CN101265105A - Method for preparing niobium-containing SiC ceramic precursor - Google Patents
Method for preparing niobium-containing SiC ceramic precursor Download PDFInfo
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- CN101265105A CN101265105A CNA2008100310498A CN200810031049A CN101265105A CN 101265105 A CN101265105 A CN 101265105A CN A2008100310498 A CNA2008100310498 A CN A2008100310498A CN 200810031049 A CN200810031049 A CN 200810031049A CN 101265105 A CN101265105 A CN 101265105A
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Abstract
The invention relates to a method for producing a niobium-containing SiC ceramic precursor. The method comprises the following steps: (1) placing a niobium chloride or an organic compound equivalent to 0.5-20 wt% the weight of a low-molecular weight polymer containing silicon in main chain in a three-mouth flask, placing the low-molecular weight polymer containing silicon in main chain in the three-mouth flask, covering with the niobium chloride or the organic compound; (2) in the presence of Ar or N2 protective gas, heating the materials in the three-mouth flask up to 350-500 DEG C at a temperature rise rate of 0.1-5 DEG C/min, controlling the temperature of a cracking column at 450-550 DEG C, allowing thermal decomposition and rearrangement reactions for 1-15 h, and cooling; and (3) dissolving the crude product with dimethylbenzene, filtering, distilling the filtrate at 250-390 DEG C under reduced pressure, and cooling. The method has the advantages of easily-accessible raw materials, low cost, controllable niobium content and performance of the product, homogenization at molecular level, good reshaping property, good resistance to ultra-high temperature, simple equipment, suitability for large-scale production, and low manufacture cost.
Description
Technical field
The present invention relates to a kind of preparation method who contains the SiC ceramic precursor of heterogeneous element niobium, especially relate to a kind of with main chain silicon-containing polymer and niobium muriate or contain the preparation method that the niobium organometallic compound is the SiC ceramic precursor that contains the heterogeneous element niobium 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 advanced aerospacecraft structure unit, high-temperature engine, turbine, atomic reactor wall, catalyzer heat exchanger and firing system, MEMS (Microelectromechani c 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.
Single-phase SiC pottery has splendid heatproof potentiality, and in theory, pure β-SiC crystal can high temperature resistantly reach 2600 ℃.But in fact, the high thermal resistance of SiC pottery does not but far reach this theoretical temperatures, and its basic reason is that the 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.
For preparation high-performance SiC pottery, maximum problem is to prevent that β under the ultrahigh-temperature-SiC crystal grain from too growing up, even makes ceramic powderization.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.The sintering process cost is higher, and the skewness of the heterogeneous element of introducing in product, particularly this method are 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 (Preceramic polymer, 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.
CN 101050117A discloses a kind of SiC ceramic setter preparation that contains the heterogeneous element zirconium, its raw materials used costing an arm and a leg, manufacturing cost height.
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, shortcoming that manufacturing cost is high, provide a kind of SiC of raising pottery superhigh temperature resistant performance, the preparation method who contains niobium SiC ceramic precursor (PNCS) of low cost of manufacture.
Further aim 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, the present invention adopts following technical proposals: with for example poly-silicon-carbon silane (PSCS) of the siliceous low-molecular weight 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 muriate of Nb, alkoxy compound 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 PNCS (Polyniobiumcarbosilane) of heterogeneous element niobium.
For realizing second purpose of the present invention, 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 niobium SiC ceramic precursor, to improve the physics rheological property of SiC ceramic precursor, help the reshaping processing of SiC ceramic precursor, contain niobium SiC ceramic fiber, preparation matrix material etc. as spinning.
The present invention specifically may further comprise the steps: (1) will be equivalent to the siliceous low-molecular weight polymer weight 0.5wt%-20wt% of main chain (preferred 1wt%-10wt%) in glove box niobium metal muriate or organic compound place there-necked flask, and the low-molecular weight polymer that main chain is siliceous places this there-necked flask to cover niobium metal muriate or organic compound; (2) the constant-pressure and high-temperature cracker that utilizes the present inventor to develop is at Ar or N
2Or the protection of their mixture down, according to 0.1-5 ℃/min temperature rise rate, make the material in the there-necked flask rise to 350-500 ℃ (preferred 390-450 ℃), the cracking column temperature is controlled at 450-550 ℃, carry out the thermolysis rearrangement reaction, reaction times 1-15h (preferred 5-8h) gets the thick product of PNCS after the cooling; (3) should thick product through xylene soluble, filtration, filtrate is carried out underpressure distillation at 250-390 ℃, promptly gets black resin shape PNCS after the cooling.
