CN111116206A - Preparation method of compact MoAlB ceramic material, product thereof and preparation method of high-purity MoAlB ceramic powder - Google Patents
Preparation method of compact MoAlB ceramic material, product thereof and preparation method of high-purity MoAlB ceramic powder Download PDFInfo
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Abstract
The invention discloses a preparation method of a compact MoAlB ceramic material, a product thereof and a preparation method of high-purity MoAlB ceramic powder, wherein the preparation method of the compact MoAlB ceramic material comprises the following steps: s1, mixing molybdenum boride powder, aluminum powder and molybdenum powder as raw materials; s2, dry-mixing the ingredients on a ball mill for 1-4 hours to obtain a mixture; s3, placing the mixture into a graphite mold, placing the graphite mold into a plasma sintering furnace for prepressing, and under a protective atmosphere, heating at a heating rate of 50-200 DEG CoC/min, the sintering temperature is 800oC～1200oC, the pressure is between 50 and 100MPa, and the heat preservation and pressure maintaining time is between 5 and 30 minutesPerforming line sintering; and S4, maintaining the temperature and pressure, and cooling to room temperature to obtain the compact MoAlB ceramic material. The scheme can realize synthesis at a relatively low sintering temperature, and the heating and cooling speed is high, so that the process period is effectively shortened, the energy consumption is reduced, and the efficiency is improved; meanwhile, the amount of impurities is greatly reduced, and the purity of the final product is improved.
Description
Technical Field
The invention relates to the field of MoAlB materials, in particular to a preparation method of a compact MoAlB ceramic material, a product of the compact MoAlB ceramic material and a preparation method of high-purity MoAlB ceramic powder.
Background
The MoAlB ceramic material is ternary nano layered transition metal boride ceramic which is newly synthesized in nearly one or two years, the unit cell structure of the MoAlB ceramic material is similar to that of MAX phase materials, and the MoAlB ceramic material has a hexagonal crystal structure and is formed by connecting a transition metal boride layer MoB with a single-layer or double-layer Al layer, so that the MoAlB ceramic has the performance similar to or more excellent than that of MAX phase ceramics. Such as MoAlB ceramics, has excellent performances of processability, high electric and thermal conductivity, low expansion coefficient, wear resistance and the like.
Compared with MAX phase materials, the MoAlB ceramic material has better mechanical properties, such as Vickers hardness of 10.6 +/-0.3 GPa and room-temperature compressive strength of 1940 +/-103 MPa [ document 1, S.Kota,2016, Sci.Rep. (6),26475]. In addition, MoAlB ceramics, unlike other binary boride ceramics, the ternary boride ceramics have excellent high temperature oxidation resistance. In air, MoAlB is 1300oC also maintains cubic oxidation kinetics, which is mainly due to the fact that during oxidation, protective aluminum oxide (Al) can be formed on the surface of MoAlB2O3) Protective layer [ document 2, s.kota,2017, j.electrochem.soc.164(13), C930]. Therefore, the MoAlB ceramic material is a material which is preferably used in the fields of high-temperature structural materials, high-temperature coatings, key components and the like.
However, the application of the MoAlB ceramic is seriously hindered by the problems of less methods for preparing the MoAlB ceramic material, more impurities and the like. Kota et Al, as described in the above document 1, use MoB powder and Al powder as raw materials and use a hot pressing method at 1200oAnd (3) at the temperature of C and under the pressure of 39MPa, preserving heat and pressure for 5 hours, and sintering to prepare the MoAlB ceramic sample. But the problems of low density, many impurity phases and the like of the prepared sample, and the problems of growth of MoAlB crystal grains, performance reduction and the like caused by overlong heat preservation and pressure maintaining time exist.
Further, in patent application No. 201710815613.4, Li ShiBo et Al selected Mo powder, Al powder, B powder as raw materials, according to Mo: al: b = 1: 1.1: 1 or 1: 1.3: 1 mol of ingredients are mixed, put into a ball milling tank for mixing for 10-24 hours, and then put into a graphite mold for mixing by 20-30 hoursoHeating to 1100-1200 ℃ at a C/min heating rateoAnd C, applying pressure of 20-30MPa, and preserving heat for 60-90min, wherein although the preparation process is optimized compared with the process of Kota and the like, the synthesis time is still longer, the time and the energy are consumed, and the efficiency is lower.
