Method for preparing zirconium-aluminum-silicon-carbon ceramic block material by in-situ reaction under hot pressure
Technical Field The present invention relates to technology for preparing ultra high temperature ceramic-resistant, special provides an in-situ reaction hot pressing preparation zirconium aluminum silicon carbon (Zr3 [Al (Si)]4 C6 and Zr2 [Al (Si)]4 C5) method of ceramic block material. Background Art zirconium aluminum silicon carbon (Zr3 [Al (Si)]4 C6 and Zr2 [Al (Si)]4 C5) ceramic block material is composed of ultra-high-temperature-resistant, oxidation-resistant the ternary material. Their comprehensive high-modulus, high hardness, oxidation resistance, corrosion resistance, high electrical conductivity, thermal conductivity, relatively strong damage tolerant, and the like. In aviation, and aerospace, nuclear industry, high-tech field of ultra-high temperature structural members, and the like have a broad application prospect. Although zirconium aluminum silicon carbon (Zr3 [Al (Si)]4 C6 and Zr2 [Al (Si)]4 C5) block material has such excellent performance, the difficulties of the restrictions on the study of the performance of the application of with it. So far on zirconium aluminum silicon carbon (Zr3 [Al (Si)]4 C6 and Zr2 [Al (Si)]4 C5) ceramic block material preparation literature report of only two press. Literature 1 (J.Mater.Res. (material research Journal) 22 (2007) 2888) and literature 2 (J.Solid State Chem. (solid-state chemical magazine) 180 (2007) 1809) sintering technology in the electric pulse is used in the 1700 [...] , 40 MPa are respectively sintered under pressure the Zr3 [Al (Si)]4 C6 and Zr2 [Al (Si)]4 C5 body material. In the vacuum furnace, they first synthetic Zr3 [Al (Si)]4 C6, Zr2 [Al (Si)]4 C5 powder, and then the obtained powder is sintered to the block body. This kind of non-in-situ synthesis of complex process, forming the sample size is relatively small, not conducive to test the mechanical property of the material and the future application. Content of the invention The aim of this invention lies in that a hot pressing preparation zirconium aluminum silicon carbon in-situ reaction (Zr3 [Al (Si)]4 C6 and Zr2 [Al (Si)]4 C5) method of ultra-high temperature ceramic block material. The method to Zr powder, powder Al, Si powder and C powder as the raw material, at a relatively low temperature, within a short period of time the synthesis of high-purity, compact zirconium aluminum silicon carbon (Zr3 [Al (Si)]4 C6 and Zr2 [Al (Si)]4 C5) bulk material, can solve the problems that the prior non-in-situ synthesis of complex process, forming the sample size is relatively small, and the like. The technical scheme of the present invention are as follows: An in-situ reaction hot pressing preparing zirconium-aluminum-silicon-carbon ceramic block material method, the method is characterized in that: 1) raw material components and component range: To Zr powder, powder Al, Si powder and C powder as the raw material, according to the stoichiometric ratio, Zr:Al:Si:C= (2-3) : (3-5) : (0.3-1.5) : (4-7); According to the stoichiometric ratio, Zr:Al:Si:C=3 : (3-5) : (0.3-1.5) : (5-7), synthetic single-phase Zr3 [Al (Si)]4 C6; According to the stoichiometric ratio, Zr:Al:Si:C=2 : (3-5) : (0.3-1.5) : (4-6), synthetic single-phase Zr2 [Al (Si)]4 C5; Synthetic Zr3 [Al (Si)]4 C6, Zr2 [Al (Si)]4 C5 composite materials, the stoichiometric ratio between the above two ratio adjusting. 