Afterwards, can carry out follow-up reshaping, prepare matrix material as the spinning ceramic fiber or as steeping fluid.
Described niobium metal muriate or organic compound can be columbium pentachloride or five oxyethyl group niobiums etc.
The siliceous low-molecular weight polymer of described main chain can be liquid poly-silicon-carbon silane (PSCS), polydimethyl silane (PDMS), Polycarbosilane (PCS) or polysilane (PS) etc.
Show that through IR, NMR, ultimate analysis the Si-H key of the SiC ceramic precursor PNCS that the present invention prepares is abundant, help reshaping processing, the infrared spectrum characteristic peak is similar to PCS, the molecular weight distribution broad.
Niobium 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 niobium, and can improve ceramic densification degree, improved the superhigh temperature resistant performance of SiC pottery greatly, and the resistivity that contains niobium SiC pottery of preparation is adjustable continuously, having good microwave absorbing property, is excellent absorbing material material standed for.
The present invention has following advantage: starting compound is various, wide material sources, cheap, the content of heterogeneous element niobium and performance index thereof are controllable in the precursor, compare with traditional metal simple-substance that in precursor, adds merely, this law preparation contain niobium SiC ceramic precursor, niobium can reach the homogenize of molecule rank in precursor and pottery thereof, and because raw material muriate oxygen-free, can reduce oxygen level in the precursor, the product purity height, reshaping is good, the superhigh temperature resistant excellent performance; Reaction process is easy to control, and processing unit is simple, and the output height is realized large-scale industrial production easily, and starting compound is cheap in addition, and manufacturing cost is only for containing 1/2 of zircon ceramic precursor.
Description of drawings
Fig. 1 prepares the structural representation of PNCS device for constant-pressure and high-temperature cracking process of the present invention;
Fig. 2 is the PNCS of embodiment 1 preparation and the infrared spectrogram of PSCS;
Fig. 3 is the PNCS of embodiment 1 preparation
1The H-NMR spectrogram;
Fig. 4 is the PNCS of embodiment 1 preparation
29The Si-NMR spectrogram.
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
2Or Ar 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, thermopair 6-1 is arranged in the there-necked flask 1, be provided with thermopair 6-2 between electric mantle 3 and the cracking post 2.The following stated PNCS preparation method of the present invention embodiment all uses said apparatus.
The operation steps of the following stated PNCS preparation method of the present invention embodiment is: (1) will be equivalent to the niobium metal muriate of the siliceous low-molecular weight polymer weight 0.5wt%-20wt% of main chain (preferred 1wt%-10wt%) or organic compound and place behind the there-necked flask 1 the poly-silicon-carbon silane (PSCS) of liquid state in glove box, polydimethyl silane (PDMS), Polycarbosilane (softening temperature is 80-150 ℃) (PCS) or polysilane (PS) place this there-necked flask to cover niobium metal muriate or organic compound and will install as shown in Figure 1 and put up; (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 350-500 ℃, carry out the polyreaction of niobium metal muriate or organic compound and silicon-containing polymer, meanwhile, the gasification of partial reaction product, enter row and separate post 2, utilize electric mantle 3 to make row separate post 2 and be 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 PNCS; (3) with the thick product of PNCS through xylene soluble, filtration, filtrate is carried out underpressure distillation at 250-390 ℃, promptly gets black resin shape PNCS after the cooling.
Embodiment 1.
With PSCS and columbium pentachloride is raw material, the two quality proportioning is: columbium pentachloride: PSCS=5: 100,460 ℃ 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 200 ℃, contains the PNCS of niobium 1.15wt%, precursor productive rate 55.6%.
The PNCS infrared spectrogram of present embodiment preparation is seen Fig. 2,
1The H-NMR spectrogram is seen Fig. 3,
29The Si-NMR spectrogram is seen Fig. 4.
Do not melt and high temperature burns till to make and contains niobium SiC ceramic fiber through melt-spinning, air with this PNCS precursor.Fibre diameter 17 μ m, tensile strength 1.6GPa.This fiber superhigh temperature resistant is functional, and after 1600 ℃ and the 1800 ℃ of processing, strength retention ratio is respectively 45% and 33%; Si-Nb-C-O fiber antioxidant property is good, and behind 1000 ℃ of thermal treatment 20h, strength retention ratio is 71%.Behind 1000 ℃ of thermal treatment 100h, strength retention ratio is 42% in the air.
