CN114213142A - Preparation method of extruded 3D printed silicon-aluminum oxide ceramic aerogel - Google Patents
Preparation method of extruded 3D printed silicon-aluminum oxide ceramic aerogel Download PDFInfo
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Abstract
The invention discloses a preparation method of an extruded 3D printed silicon-aluminum oxide ceramic aerogel, aiming at realizing additive manufacturing of the aluminum oxide ceramic aerogel and meeting the performance requirements of low density, low thermal conductivity and high temperature resistance of the silicon-aluminum oxide ceramic aerogel, and the silicon-aluminum oxide ceramic ink can realize controllable heat curing by temperature induction to obtain the 3D printed silicon-aluminum oxide ceramic aerogel with high structural integrity and high shape fidelity. The technical scheme is as follows: preparing silicon-aluminum oxide ceramic ink capable of being thermally cured, 3D printing the silicon-aluminum oxide ceramic ink, carrying out temperature control thermal curing, carrying out supercritical drying, and carrying out high-temperature heat treatment to obtain the 3D printing silicon-aluminum oxide ceramic aerogel. The invention can realize the controllable heat curing of the silicon-aluminum oxide ceramic ink, and obtain the 3D printing silicon-aluminum oxide ceramic with low density, low heat conductivity, high temperature resistance, high structural integrity and high shape fidelity, and the aerogel can keep a hollow porous structure after being calcined at 1100 ℃.
Description
Technical Field
The invention relates to the technical field of additive manufacturing of ceramic aerogel, in particular to a preparation method of 3D extruded and printed silicon-aluminum oxide ceramic aerogel.
Background
Ceramic aerogels have high porosity, large surface area, low density, low thermal conductivity, and excellent thermal oxidation resistance, and are widely used in the fields of thermal/acoustic/electrical insulation, catalyst supports, filters, energy storage materials, and the like. However, the ceramic aerogel has the intrinsic brittleness problem, and the complex structure and shape of the ceramic aerogel are difficult to be endowed by the traditional material reducing manufacturing processes such as turning, milling, planing, grinding and the like. Compared with a material reduction manufacturing process, additive manufacturing (also called three-dimensional printing, 3D printing) provides a new idea and a new solution for custom molding and complex structural design of ceramic aerogel.
3D prints to be one kind and relies on the successive layer to accumulate the material and realize the new technology that 3D model to entity object transformation, is known as the main promoter of the fourth industrial revolution, and its advancement lies in low cost, low time consumption and need not the mould supplementary. To date, there are three main 3D printing techniques applied to the manufacture of ceramic aerogels, which include extrusion 3D printing, inkjet 3D printing, and photo-curing 3D printing. Of these printing strategies, the greatest advantage of extrusion 3D printing is its good compatibility of the inks. Various existing materials, including zero-dimensional nanoparticles, one-dimensional nanowires or nanofibers, and two-dimensional nanosheets, can be integrated into an ink formulation to obtain adjustable printing rheological properties and to impart a 3D printing aerogel design function. Given the low complexity of the extrusion 3D printing apparatus and negligible printing condition limitations, existing aerogels such as graphene, graphene oxide, carbon nanotubes, silver nanowires, boron carbide, cellulose, resorcinol-formaldehyde, and carbon can all be made additive manufacturing, which provides precedent demonstration and theoretical support for 3D printing ceramic aerogels.