2) preparation process: Raw material passes through the ball milling 5-50 hours, to 5-20MPa normal temperature under the pressure of cold pressed into the cake, into the graphite die, in with an inert gas (such as argon) as protective gas (or under vacuum, vacuum degree higher than 10-1 Pa) in the hot pressing furnace the 2-50 [...] /min (preferably 5-30 the [...] /min) to the temperature increasing rate of the 1600 [...] -2400 the hot-pressing reaction in situ [...] 0.1-4 hours (preferably 0.5-2 hours), hot pressing pressure is 20-40MPa. In the present invention, Zr powder, Al the particle size of the powder and the powder C 200-400 mesh; obtained by adopting the method of the invention zirconium-aluminum-silicon-carbon ceramic block material size in the range of Φ (25-100) mm× (2-50) mm. The characteristic feature of the invention is: 1. The invention selects the raw materials are simple, are Zr powder, powder Al, Si powder and C powder. 2. The present invention through in-situ reaction hot pressing, sintering and densification carried out at the same time, obtaining single-phase dense zirconium aluminum silicon carbon (Zr3 [Al (Si)]4 C6 and Zr2 [Al (Si)]4 C5) bulk material. 3. By adopting the method of the invention for the material obtained in the environmental temperature can be room temperature to greater than 1600 the use of the ultra-high-temperature [...] , than Zr3 Al3 C5, Zr2 Al3 C4 and ZrC having better anti-high-temperature oxidation resistance. Description of drawings Figure 1. Zr3 [Al (Si)]4 C6 of the X-ray diffraction pattern. Figure 2. Reaction product Zr3 [Al (Si)]4 C6 the scanning electron microscope photo. Figure 3. Zr2 [Al (Si)]4 C5 of the X-ray diffraction pattern. Figure 4. Reaction product Zr2 [Al (Si)]4 C5 grain topography the scanning electron microscope photo. Figure 5. Zr3 [Al (Si)]4 C6, Zr2 [Al (Si)]4 C5 and Zr3 Al3 C5 three-phase composite material of the scanning electron microscope photo. Mode of execution Below in detail by embodiments of the invention. Embodiment 1. The raw material particle size of 300 mesh and Zr powder of 100.0 g, powder Al 39.5 g, Si powder 8.2 grams and C powder 25.9 g, ball milling 10 hours, in 15 MPa under the pressure of cold pressed into the cake, into the graphite die, with the inert gas as protective gas (argon gas) in the hot pressing furnace 10 the rate of rise of temperature [...] /min to 2000 the in situ reaction heat pressing [...] 1 hours, hot pressing pressure is 30 MPa. The major reaction product obtained by the X-ray diffraction analysis for Zr3 [Al (Si)]4 C6. The corresponding X-ray diffraction pattern, scanning electron microscope photographs, are respectively listed in the with photos 1-2 the upper. The reaction product of the shear modulus and the dynamic Young's modulus are 367GPa and 156GPa. Embodiment 2. The raw material particle size of 400 mesh powder Zr of about 100.0 g, powder Al 59.1 g, Si powder 12.3 grams and C powder 32.3 g, ball milling 15 hours, at 20 MPa under the pressure of cold pressed into the cake, into the graphite die, under the vacuum (vacuum degree is 10-2 Pa) the hot pressing furnace in order to 15 the rate of rise of temperature [...] /min to 1900 the in situ reaction heat pressing [...] 0.5 hours, hot pressing pressure is 30 MPa. The major reaction product obtained by the X-ray diffraction analysis for Zr2 [Al (Si)]4 C5. The corresponding X-ray diffraction pattern, the crystalline grain topography scanning electron microscope photographs, are respectively listed in the with photos 3-4 the upper. The reaction product of the shear modulus and the dynamic Young's modulus are 361GPa and 153GPa. Embodiment 3. The raw material particle size of 200 mesh and Zr powder of 100.0 g, powder Al 45.5 g, powder Si 10.2 grams and C powder 29.3 g, ball mill 20 hours, in the 10 MPa under the pressure of cold pressed into the cake, into the graphite die, with argon as the protective gas in the hot pressing furnace in order to 20 the rate of rise of temperature [...] /min to 1800 the in situ reaction heat pressing [...] 