CN106316440B - Preparation method of porous ceramic with complex structure based on selective laser sintering - Google Patents
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Abstract
The invention discloses a preparation method of porous ceramic with a complex structure based on selective laser sintering, which comprises the following steps: 1) designing a CAD model of porous ceramics with a complex structure, carrying out slicing processing and storing the CAD model as an STL file, and importing data information of the STL file into SLS equipment; 2) preparing binder/ceramic composite powder by using initial ceramic powder and binder, and controlling the micro-pore characteristics of the porous ceramic by adjusting the type and the addition amount of the binder; 3) presetting SLS forming process parameters, and forming a biscuit by combining data information; 4) and 3) carrying out glue discharging and sintering treatment on the biscuit formed in the step 3) to obtain the required porous ceramic. The method can prepare the porous ceramic with any complex macroscopic pore structure and unique microscopic pore characteristics, and has the advantages of simple and efficient process, no need of a die, low production cost and the like.
Description
Technical Field
The invention belongs to the field of ceramic preparation, and particularly relates to a preparation method of porous ceramic with a complex structure based on selective laser sintering.
Background
The porous ceramic material has the advantages of extremely high specific surface area, good chemical stability, high corrosion resistance, high hardness, wear resistance, high temperature resistance, no toxicity, no harm and the like, and is widely used as a catalyst carrier, a filter material, a heat preservation and insulation material, a sound absorption material and the like. With the development requirements of science and technology, the requirements of new application fields such as aerospace, military equipment, metal ceramic composite materials and the like are more urgent, and higher requirements are put forward on the performance of the porous ceramic materials.
The performance of the porous ceramic mainly depends on the porosity, the pore size and the pore channel distribution condition, the traditional methods for preparing the porous ceramic at present comprise an extrusion forming method, a particle stacking method, a gas foaming method, an organic foam impregnation method, a pore-forming agent adding method and the like, but the methods for preparing the porous ceramic generally have the problems that the high-complexity porous ceramic is difficult to prepare, the size and the shape of pores in the preparation process are difficult to control and the like.
Disclosure of Invention
Aiming at the defects or improvement requirements in the prior art, the invention provides a preparation method of porous ceramic with a complex structure based on selective laser sintering, aiming at overcoming the problem that the complex porous structure ceramic is difficult to prepare in the prior art, making full use of the characteristics of an SLS (selective laser sintering) forming process to prepare the porous ceramic with any complex macroscopic pore structure and unique microscopic pore characteristics, and solving the problem that the high-complexity porous ceramic is difficult to controllably form in the traditional process.
In order to achieve the aim, the invention provides a preparation method of porous ceramic with a complex structure based on selective laser sintering, which comprises the following steps:
(1) designing a CAD model of porous ceramic with a complex structure, slicing the CAD model, storing the sliced CAD model as an STL file, and importing data information of the STL file into SLS forming equipment;
(2) preparing the initial ceramic powder and the binder for preparing the porous ceramic with the complex structure into the binder/ceramic composite powder suitable for SLS (selective laser sintering) molding by adopting a mechanical mixing method or a solvent precipitation method, and controlling the final microscopic pore characteristics of the porous ceramic by adjusting the type and the addition amount of the binder;
(3) presetting SLS forming process parameters of SLS forming equipment, and forming a biscuit of the porous ceramic on the SLS forming equipment by combining the data information imported in the step (1);
(4) and (4) carrying out binder removal and sintering treatment on the biscuit of the porous ceramic formed in the step (3), so as to obtain the required porous ceramic with a complex structure.
Further preferably, the CAD model of the porous ceramic having a complex structure described in step (1) is preferably a honeycomb porous structure or a spatial topology structure having interconnected pores.
More preferably, the initial ceramic powder in step (2) includes non-oxide ceramic powder and oxide ceramic powder, wherein the non-oxide ceramic powder is preferably Si3N4SiC, the oxide ceramic powder is preferably cordierite or Al2O3。
More preferably, the binder used in the step (2) of preparing the composite powder for SLS molding by mechanical mixing is an inorganic binder, an organic binder, or a metal binder.