Therefore, how to rapidly prepare the high-purity MoAlB compact block, shorten the preparation time of the material, improve the purity of the sample and promote the large-scale production of the MoAlB needs to be further improved.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a compact MoAlB ceramic material, a compact MoAlB ceramic block and a preparation method of high-purity MoAlB ceramic powder.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the compact MoAlB ceramic material comprises the following steps:
s1, mixing molybdenum boride powder, aluminum powder and molybdenum powder as raw materials;
s2, putting the ingredients into a plastic bottle, adding a ball milling medium, and dry-mixing for 1-4 hours on a ball mill to obtain a mixture;
s3, placing the mixture into a graphite mold, placing the graphite mold into a plasma sintering furnace for prepressing, and then heating at a heating rate of 50-200 ℃ in a vacuum environment or a protective atmosphereoC/min, the sintering temperature is 800oC～1200oC, sintering under the parameter conditions that the pressure is between 50 and 100MPa and the heat preservation and pressure maintaining time is between 5 and 30 minutes;
and S4, maintaining the temperature and pressure, and cooling to room temperature to obtain the compact MoAlB ceramic material.
Preferably, in the preparation method of the dense MoAlB ceramic material, in the step S1, the molybdenum boride powder, the aluminum powder and the molybdenum powder are mixed according to a ratio of 1: 2-2.2: 1, the raw materials are mixed according to a molar ratio of 1.
Preferably, in the preparation method of the dense MoAlB ceramic material, in the step S2, the ball milling medium is zirconia balls.
Preferably, in the preparation method of the dense MoAlB ceramic material, the step S3 includes the following steps:
s31, placing the mixture in a graphite mold with the diameter of 20cm or 40 cm;
s32, placing the graphite mould into a cleaned plasma sintering furnace;
s33, pre-pressing the mixture in the graphite mold under the pressure of 50Pa, and then unloading the pressure;
s34, introducing argon into the plasma sintering furnace for protection;
s35, starting to heat, and in the process of heating to the sintering temperature, not applying pressure;
s36, heating to a sintering temperature, and then preserving heat for 1-5 minutes;
s37, after heat preservation, loading pressure to a set pressure value;
and S38, preserving heat and pressure for 5-30 minutes.
Preferably, in the preparation method of the dense MoAlB ceramic material, in the step S32, the plasma sintering furnace is cleaned by repeating vacuumizing and argon filling for three times.
Preferably, in the preparation method of the dense MoAlB ceramic material, in the step S37, the pressure is applied at a rate of 20-30 MPa/min.
Preferably, in the preparation method of the dense MoAlB ceramic material, in the step S4, the ratio is 50-200oAnd C/min cooling rate.
The compact MoAlB ceramic block is prepared by any one of the methods.
The preparation method of the high-purity MoAlB ceramic powder is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing molybdenum boride powder, aluminum powder and molybdenum powder as raw materials;
s2, putting the ingredients into a plastic bottle, adding a ball milling medium, and dry-mixing for 1-4 hours on a ball mill to obtain a mixture;
s3, placing the mixture into a graphite mold, placing the graphite mold into a plasma sintering furnace for prepressing, and then heating at a heating rate of 50-200 ℃ in a vacuum environment or a protective atmosphereoThe sintering temperature is 800 ℃ between C/minoC～1200oSintering under the parameter conditions that the pressure is 50-100 MPa and the heat preservation and pressure maintaining time is 5-30 minutes;
s4, cooling to room temperature after heat preservation and pressure maintaining to obtain a compact MoAlB ceramic material;
and S5, crushing the MoAlB ceramic material to obtain high-purity MoAlB ceramic powder.
The technical scheme of the invention has the advantages that:
the scheme has the advantages of ingenious design and simple process, can realize synthesis at relatively low sintering temperature by optimizing raw materials and utilizing the advantage that the plasma sintering technology can heat to the set temperature in a short time and combining the design of sintering process parameters, effectively shortens the process period, effectively reduces the energy consumption and improves the synthesis efficiency; meanwhile, the amount of impurities is greatly reduced, the purity of the final product is improved, and the requirement of industrial application is met.
The scheme has the advantages of simple raw materials, easy acquisition, low price and convenient realization of the process, and is sold in the market.
The zirconia balls are used as grinding media, so that on one hand, the grinding efficiency and the grinding quality can be effectively improved, the grinding time can be reduced, and the integral synthesis efficiency can be improved; meanwhile, impurities doped in the raw materials can be reduced, and the quality of the final product is improved.
Due to the rapid temperature rise and the short heat preservation time of the plasma sintering technology, the growth of crystal grains can be effectively avoided, and the purpose of improving the material performance is achieved.