With PSCS and five oxyethyl group niobiums is raw material, the two quality proportioning is: five oxyethyl group niobium: PSCS=10: 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 350 ℃, making softening temperature is 185 ℃, contains the PNCS of niobium 2.75wt%, precursor productive rate 52.9%.
Do not melt and high temperature burns till to make and contains niobium SiC ceramic fiber through melt-spinning, air with this PNCS precursor.Fibre diameter 15 μ m, tensile strength 1.9GPa.This fiber superhigh temperature resistant is functional, and after 1600 ℃ and the 1800 ℃ of processing, strength retention ratio is respectively 40% and 22%; Si-Nb-C-O fiber antioxidant property is good, and behind 1000 ℃ of thermal treatment 20h, strength retention ratio is 69%.Behind 1000 ℃ of thermal treatment 100h, strength retention ratio is 38% in the air.
With PS and columbium pentachloride is raw material, columbium pentachloride: PS=10: 100,350 ℃ of temperature of reaction, 500 ℃ of cracking temperatures are behind the insulation reaction time 10h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 370 ℃, making softening temperature is 190 ℃, contains the PNCS of niobium 2.18wt%, precursor productive rate 50.9%.
Do not melt and high temperature burns till to make and contains niobium SiC ceramic fiber through melt-spinning, air with this PNCS precursor.Fibre diameter 16 μ m, tensile strength 2.0GPa.This fiber superhigh temperature resistant is functional, and after 1600 ℃ and the 1800 ℃ of processing, strength retention ratio is respectively 40% and 28%; Si-Nb-C-O fiber antioxidant property is good, and behind 1000 ℃ of thermal treatment 20h, strength retention ratio is 65%.Behind 1000 ℃ of thermal treatment 100h, strength retention ratio is 32% in the air.
With PDMS and columbium pentachloride is raw material, columbium pentachloride: PDMS=15: 100,440 ℃ of temperature of reaction, 500 ℃ of cracking temperatures are behind the insulation reaction 10h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 350 ℃, making softening temperature is 220 ℃, contains the PNCS of niobium 3.76wt%, precursor productive rate 53.8%.
Do not melt and high temperature burns till to make and contains niobium SiC ceramic fiber through melt-spinning, air with this PNCS precursor.Fibre diameter 19 μ m, tensile strength 1.4GPa.This fiber superhigh temperature resistant is functional, and after 1600 ℃ and the 1800 ℃ of processing, strength retention ratio is respectively 33% and 21%; Si-Nb-C-O fiber antioxidant property is good, and behind 1000 ℃ of thermal treatment 20h, strength retention ratio is 61%.Behind 1000 ℃ of thermal treatment 100h, strength retention ratio is 34% in the air.
With PCS and columbium pentachloride is raw material, columbium pentachloride: PCS=5: 100, temperature of reaction is 400 ℃, 500 ℃ of cracking temperatures are behind the insulation reaction time 12h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 350 ℃, making softening temperature is 215 ℃, contains the PNCS of niobium 1.03wt%, precursor productive rate 53.7%.
Do not melt and high temperature burns till to make and contains niobium SiC ceramic fiber through melt-spinning, air with this PNCS precursor.Fibre diameter 14 μ m, tensile strength 2.1GPa.This fiber superhigh temperature resistant is functional, and after 1600 ℃ and the 1800 ℃ of processing, strength retention ratio is respectively 43% and 31%; Si-Nb-C-O fiber antioxidant property is good, and behind 1000 ℃ of thermal treatment 20h, strength retention ratio is 73%.Behind 1000 ℃ of thermal treatment 100h, strength retention ratio is 40% in the air.
When being raw material with PCS and five oxyethyl group niobiums, five oxyethyl group niobium: PCS=5: 100,420 ℃ of temperature of reaction, 500 ℃ of cracking temperatures are behind the insulation reaction time 8h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 320 ℃, making softening temperature is 165 ℃, contains the PNCS of niobium 1.36wt%, precursor productive rate 56.4%.
Do not melt and high temperature burns till to make and contains niobium SiC ceramic fiber through melt-spinning, air with this PNCS precursor.Fibre diameter 16 μ m, tensile strength 1.7GPa.This fiber superhigh temperature resistant is functional, and after 1600 ℃ and the 1800 ℃ of processing, strength retention ratio is respectively 40% and 26%; Si-Nb-C-O fiber antioxidant property is good, and behind 1000 ℃ of thermal treatment 20h, strength retention ratio is 68%.Behind 1000 ℃ of thermal treatment 100h, strength retention ratio is 39% in the air.