Further preferably, the inorganic binder is ammonium dihydrogen phosphate, the organic binder is epoxy resin, polymethyl methacrylate, stearic acid or nylon, and the metal binder is aluminum powder.
More preferably, when the composite powder is prepared by adopting a mechanical mixing method, the binder accounts for 5-25% of the total powder by mass, and the powder mixing time is 24 hours.
As a further preferred method, the method for preparing the composite powder by using the solvent precipitation method specifically comprises the following steps: adding a binder accounting for 10-25% of the volume ratio of the total powder and ceramic powder accounting for 75-90% of the volume fraction into absolute ethyl alcohol, uniformly mixing, pouring into a reaction kettle, heating to 140 ℃, keeping the temperature for 3 hours, naturally cooling to obtain a suspension, carrying out suction filtration and drying on the obtained suspension, and thus obtaining the binder-coated ceramic powder.
Preferably, the SLS molding process parameters in step (3) are specifically: the preheating temperature is 45-150 ℃, the powder spreading layer thickness is 0.1-0.3 mm, the scanning interval of laser equipment is 0.1-0.3 mm, the diameter of a laser spot is 0.1-0.3 mm, the laser power is 5-18W, and the scanning speed is 1000-3000 mm/s.
As a further preference, for the preferred binder E12 for mechanical mixing, the preferred SLS forming process parameters are: the preheating temperature is set to be 45 ℃, the powder layer spreading thickness is 0.1mm, the scanning interval of laser equipment is 0.1mm, the diameter of a laser spot is 0.2mm, the laser power is 7W, the scanning speed is 2000mm/s, and the adhesive E12 can generate appropriate viscous flow when heated under the optimized process, so that a good forming effect is obtained.
As a further preference, for the preferred binder PA12 for the solvent precipitation method, the preferred SLS forming process parameters are: the preheating temperature is set to be 135 ℃, the powder layer spreading thickness is 0.1mm, the scanning interval of laser equipment is 0.1mm, the laser spot diameter is 0.2mm, the laser power is 10W, the scanning speed is 2000mm/s, and the bonding agent PA12 can generate a proper amount of viscous flow when being heated under the optimized process, so that a good forming effect is obtained.
As a further preferred option, the glue removing process in the step (4) is as follows: heating the mixture from room temperature to 600-800 ℃ at the speed of 0.3-2 ℃/min, preserving the heat for 1-3 h, and cooling the mixture to room temperature along with the furnace.
Further preferably, the sintering treatment process in the step (4) is as follows: heating the mixture from room temperature to 1450-2000 ℃ at the speed of 3-5 ℃/min, preserving the heat for 2-4 h, and cooling the mixture to the room temperature along with the furnace.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1. the selective laser sintering is applied to the forming of the ceramic with the complex porous structure, the part is directly manufactured by the three-dimensional data driving of the part, and the arbitrary complex porous structure can be designed by using three-dimensional software according to the application requirement, so that the control of the macroscopic pore structure of the porous ceramic is realized.
2. In the porous ceramic biscuit prepared by selective laser sintering, the binder with the binding effect is burnt out in the later degumming process, so that the finally obtained porous ceramic has a unique micro-pore structure.
3. The preparation method of the invention matches the macroscopic porous structure and the microscopic pore characteristics of the porous ceramic part, increases the adjustment range and controllability of the pore characteristics of the porous ceramic, and is beneficial to preparing the porous ceramic meeting various performance requirements.
4. The preparation method disclosed by the invention is simple and efficient in process, does not need a die, and reduces the production cost.