Pressure loading is not carried out in the temperature rising process, so that the phenomenon that a large amount of impurity phases are generated in the synthesized MoAlB ceramic material due to the loss of simple substance aluminum in the sintering process can be effectively avoided, and the purity and the density are favorably improved.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is an XRD diffractogram of example 1 of the present invention;
FIG. 3 is an SEM scanning electron micrograph of example 2 of the present invention;
FIG. 4 is a SEM scanning electron micrograph of example 3 of the present invention.
Detailed Description
Objects, advantages and features of the present invention will be illustrated and explained by the following non-limiting description of preferred embodiments. The embodiments are merely exemplary for applying the technical solutions of the present invention, and any technical solution formed by replacing or converting the equivalent thereof falls within the scope of the present invention claimed.
In the description of the schemes, it should be noted that the terms "center", "upper", "lower", "left", "right", "front", "rear", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. In the description of the embodiment, the operator is used as a reference, and the direction close to the operator is a proximal end, and the direction away from the operator is a distal end.
The method for preparing the dense MoAlB ceramic material disclosed by the invention is explained in the following with reference to the attached drawings, as shown in fig. 1, and comprises the following steps:
s1, mixing molybdenum boride powder, aluminum powder and molybdenum powder according to a certain ratio; specifically, the molybdenum boride powder, the aluminum powder and the molybdenum powder are mixed according to the proportion of 1: 2-2.2: 1, the raw materials are mixed according to a molar ratio of 1.
S2, putting the ingredients into a plastic bottle, adding a ball milling medium, and dry-mixing for 1-4 hours on a ball mill to obtain a mixture. The zirconia balls are selected because the zirconia density is high, the specific gravity is high, the impact force is high, the crushing energy is high, the density of the high-quality zirconia ceramics can reach 6.0g/cm, the impact force is high, the required grinding time can be greatly reduced under the same condition, and the material grinding process section is more efficient. Secondly, the hardness of the zirconia ceramic is similar to that of the alumina ceramic, about 12-14GPa, the strength is as high as 800-1000MPa, the fracture toughness can reach 10 MPa.m 1/2, and the fracture toughness is 2-3 times of that of the alumina ceramic, so that the zirconia has high crushing strength and is not easy to damage, and the extremely low abrasion can obviously reduce the introduction of impurities between the materials to be ground.
S3, placing the mixture into a graphite mold, placing the graphite mold into a plasma sintering furnace for prepressing, and then heating at a heating rate of 50-200 ℃ in a vacuum environment or a protective atmosphereoC/min, the sintering temperature is 800oC～1200oAnd C, sintering under the parameter conditions that the pressure is between 50 and 100MPa and the heat preservation and pressure maintaining time is between 5 and 30 minutes. The plasma sintering furnace may be any known plasma sintering equipment, such as a DCS plasma sintering furnace manufactured by Thermal Technology, or a sps-30 plasma sintering furnace manufactured by chenxin equipment technologies ltd, beijing, and the like, without limitation.
The sintering process is as follows:
s31, placing the mixture into a graphite mold with the diameter of 20cm or 40 cm.
S32, placing the graphite mould into a cleaned plasma sintering furnace; the cleaning of the sintering furnace is realized by repeatedly vacuumizing and filling argon for three times, the cleanliness of the environment in the furnace can be effectively ensured by cleaning for three times, and impurities caused by the existence of impurity gases during subsequent sintering are avoided.
And S33, pre-pressing the mixture in the graphite mold under the pressure of 50Pa, and then unloading the pressure.
And S34, flowing argon is introduced into the plasma sintering furnace for protection.
S35, according to the proportion of 50-200oThe temperature rise is started at the temperature rise rate of C/min, and in the process of rising the temperature to the sintering temperature,the operation can effectively avoid the loss of simple substance aluminum in the sintering process due to no pressure application, so that a large amount of impurity phases in the synthesized MoAlB ceramic material are generated, and the purity of the final MoAlB material is improved.
S36, heating to 800 DEGoC～1200oAnd C, preserving the heat for 1-5 minutes after the sintering temperature of C, so that the temperature in the furnace is kept stable.
And S37, after heat preservation, loading pressure to 50-100 MPa at the rate of 20-30 MPa/min, wherein the pressurizing time is only a few minutes.
And S38, keeping the temperature and pressure for 5-30 minutes under the temperature and pressure conditions.
S4, after the heat preservation and pressure maintaining are finished, the temperature is 50-200 DEGoAnd cooling to room temperature at the cooling rate of C/min to obtain the MoAlB ceramic material, wherein the rapid cooling can effectively avoid the growth of crystal grains, and is beneficial to improving the performance of the material.