Above result shows, prepares in the process of the SiC ceramic precursor that contains the heterogeneous element niobium 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 PNCS precursor that availability is good: when being raw material with PSCS and columbium pentachloride, columbium pentachloride/PSCS mass ratio is 2-15%, temperature of reaction is 400-480 ℃, cracking temperature 480-540 ℃, behind the insulation reaction time 4-15h, through xylene soluble, filtration, filtrate is carried out underpressure distillation at 350-390 ℃, and making softening temperature is 180-240 ℃, contains the PNCS of niobium 0.4-1.56wt%, productive rate 50-60%, the precursor performance ideal that makes helps reshaping processing, thus the precursor preparation to contain niobium SiC pottery heat resistance good.
The foregoing description shows, with the silicon-containing polymer is reaction raw materials, the muriate of Nb and organometallic compound are reaction additives, adopt the preparation of constant-pressure and high-temperature cracking process to contain the SiC ceramic precursor PTCS of heterogeneous element niobium, the niobium element reaches the homogenize of molecule rank in precursor, character such as content of niobium and PNCS softening temperature are controllable, can adjust the PNCS that reaction conditions prepares different size according to producing needs.By PNCS preparation to contain niobium SiC pottery superhigh temperature resistant functional, niobium can make ceramic densifying in containing niobium 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.
Claims (5)
1. preparation method who contains the SiC ceramic precursor of niobium, it is characterized in that, may further comprise the steps: (1) will be equivalent to the siliceous low-molecular weight polymer weight 0.5wt%-20wt% of main chain in glove box niobium metal muriate or organic compound place there-necked flask, and the low-molecular weight polymer that main chain is siliceous places this there-necked flask to cover niobium metal muriate or organic compound; (2) at Ar or N
2Or the protection of their mixture down, according to 0.1-5 ℃/min temperature rise rate, makes the material in the there-necked flask be warming up to 350-500 ℃, and the cracking column temperature is controlled at 450-550 ℃, carries out the thermolysis rearrangement reaction, and reaction times 1-15h gets the thick product of PNCS after the cooling; (3) should thick product through xylene soluble, filtration, filtrate is carried out underpressure distillation at 250-390 ℃, promptly gets the black resin shape after the cooling and contains niobium SiC ceramic precursor.
2. the preparation method who contains the SiC ceramic precursor of niobium according to claim 1, it is characterized in that, in described (1) step, place the niobium metal muriate of there-necked flask or the 1wt%-10wt% that organic compound weight is equivalent to the siliceous low-molecular weight polymer weight of main chain.
3. the preparation method who contains the SiC ceramic precursor of niobium according to claim 1 and 2 is characterized in that, in described (2) step, makes the material in the there-necked flask be warming up to 390-450 ℃, reaction times 5-8h.
4. the preparation method who contains the SiC ceramic precursor of niobium according to claim 1 and 2 is characterized in that described niobium metal muriate is a columbium pentachloride, and the niobium metal organic compound is five oxyethyl group niobiums.
5. the preparation method who contains the SiC ceramic precursor of niobium according to claim 1 and 2 is characterized in that, the siliceous low-molecular weight polymer of described main chain is liquid poly-silicon-carbon silane, polydimethyl silane, Polycarbosilane or polysilane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674848A (en) * | 2012-05-07 | 2012-09-19 | 北京科技大学 | Method for preparing SiC ceramic precursor for chemical liquid-vapor deposition process |
| CN107555997A (en) * | 2017-09-05 | 2018-01-09 | 湖南博翔新材料有限公司 | A kind of preparation method of the precursor body of poly carbon silane ceramics containing beryllium |
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2008
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674848A (en) * | 2012-05-07 | 2012-09-19 | 北京科技大学 | Method for preparing SiC ceramic precursor for chemical liquid-vapor deposition process |
| CN107555997A (en) * | 2017-09-05 | 2018-01-09 | 湖南博翔新材料有限公司 | A kind of preparation method of the precursor body of poly carbon silane ceramics containing beryllium |
| CN107555997B (en) * | 2017-09-05 | 2020-11-03 | 湖南泽睿新材料有限公司 | Preparation method of beryllium-containing polycarbosilane ceramic precursor |
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