Drawings
FIG. 1 is a schematic diagram of a CAD model of a ceramic having a complex porous structure, wherein (a) is a cellular porous model having internal interconnected pores, and (b) is a icosahedral spatial topology model;
FIG. 2 is a graph of E12/Si with 15 wt% E12 made by the mechanical mixing method of example 13N4SEM image of composite powder;
FIG. 3 is a diagram of a biscuit object formed on an SLS device by using the three-dimensional model shown in FIG. 1 and the composite powder shown in FIG. 2;
FIG. 4 is a sectional SEM photograph of a shaped greenbody of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The embodiment of the invention provides a preparation method of porous ceramic with a complex structure based on Selective Laser Sintering (SLS), which comprises the following steps:
(1) according to application requirements, a CAD model of porous ceramics with a complex structure is optimally designed (namely, according to the use occasion and performance requirements of the porous ceramics, the optimal design is carried out on a macroscopic porous structure, such as increasing or reducing a through hole structure, the inner wall of a smooth hole or adding a special-shaped bulge on the inner wall of the hole), the macroscopic porous structure is sliced by slicing software and then stored into an STL file, data information of the STL file is imported into SLS forming equipment, wherein the CAD three-dimensional model can be an optimized cellular porous structure with internal through holes or a space topological structure such as an octahedron, a twenty-tetrahedron and the like.
(2) The method comprises the steps of preparing binder/ceramic composite powder suitable for SLS (selective laser sintering) molding from initial ceramic powder and binder by adopting a mechanical mixing method or a solvent precipitation method, and adjusting the type and the addition amount of the binder according to needs to control the micro-pore characteristics of a final ceramic part.
Wherein the initial ceramic powder is Si3N4Non-oxide ceramic powder such as SiC, cordierite, Al2O3And the like. The binder used in preparing composite powder for SLS molding by mechanical mixing method is inorganic binder, organic binder or metal binder, wherein the inorganic binder is ammonium dihydrogen phosphate, etc., and the organic binder is epoxy resin (may be E)06, E10, E12, preferably E12), polymethyl methacrylate, stearic acid or nylon (which may be PA6, PA66, PA12, preferably PA12), etc., and the metal binder is aluminum powder, etc. The binder used in the preparation of the composite powder for SLS molding by the solvent precipitation method is polypropylene, nylon and the like.
Specifically, the mechanical mixing method for preparing the composite powder comprises the following steps: the binder accounts for 5-25% of the total powder mass, and is placed on a powder mixing frame to roll for 24 hours, so that the powder is uniformly mixed. The preparation method of the composite powder by adopting a solvent precipitation method comprises the following steps: adding a binder accounting for 10-25% of the total powder volume ratio and ceramic powder accounting for 75-90% of the corresponding volume fraction into absolute ethyl alcohol, uniformly mixing, pouring into a reaction kettle, heating to the maximum temperature of about 140 ℃, preserving heat for 3 hours, naturally cooling, carrying out suction filtration and drying on the obtained suspension, and obtaining the binder-coated ceramic powder.
(3) And (3) adjusting parameters such as laser power, scanning speed and scanning layer thickness according to the type of the binder and the characteristics of the composite powder, and combining the data information introduced in the step (1) to form a biscuit on an SLS device.
In the SLS forming process parameters in the step (3), according to the type of the used binder and the property of the composite powder, the preheating temperature is set to be 45-150 ℃, the thickness of the powder spreading layer is 0.1-0.3 mm, the scanning distance of laser equipment is 0.1-0.3 mm, the diameter of a laser spot is 0.1-0.3 mm, the laser power is 5-18W, and the scanning speed is 1000-3000 mm/s. For the preferred binder E12 for mechanical powder mixing, SLS forming process parameters are preferably set to 45 ℃ of preheating temperature, 0.1mm of powder laying layer thickness, 0.1mm of scanning interval of laser equipment, 0.2mm of laser spot diameter, 7W of laser power and 2000mm/s of scanning speed, and the binder E12 can generate proper viscous flow when heated in the preferred process, so that a good forming effect is obtained. For the preferred adhesive PA12 for the solvent precipitation method, the preferred SLS forming process parameters are that the preheating temperature is set to be 135 ℃, the powder layer spreading thickness is 0.1mm, the scanning distance of a laser device is 0.1mm, the laser spot diameter is 0.2mm, the laser power is 10W, and the scanning speed is 2000mm/s, and the adhesive PA12 can generate a proper amount of viscous flow when being heated in the preferred process, so that a good forming effect is obtained.