The scheme further discloses a preparation method of the high-purity MoAlB ceramic powder, which comprises the steps of S1-S4 and S5, and the high-purity MoAlB ceramic powder is obtained by crushing the MoAlB material.
During crushing, the dense MoAlB material obtained in the step S4 can be crushed in a ball mill, and high-purity MoAlB ceramic powder with different particle sizes can be obtained through sieves with different meshes.
Example 1
S1, molybdenum boride powder (MoB)2) Aluminum powder (Al) and molybdenum powder (Mo) according to a molar ratio of 1: 2.1: 1, preparing the materials.
S2, filling the ingredients into a plastic bottle, taking zirconia balls as a ball milling medium, and mixing the ingredients in a ball mill for 2 hours to obtain a mixture.
And S3, filling the mixture into a graphite mold with the diameter of 20cm, then placing the graphite mold into a plasma sintering furnace, and then washing the furnace chamber of the plasma sintering furnace by repeating the operations of vacuumizing and filling argon for three times. And then applying 50MPa pressure to the powder in the graphite mould for prepressing, unloading the pressure after prepressing, and introducing flowing argon into the plasma sintering furnace for protection. By 100oThe furnace temperature is increased to 1100 ℃ at the temperature increase rate of C/minoC, during the whole temperature rising processAny pressure is applied, and the temperature is kept for 2 minutes after the temperature reaches the set temperature. After the completion of the heat preservation, the pressure loading was started, the pressure was increased to 50MPa at a rate of 25MPa/min, and then the heat preservation and pressure holding were carried out at a temperature of 1100 ℃ and a pressure of 50MPa for 15 minutes.
S4, keeping the temperature and pressure at 100 deg.CoAnd cooling to room temperature at the speed of C/min. The compact high-purity MoAlB bulk material can be obtained.
And (3) performing phase analysis, wherein as shown in an XRD diffraction pattern of figure 2, all the detected diffraction peaks are diffraction peaks of MoAlB ceramic, and no other impurity phase is detected, which indicates that the purity of the product is high.
Example 2
S1, molybdenum boride powder (MoB)2) Aluminum powder (Al) and molybdenum powder (Mo) according to a molar ratio of 1: 2.2: 1, preparing the materials.
S2, filling the ingredients into a plastic bottle, taking zirconia balls as a ball milling medium, and mixing the ingredients in a ball mill for 4 hours to obtain a mixture.
S3, the mixture is placed in a graphite die with the diameter of 40cm and then placed in a plasma sintering furnace, and then the furnace chamber of the plasma sintering furnace is subjected to gas washing by repeating the operations of vacuumizing and argon filling for three times. And then applying 50MPa pressure to the powder in the graphite mould for prepressing, unloading the pressure after prepressing, and introducing flowing argon into the plasma sintering furnace for protection. At 50 deg.CoThe furnace temperature is increased to 1200 ℃ at the temperature increase rate of C/minoAnd C, no pressure is loaded in the whole temperature rising process. After the temperature reaches the set temperature and the temperature is kept for 5 minutes, the pressure is loaded, and the pressure is increased to 50MPa at the speed of 25 MPa/min. Next, at 1200oAnd C, keeping the temperature and the pressure for 10 minutes under the condition of 50 MPa.
S4, keeping the temperature and pressure, and then adding 50oAnd cooling to room temperature at the speed of C/min to obtain the compact high-purity MoAlB block material.
The microstructure is shown in figure 3, wherein the black particles are alumina, a few light gray phases are MoB phases, and the rest are MoAlB phase ceramics. From SEM image analysis, the sample is very dense and substantially free of air holes, and contains about 1 according to image analysis and statistics8 ± 0.6vol.% Al2O3And less than 1vol.% MoB2The phases show that the MoAlB ceramic bulk material prepared by the process is very dense and has very few impurity phases.
Example 3
S1, molybdenum boride powder (MoB)2) Aluminum powder (Al) and molybdenum powder (Mo) according to a molar ratio of 1: 2: 1, preparing materials.
S2, filling the ingredients into a plastic bottle, taking zirconia balls as a ball milling medium, and mixing the ingredients in a ball mill for 2 hours to obtain a mixture.
S3, the mixture is placed in a graphite mold with the diameter of 20cm and then placed in a plasma sintering furnace, and then the furnace chamber of the plasma sintering furnace is subjected to gas washing by repeating the operations of vacuumizing and argon filling for three times. And then applying 50MPa pressure to the powder in the graphite mould for prepressing, unloading the pressure after prepressing, and introducing flowing argon into the plasma sintering furnace for protection. At 200 deg.CoThe temperature of the furnace is increased to 1000 ℃ at the temperature increase rate of C/minoAnd C, loading no pressure in the whole temperature rise process, and starting to load the pressure after the temperature reaches the set temperature and is kept for 5 minutes. Pressurizing to 50MPa at the speed of 25MPa/min, and then keeping the temperature and the pressure for 30 minutes at the temperature of 1000 ℃ and the pressure of 50 MPa.