4 hours, hot pressing pressure is 40 MPa. The major reaction product obtained by the X-ray diffraction analysis for Zr3 [Al (Si)]4 C6, Zr2 [Al (Si)]4 C5 and Zr3 Al3 C5 three-phase composite material, Zr3 [Al (Si)]4 C6, Zr2 [Al (Si)]4 C5 and Zr3 Al3 C5 respectively to the weight percentage of 60%, 20% and 20%. The corresponding X-ray diffraction diagram spectrum row in Figure 5 the upper. The embodiment 3 can be seen, to obtain Zr3 [Al (Si)]4 C6, Zr2 [Al (Si)]4 C5 and Zr3 Al3 C5 three-phase composite material according to the following regulating Zr raw material: Al:Si:C= (2-3) : (3-5) : (0.3-1.5) : (4-7). The invention relates to the technology for preparing ultrahigh temperature resistant ceramics and particularly provides a method for preparing ceramic zirconium-aluminum-silicon-carbon (Zr3 [Al(Si)]4C6 and Zr2 [Al(Si)]4C5) block material by in-situ hot pressure reaction, and the method can solve the problems of complicated process and small molding size of samples of non-in-situ synthesizing method. The method adopts Zr powder, Al powder, Si powder and C powder as the raw materials according to certain stoichiometric ratio; the raw materials are ball-milled for 5 to 50 hours, cold-pressed into disc shape under the pressure of 5 to 20MPa, loaded in a graphite mold, and heated to 1,600 DEG C to 2,400 DEG C in a hot pressing furnace at a heating rate of 2 to 50 DEG C per minute, wherein inert gas (such as argon) is pumped into the hot pressing furnace as the protecting gas (or the hot pressing furnace is in vacuum); the in-situ hot pressure reaction is carried out for 0.1 to 4 hours, and the hot pressure is 20 to 40MPa. By adopting the method, the zirconium-aluminum-silicon-carbon block material with the properties of high purity, high strength, corrosion resistance, and the like, can be synthesized at lower temperature in short time, and the material obtained by the method can be used at ultrahigh temperature more than 1,600 DEG C. 1, an in-situ reaction hot pressing preparing zirconium-aluminum-silicon-carbon ceramic block material method, characterized in that 1) raw material components and component range: To Zr powder, powder Al, Si powder and C powder as the raw material, according to the stoichiometric ratio, Zr:Al:Si:C= (2-3) : (3-5) : (0.3-1.5) : (4-7); 2) preparation process: Raw material passes through the ball milling 5-50 hours, to 5-20MPa pressure cold pressed into the cake, into the graphite die, in with an inert gas as protective gas or vacuum to the hot pressing furnace in the 1600 [...] -2400 the in situ reaction heat pressing [...] 0.1-4 hours, hot pressing pressure is 20-40MPa. 2, in accordance with the in-situ reaction hot pressing preparing zirconium-aluminum-silicon-carbon ceramic block material method according to Claim 1, characterized in that said step 2) in, hot pressing furnace for the rate of rise of temperature the 2-50 [...] /min. 3, in accordance with the in-situ reaction hot pressing preparing zirconium-aluminum-silicon-carbon ceramic block material method according to Claim 1, characterized in that the stated step 1) in, according to the stoichiometric ratio, Zr:Al:Si:C=3 : (3-5) : (0.3-1.5) : (5-7), synthetic single-phase Zr3 [Al (Si)]4 C6. 4, in accordance with the in-situ reaction hot pressing preparing zirconium-aluminum-silicon-carbon ceramic block material method according to Claim 1, characterized in that the stated step 1) in, according to the stoichiometric ratio, Zr:Al:Si:C=2 : (3-5) : (0.3-1.5) : (4-6), synthetic single-phase Zr2 [Al (Si)]4 C5.