(4) And (4) carrying out glue discharging and sintering treatment on the biscuit formed in the step (3) to obtain the required porous ceramic product with the complex structure.
Wherein, the glue discharging process specifically comprises the following steps: heating the biscuit to 600-800 ℃ from room temperature at the speed of 0.3-2 ℃/min, preserving heat for 1-3 h, and cooling the biscuit to room temperature along with a furnace.
The sintering treatment process specifically comprises the following steps: raising the temperature from room temperature to 1450-2000 ℃ at the speed of 3-5 ℃/min, preserving the temperature for 2-4 h, and cooling to the room temperature along with the furnace, wherein the preferable process is as follows: the temperature is increased from room temperature to 1450-2000 ℃ at the speed of 3-5 ℃/min, the temperature is kept for 2-4 h, the temperature is cooled to room temperature along with the furnace, and ceramic particles can slowly and fully grow up under the process, so that the strength of the porous ceramic is improved.
The method adopts an SLS (selective laser sintering) technology to form the porous ceramic product with a complex structure, the technology is used as one of Additive Manufacturing (AM), parts are directly manufactured by three-dimensional data drive of the parts, the traditional 'removal' material Manufacturing or 'isometric' Manufacturing is changed into 'addition' material Manufacturing, and the method has incomparable advantages in the aspect of preparing parts with complex shapes and structures, so that the ceramic forming with the complex porous structure can be prepared. The basic principle is that a binder is added into ceramic powder, the melting, flowing and solidifying of the binder among the ceramic powder are realized by inputting energy through laser scanning, the bonding among the ceramic powder is completed, the binder is removed through later glue discharging and the ceramic part with certain strength is obtained through high-temperature sintering, and a large number of micro pores exist in the finally-formed ceramic part due to the action of the binder in the forming process, so that the porous ceramic with a complex macro porous structure, unique micro pore characteristics and high porosity can be formed by adopting the SLS forming process.
Based on the characteristic that the ceramic prepared by the SLS technology is loose and porous, the macroscopic pore structure is controlled by the optimized design of a CAD model, the microscopic pores are controlled by adjusting the type and the adding amount of the binder in the powder preparation process, the macroscopic pore structure and the microscopic pores are matched with each other, a mold is not needed, the porous ceramic with any complex macroscopic pore structure and unique microscopic pore characteristics can be quickly prepared, and the problem that the high-complexity porous ceramic is difficult to controllably mold by the traditional process is solved.
The technical scheme of the invention is further explained by combining specific examples.
Example 1
(1) Establishing a part CAD model (shown in figure 1) with an internally communicated cellular porous structure, processing the part CAD model by slicing software, storing the part CAD model as an STL file, and importing data information of the STL file into SLS forming equipment;
(2) get 300gSi3N4Adding 15.79g, 33.33g, 52.94g, 75.00g and 100.00g of epoxy resin E12 into the granulated powder respectively, placing the mixture into a nylon tank for uniform mixing, and rotating the nylon tank on a powder mixing rack for 24 hours to obtain E12/Si with the E12 content of 5 wt%, 10 wt%, 15 wt%, 20 wt% and 25 wt%3N4Composite powder (see fig. 2, wherein a in fig. 2 is ceramic powder, and B is epoxy resin);
(3) forming the composite powder on SLS equipment, wherein the diameter of a laser spot is 0.15mm, the preheating temperature is 45 ℃, the thickness of a powder spreading layer is 0.15mm, the scanning distance is 0.15mm, the laser power is 9W, and the scanning speed is 2000mm/s (a formed biscuit is shown in figure 3, and the microstructure of a section is shown in figure 4);
(4) placing the biscuit in a glue discharging furnace, heating to 600 ℃ at the speed of 0.3 ℃/min, preserving heat for 1h, and cooling along with the furnace;
(5) and placing the biscuit subjected to binder removal in a nitrogen atmosphere sintering furnace, heating to 1800 ℃ at the speed of 3 ℃/min, preserving heat for 3h, and cooling to room temperature along with the furnace.