S4, keeping the temperature and pressure, and adding 200oAnd cooling to room temperature at the speed of C/min to obtain the compact high-purity MoAlB block material.
The microstructure is shown in figure 4, wherein the black small particles are alumina, a small amount of light gray phase is MoB phase, the rest is MoAlB phase ceramic, the grain size is less than 10 μm, the sample is very compact and basically has no air holes from SEM picture, and the material contains about 2.1 +/-0.9 vol.% Al according to image analysis and statistics2O3And less than 1.8 ± 0.8vol.% MoB2The phases show that the MoAlB ceramic bulk material prepared by the process is very dense and has very few impurity phases.
The invention has various embodiments, and all technical solutions formed by adopting equivalent transformation or equivalent transformation are within the protection scope of the invention.
Claims (9)
1. The preparation method of the compact MoAlB ceramic material is characterized by comprising the following steps:
s1, mixing molybdenum boride powder, aluminum powder and molybdenum powder as raw materials;
s2, putting the ingredients into a plastic bottle, adding a ball milling medium, and dry-mixing for 1-4 hours on a ball mill to obtain a mixture;
s3, placing the mixture into a graphite mold, placing the graphite mold into a plasma sintering furnace for prepressing, and then heating at a heating rate of 50-200 ℃ in a vacuum environment or a protective atmosphereoC/min, the sintering temperature is 800oC～1200oC, sintering under the parameter conditions that the pressure is between 50 and 100MPa and the heat preservation and pressure maintaining time is between 5 and 30 minutes;
and S4, maintaining the temperature and pressure, and cooling to room temperature to obtain the compact MoAlB ceramic material.
2. The method of preparing a dense MoAlB ceramic material according to claim 1, wherein in the step S1, the molybdenum boride powder, the aluminum powder, and the molybdenum powder are mixed in a ratio of 1: 2-2.2: 1, the raw materials are mixed according to a molar ratio of 1.
3. The method of preparing a dense MoAlB ceramic material of claim 1, wherein in step S2, the ball milling media are zirconia balls.
4. The method of making dense MoAlB ceramic material of any of claims 1 to 3, wherein the step S3 comprises the following steps:
s31, placing the mixture in a graphite mold with the diameter of 20cm or 40 cm;
s32, placing the graphite mould into a cleaned plasma sintering furnace;
s33, pre-pressing the mixture in the graphite mold under the pressure of 50Pa, and then unloading the pressure;
s34, flowing argon is introduced into the plasma sintering furnace for protection;
s35, starting to heat, and in the process of heating to the sintering temperature, not applying pressure;
s36, heating to a sintering temperature, and then preserving heat for 1-5 minutes;
s37, after heat preservation, loading pressure to a set pressure value;
and S38, preserving heat and pressure for 5-30 minutes.
5. The method of claim 4, wherein the plasma sintering furnace is cleaned by repeating the evacuation and the filling of argon three times in step S32.
6. The method for preparing a dense MoAlB ceramic material according to claim 4, wherein in the step S37, the pressurizing is performed at a rate of 20-30 MPa/min.
7. The method for preparing the dense MoAlB ceramic material according to claim 1, wherein the concentration of the MoAlB ceramic material in the step S4 is 50-200%oAnd C/min cooling rate.
8. The compact MoAlB ceramic block is characterized in that: prepared by the process of any one of claims 1 to 7.
9. The preparation method of the high-purity MoAlB ceramic powder is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing molybdenum boride powder, aluminum powder and molybdenum powder as raw materials;
s2, putting the ingredients into a plastic bottle, adding a ball milling medium, and dry-mixing for 1-4 hours on a ball mill to obtain a mixture;
s3, placing the mixture into a graphite mold, placing the graphite mold into a plasma sintering furnace for prepressing, and then heating at a heating rate of 50-200 ℃ in a vacuum environment or a protective atmosphereoThe sintering temperature is 800 ℃ between C/minoC～1200oC, sintering under the parameter conditions that the pressure is 50-100 MPa and the heat preservation and pressure maintaining time is 5-30 minutes；
S4, cooling to room temperature after heat preservation and pressure maintaining to obtain a compact MoAlB ceramic material;
and S5, crushing the MoAlB ceramic material to obtain high-purity MoAlB ceramic powder.
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