaction in the post 2, the decomposition rearrangement product enters separating funnel 9, the piston of control separating funnel 9 after cooling off by prolong 4, adjust the speed of liquid return to there-necked flask, phegma flows into there-necked flask and continues to participate in reaction, and whole process reaction 0.5 ~ 20h is after reaction finishes, cool to room temperature gets the thick product of PZCS.(3) with the thick product of PZCS through xylene soluble, filtration, filtrate is carried out underpressure distillation at 300 ~ 390 ℃, promptly gets light yellow resin shape PZCS after the cooling.
Embodiment 1.
With PSCS and methyl ethyl diketone zirconium is raw material, the two quality proportioning (the described proportioning of following each embodiment is the quality proportioning) is: methyl ethyl diketone zirconium: PSCS=4: 100,420 ℃ of temperature of reaction, 500 ℃ of cracking temperatures are behind the insulation reaction 6h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 390 ℃, making softening temperature is 215 ℃, contains the PZCS of zirconium 1.31wt%, productive rate 51.1%.N
2The following 1250 ℃ of insulations of atmosphere 1 hour, ceramic yield is 68.3%.Its reaction mechanism is shown below:
The infrared spectrogram of present embodiment synthetic PZCS, GPC spectrogram, TG spectrogram are seen Fig. 2, Fig. 3, Fig. 4 respectively.
Embodiment 2.
With PCS and tetraethoxy zirconium is raw material, tetraethoxy zirconium: PCS=1: 100, temperature of reaction is 450 ℃, 450 ℃ of cracking temperatures are behind the insulation reaction time 1h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 350 ℃, making softening temperature is 242 ℃, contains the PZCS of zirconium 0.61wt%, productive rate 48.2%.N
2The following 1250 ℃ of insulations of atmosphere 1 hour, ceramic yield is 66.5%.
With PS and methyl ethyl diketone zirconium is raw material, methyl ethyl diketone zirconium: PS=20: 100,350 ℃ of temperature of reaction, 550 ℃ of cracking temperatures are behind the insulation reaction time 20h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 370 ℃, making softening temperature is 195 ℃, contains the PZCS of zirconium 6.63wt%, productive rate 46.8%.N
2The following 1250 ℃ of insulations of atmosphere 1 hour, ceramic yield is 73.5%.
Embodiment 4.
With PDMS and methyl ethyl diketone zirconium is raw material, methyl ethyl diketone zirconium: PDMS=10: 100,450 ℃ of temperature of reaction, 500 ℃ of cracking temperatures are behind the insulation reaction 8h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 350 ℃, making softening temperature is 256 ℃, contains the PZCS of zirconium 3.85wt%, productive rate 43.4%.N
2The following 1250 ℃ of insulations of atmosphere 1 hour, ceramic yield is 71.2%.
With PSCS and bis cyclopentadienyl zirconium dichloride is raw material, bis cyclopentadienyl zirconium dichloride: PSCS=8: 100, temperature of reaction is 390 ℃, 520 ℃ of cracking temperatures are behind the insulation reaction time 15h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 330 ℃, making softening temperature is 221 ℃, contains the PZCS of zirconium 4.78wt%, productive rate 45.7%.N
2The following 1250 ℃ of insulations of atmosphere 1 hour, ceramic yield is 62.9%.
Embodiment 6.
When being raw material with PCS and methyl ethyl diketone zirconium, methyl ethyl diketone zirconium: PSCS=4: 100,420 ℃ of temperature of reaction, 500 ℃ of cracking temperatures are behind the insulation reaction time 6h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 300 ℃, making softening temperature is 208 ℃, contains the PZCS of zirconium 1.34wt%, productive rate 52.7%.N
2The following 1250 ℃ of insulations of atmosphere 1 hour, ceramic yield is 67.8%.
Above result shows, prepares in the process of the precursor body of poly carbon silane ceramics that contains the heterogeneous element zirconium at the constant-pressure and high-temperature cracking process, and product characteristics depends on reaction raw materials and reaction conditionss such as proportioning, temperature of reaction, cracking temperature, reaction times and vacuum distillation temperature.Under following reaction conditions, the PZCS precursor that availability is good: when being raw material with PSCS and methyl ethyl diketone zirconium, methyl ethyl diketone zirconium/PSCS mass ratio is 2 ~ 10%, temperature of reaction is 390 ~ 420 ℃, 480 ~ 530 ℃ of cracking temperatures, behind insulation reaction time 4 ~ 20h, through xylene soluble, filter, filtrate is carried out underpressure distillation at 350 ~ 390 ℃, and making softening temperature is 190 ~ 240 ℃, the PZCS that contains zirconium 0.4 ~ 1.7wt%, productive rate 40 ~ 60%, the precursor performance ideal that makes helps reshaping processing, thus precursor preparation to contain zirconium SiC pottery heat resistance good, ceramic yield 60 ~ 75%.