Example 2
(1) Establishing a CAD model of the octahedral space topological structure, processing the CAD model by slicing software, storing the CAD model as an STL file, and importing data information of the STL file into SLS forming equipment;
(2) adding 15.79g, 33.33g, 52.94g, 75.00g and 100.00g of epoxy resin E12 into each group of 300g of SiC granulated powder, placing the mixture into a nylon tank, uniformly mixing the mixture, and rotating the mixture on a powder mixing frame for 24 hours to obtain E12/SiC composite powder with E12 contents of 5 wt%, 10 wt%, 15 wt%, 20 wt% and 25 wt%;
(3) forming the composite powder on SLS equipment, wherein the diameter of a laser spot is 0.2mm, the preheating temperature is 45 ℃, the thickness of a powder spreading layer is 0.2mm, the scanning interval is 0.2mm, the laser power is 5W, and the scanning speed is 1000 mm/s;
(4) placing the biscuit in a glue discharging furnace, heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 2h, and cooling along with the furnace;
(5) and (3) placing the biscuit subjected to binder removal in a vacuum sintering furnace, heating to 2000 ℃ at the speed of 4 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with the furnace.
Example 3
(1) Establishing a CAD model of a regular icosahedron spatial topological structure, processing the CAD model by slicing software, storing the CAD model as an STL file, and importing data information of the STL file into SLS forming equipment;
(2) respectively adding 33.33g, 52.94g, 75.00g and 100.00g of epoxy resin E12 into 300g of cordierite powder, placing the mixture into a nylon tank, uniformly mixing, and rotating on a powder mixing frame for 24 hours to obtain E12/cordierite composite powder with E12 contents of 10 wt%, 15 wt%, 20 wt% and 25 wt%;
(3) forming the composite powder on SLS equipment, wherein the diameter of a laser spot is 0.3mm, the preheating temperature is 80 ℃, the thickness of a powder spreading layer is 0.3mm, the scanning interval is 0.3mm, the laser power is 18W, and the scanning speed is 3000 mm/s;
(4) placing the biscuit in a glue discharging furnace, heating to 600 ℃ at the speed of 2 ℃/min, preserving heat for 3h, and cooling along with the furnace;
(5) and (3) placing the biscuit after the binder removal into a sintering furnace, heating to 1450 ℃ at the speed of 5 ℃/min, preserving the temperature for 4h, and cooling to room temperature along with the furnace.
Example 4
(1) Establishing an application-optimization-oriented regular octahedral space topological structure CAD model, processing the model by slicing software, storing the model as an STL file, and importing data information of the STL file into SLS forming equipment;
(2) taking each group 300gSi3N4Adding 10.52g, 16.71g, 23.67g and 31.56g of nylon PA12 into the powder respectively, mixing with a proper amount of absolute ethyl alcohol uniformly, pouring into a reaction kettle, heating and maintaining the pressureHeating to the maximum temperature of 140 ℃, preserving heat for 3 hours, naturally cooling, and then carrying out suction filtration and drying on the obtained suspension to obtain PA/Si with the PA contents of 10 vol%, 15 vol%, 20 vol% and 25 vol% respectively3N4Composite powder;
(3) forming the composite powder on SLS equipment, wherein the diameter of a laser spot is 0.1mm, the preheating temperature is 150 ℃, the thickness of a powder spreading layer is 0.15mm, the scanning interval is 0.25mm, the laser power is 10W, and the scanning speed is 2000 mm/s;
(4) placing the biscuit in a glue discharging furnace, heating to 700 ℃ at the speed of 0.5 ℃/min, preserving heat for 2h, and cooling along with the furnace;
(5) and placing the biscuit subjected to binder removal in a nitrogen atmosphere sintering furnace, heating to 1800 ℃ at the speed of 3 ℃/min, preserving heat for 4h, and cooling to room temperature along with the furnace.
Example 5
(1) Establishing a honeycomb ceramic three-dimensional model with an internal connection hole structure, generating an STL file, importing the STL file into SLS equipment, and completing automatic layering;
(2) adding 10.52g, 16.71g, 23.67g and 31.56g of nylon into each group of 300g of SiC powder, mixing the mixture with a proper amount of absolute ethyl alcohol uniformly, pouring the mixture into a reaction kettle, heating and maintaining the pressure, heating to the maximum temperature of about 140 ℃, preserving the temperature for 3 hours, naturally cooling, and performing suction filtration and drying on the obtained suspension to obtain PA/SiC composite powder with the PA contents of 10 vol%, 15 vol%, 20 vol% and 25 vol%;
(3) forming the composite powder on SLS equipment, wherein the diameter of a laser spot is 0.1mm, the preheating temperature is 150 ℃, the thickness of a powder spreading layer is 0.1mm, the scanning interval is 0.1mm, the laser power is 7W, and the scanning speed is 2000 mm/s;
(4) placing the biscuit in a glue discharging furnace, heating to 800 ℃ at the speed of 1.5 ℃/min, preserving heat for 2h, and cooling along with the furnace;
(5) and (3) placing the biscuit subjected to binder removal in a vacuum sintering furnace, heating to 2000 ℃ at the speed of 3 ℃/min, preserving heat for 2h, and cooling to room temperature along with the furnace.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (2)
1. A preparation method of porous ceramic with a complex structure based on selective laser sintering is characterized by comprising the following steps:
(1) designing a CAD model of porous ceramic with a complex structure, slicing the CAD model, storing the sliced CAD model as an STL file, and importing data information of the STL file into SLS forming equipment; the CAD model of the porous ceramic with the complex structure is a honeycomb porous structure or a space topological structure with internal connecting holes;
(2) preparing initial ceramic powder and binder for preparing porous ceramic with complex structure by solvent precipitation method to obtain binder/ceramic composite powder suitable for SLS molding, and controlling final microscopic pore characteristics of porous ceramic by adjusting binder type and addition amount, wherein the initial ceramic powder is Si3N4The binder is PA12, and the steps of preparing the binder/ceramic composite powder suitable for SLS forming by adopting a solvent precipitation method are as follows: taking each group 300gSi3N4Adding 10.52g, 16.71g, 23.67g and 31.56g of nylon PA12 into the powder respectively, mixing the powder with a proper amount of absolute ethyl alcohol uniformly, pouring the mixture into a reaction kettle, heating the mixture to the maximum temperature of 140 ℃, preserving the heat for 3 hours, naturally cooling the mixture, and then carrying out suction filtration and drying on the obtained suspension to obtain PA12/Si with the PA12 contents of 10 vol%, 15 vol%, 20 vol% and 25 vol%, respectively3N4Composite powder;
(3) presetting SLS forming process parameters of SLS forming equipment, and forming a biscuit of the porous ceramic on the SLS forming equipment by combining the data information imported in the step (1), wherein the SLS forming process parameters are as follows: the diameter of a laser spot is 0.1mm, the preheating temperature is 150 ℃, the thickness of a powder layer is 0.15mm, the scanning interval is 0.25mm, the laser power is 10W, and the scanning speed is 2000mm/s, so that the control on the macroscopic pore structure of the porous ceramic is realized;
(4) and (4) carrying out binder removal and sintering treatment on the biscuit of the porous ceramic formed in the step (3), thus obtaining the required porous ceramic with a complex structure with any macroscopic pore structure and microscopic pore characteristics.
2. The preparation method of the porous ceramic with the complex structure based on the selective laser sintering, according to claim 1, wherein the glue removing process in the step (4) is as follows: heating the mixture from room temperature to 600-800 ℃ at the speed of 0.3-2 ℃/min, preserving the heat for 1-3 h, and cooling the mixture to room temperature along with the furnace; the sintering treatment process in the step (4) comprises the following steps: heating the mixture from room temperature to 1450-2000 ℃ at the speed of 3-5 ℃/min, preserving the heat for 2-4 h, and cooling the mixture to the room temperature along with the furnace.
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