The foregoing description shows, with the silicon-containing polymer is reaction raw materials, the organometallic compound of Zr is a reaction additives, adopt the preparation of constant-pressure and high-temperature cracking process to contain the precursor body of poly carbon silane ceramics PZCS of heterogeneous element zirconium, zr element reaches the homogenize of molecule rank in precursor, character such as zirconium content and PZCS softening temperature are controllable, can adjust the PZCS that reaction conditions prepares different size according to producing needs.By PZCS preparation to contain zirconium SiC pottery superhigh temperature resistant functional, zirconium can make ceramic densifying in containing zirconium SiC ceramic high temperature sintering oxygen removal process, and can control grain growth in the pottery, make the SiC pottery keep higher intensity, thereby reach the purpose that improves SiC pottery superhigh temperature resistant performance, zirconic SiC ceramic resistor rate is adjustable continuously, has good microwave absorbing property, is excellent absorbing material material standed for.
Claims (10)
1, a kind of preparation method of precursor body of poly carbon silane ceramics of containing zirconium, it is characterized in that, may further comprise the steps: (1) lower molecular weight organic polymer that main chain is siliceous adds in the reactor there-necked flask, and adds the zirconium organometallics that is equivalent to organic polymer 0.5wt%-20wt%; (2) the constant-pressure and high-temperature cracker that utilizes the present inventor to develop is at Ar or N
2Under the protection, reactor there-necked flask temperature rises to 350-480 ℃ according to 0.1-1 ℃/min temperature rise rate, and the cracking column temperature is controlled at 450-550 ℃, carries out the thermolysis rearrangement reaction, and reaction times 0.5-20h gets the thick product of PZCS after the cooling; (3) should thick product through xylene soluble, filtration, filtrate is carried out underpressure distillation at 300-390 ℃, promptly gets the translucent PZCS of light yellow resin shape after the cooling.
2, the preparation method of precursor body of poly carbon silane ceramics of containing zirconium according to claim 1 is characterized in that, described reactor there-necked flask temperature is 390-450 ℃.
3, the preparation method of precursor body of poly carbon silane ceramics of containing zirconium according to claim 1 and 2 is characterized in that, the described reaction times is 4-15h.
4, the preparation method of precursor body of poly carbon silane ceramics of containing zirconium according to claim 1 and 2 is characterized in that, the siliceous lower molecular weight organic polymer of described main chain is poly-silicon-carbon silane, polysilane, Polycarbosilane or polydimethyl silane.
5, the preparation method of precursor body of poly carbon silane ceramics of containing zirconium according to claim 3 is characterized in that, the siliceous lower molecular weight organic polymer of described main chain is poly-silicon-carbon silane, polysilane, Polycarbosilane or polydimethyl silane.
6, the preparation method of precursor body of poly carbon silane ceramics of containing zirconium according to claim 1 and 2 is characterized in that, acetylacetonate compound, carbonyl compound, keto compounds and dis-cyclopentadiene compounds that described zirconium organometallics is a zirconium.
7, the preparation method of precursor body of poly carbon silane ceramics of containing zirconium according to claim 3 is characterized in that, acetylacetonate compound, carbonyl compound, keto compounds and dis-cyclopentadiene compounds that described zirconium organometallics is a zirconium.
8, the preparation method of precursor body of poly carbon silane ceramics of containing zirconium according to claim 4 is characterized in that, acetylacetonate compound, carbonyl compound, keto compounds and dis-cyclopentadiene compounds that described zirconium organometallics is a zirconium.
9, the preparation method of precursor body of poly carbon silane ceramics of containing zirconium according to claim 5 is characterized in that, acetylacetonate compound, carbonyl compound, keto compounds and dis-cyclopentadiene compounds that described zirconium organometallics is a zirconium.
10, the constant-pressure and high-temperature cracker that uses according to the preparation method of one of claim 1-9 described precursor body of poly carbon silane ceramics of containing zirconium is characterized in that comprise the reactor there-necked flask that places well heater, described there-necked flask is provided with thermopair, N
2Inlet mouth and from the phegma of separating funnel inlet, described there-necked flask is communicated with the material inlet of the cracking post that places electric mantle, the material outlet of described cracking post is communicated with prolong, described prolong is communicated with vapor pipe, vacuum system interface and separating funnel by transfer tube, the lower part outlet of described separating funnel is communicated with there-necked flask, also is provided with thermopair between electric mantle and the cracking post.
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