Silica aerogel is one of the ceramic aerogel species, and its additive manufacturing technology is the hot spot of current research. [ ACS Applied Materials&Interfaces,2018,10(26):22718-22730]Reports a preparation method of silica aerogel containing silk protein by extrusion 3D printing, and the 3D printing aerogel presents low density (0.11-0.20 g cm)-3) And low thermal conductivity (0.033-0.039 W.m)-1·K-1). However, the silica aerogel prepared by the extrusion 3D printing method is an organic-inorganic hybrid material essentially, and a large amount of organic matters are decomposed easily when the temperature exceeds 300 ℃, so that the requirement of high-temperature application cannot be met; [ Applied Materials Today,2021,24:101083]A preparation method of photocuring 3D printing silica aerogel is reported, the 3D printing method can realize the construction of the aerogel on a submicron scale and endow the aerogel with a fine and complex structure, and the finally obtained 3D printing silica aerogel has low density (0.16g cm)-3) And a high specific surface area (580 m)2·g-1) The performance is comparable to that of the traditional silica aerogel. However, a significant disadvantage of this photocuring 3D printing method for preparing silica aerogel is its harsh molding conditions, typically requiring reliance on photosensitive resins to maintain material molding, and ceramic conversion by heat treatment at about 700 ℃. In addition to the above methods, [ Nature,2020,584(7821):387-]A method of preparing an extruded 3D printed silica aerogel is reported in which ammonia vapor induces a condensation polymerization reaction of silica sol in the ink, which macroscopically appears as the ink's own accord in an ammonia vapor atmosphereCuring, and after supercritical drying, the 3D printed silica aerogel exhibits high structural integrity and high shape fidelity. However, this method is intended to obtain pure 3D printed silica aerogels, according to the literature [ Advances in Colloid and Interface Science 282(2020): 102189)]It is reported that the temperature resistance of pure silica aerogels is theoretically difficult to exceed 600 ℃, which limits their high temperature applications.
At present, although certain progress is made in a silica aerogel additive manufacturing technology, the existing 3D printing silica aerogel method has design defects and is difficult to be widely applied to ceramic aerogel additive manufacturing, particularly 3D printing of silicon-aluminum oxide ceramic aerogel, and related documents report 3D printing processes and methods. Compared with the silica aerogel, the silica-alumina oxide ceramic aerogel has higher high temperature resistance, the use temperature is higher than the silica aerogel limit temperature (600 ℃), and the high-temperature heat insulation design requirement is favorably met. Therefore, the realization of the additive manufacturing of the silicon-aluminum oxide ceramic aerogel has practical significance for the high-temperature application of the porous ceramic material.
In summary, the silicon-aluminum oxide ceramic aerogel has excellent high temperature resistance, and is an ideal material for high-temperature heat insulation, the existing 3D printing silicon oxide aerogel method is difficult to be applied to additive manufacturing of the silicon-aluminum oxide ceramic aerogel, and meanwhile, a method for preparing the silicon-aluminum oxide ceramic aerogel by means of an extrusion 3D printing technology has not been reported. Therefore, under the condition of meeting the performance requirements of low density, low thermal conductivity and high temperature resistance of the ceramic aerogel, the development of a preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel is still a great technical problem, which is also the key point for realizing the preparation and application of the 3D printed oxide ceramic aerogel in the industrial and civil fields in the future.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel, under the condition that the performance requirements of low density, low thermal conductivity and high temperature resistance of the silicon-aluminum oxide ceramic aerogel are met, the silicon-aluminum oxide ceramic ink can realize controllable heat curing by means of temperature induction, and then the 3D printed silicon-aluminum oxide ceramic aerogel with high structural integrity and high shape fidelity is obtained.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
according to the extruded 3D printed silicon-aluminum oxide ceramic aerogel, after supercritical drying, the primary 3D printed silicon-aluminum oxide aerogel mainly comprises amorphous silicon oxide and crystalline boehmite. Wherein the mass fraction of the silicon oxide in the initial 3D-printed silicon-aluminum oxide aerogel is 60-100%, and the mass fraction of the boehmite in the initial 3D-printed silicon-aluminum oxide aerogel is 0-40%; after heat treatment, boehmite in the initial 3D-printed silicon-aluminum oxide aerogel is converted into corresponding gamma-phase alumina to obtain the 3D-printed silicon-aluminum oxide ceramic aerogel.
The preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel mainly comprises the following steps: preparing silicon-aluminum oxide ceramic ink capable of being thermally cured, extruding 3D printing silicon-aluminum oxide ceramic ink, carrying out temperature control thermal curing, carrying out supercritical drying and carrying out high-temperature heat treatment.
The method comprises the following specific steps:
firstly, preparing the heat-curable silicon-aluminum oxide ceramic ink, which comprises the following steps:
1.1 mixing the nano silicon oxide powder, the aqueous silica sol, the aqueous aluminum sol, the polyvinyl alcohol, the urea and the water, and uniformly stirring to prepare the primary mixed slurry. Wherein, the nano silicon oxide powder is used as an ink thickener to adjust the rheological property of the ink; the polyvinyl alcohol is used as an ink cross-linking agent to assist the nano silicon oxide powder to adjust the rheological property of the ink; the urea is used as a temperature induction catalyst, is decomposed to release alkaline ammonia, can promote the condensation polymerization reaction of the aqueous silica sol and the aqueous aluminum sol, and is the key point that the silicon-aluminum oxide ceramic ink can realize thermal curing. In the ink composition, the mass fractions of the nano silicon oxide powder, the aqueous silica sol, the aqueous aluminum sol, the polyvinyl alcohol, the urea and the water in the silicon-aluminum oxide ceramic ink are respectively 10, 15-55, 0-50, 0-5, 1-5 and 1-40.
The nano silicon oxide powder has a specific surface area of 50-1000 m2·g-1The gas-phase silicon oxide powder of (2);
the aqueous silica sol is nano silica colloidal particle aqueous dispersion with the solid content of about 40 weight percent;
the aqueous alumina sol is a boehmite aqueous dispersion with a solid content of about 20 wt%;
and 1.2, placing the primarily mixed slurry in a centrifugal defoaming stirrer, and stirring for 1-30 minutes to obtain the silicon-aluminum oxide ceramic ink which is bubble-free, thermocurable and capable of being formed in a self-supporting mode. In the preparation process, the revolution speed of the stirrer is controlled to be 400-1000 rpm, and the rotation speed is controlled to be 100-800 rpm;
and secondly, extruding the silicon-aluminum oxide ceramic ink for 3D printing to obtain a 3D printed piece, wherein the method comprises the following steps:
packaging silicon-aluminum oxide ceramic ink in a 3D printer bin, designing the structural shape of silicon-aluminum oxide ceramic aerogel by means of three-dimensional modeling software, selecting a 3D printer nozzle with a corresponding discharge port diameter according to the surface precision requirement, planning a printing path according to a numerical control programming language (G code), controlling the 3D printer nozzle to print on a two-dimensional plane at a certain printing speed, and after printing one layer of ink, automatically lifting the printer nozzle upwards according to the programming path, and printing the next layer until a 3D printed part is obtained;
the diameter of a discharge hole of the 3D printer nozzle is 0.1-3.0 mm;
the certain printing speed means that the movement speeds of the 3D printer in the x-axis and y-axis directions are controlled to be 0.2-40 mm/s;
thirdly, controlling temperature and performing thermocuring, wherein the method comprises the following steps:
placing the 3D printing piece prepared in the second step into a closed container, heating the 3D printing piece in a water bath kettle with constant temperature to decompose urea contained in the 3D printing piece and release alkaline ammonia, carrying out polycondensation reaction between nano silica particles and boehmite particles in the 3D printing piece under the catalysis of the alkaline ammonia, and carrying out gel curing on the 3D printing piece to obtain a thermocured 3D printing piece;
the constant temperature range means that the external heating temperature is controlled to be 60-90 ℃;
and fourthly, supercritical drying to obtain the initial 3D printed silicon-aluminum oxide aerogel, wherein the method comprises the following steps:
and (3) soaking the thermocuring 3D printing piece prepared in the third step in absolute ethyl alcohol (the concentration is more than or equal to 99.5%) at a certain temperature, and removing impurities by solvent replacement for 3-8 times, wherein the replacement time is 6-36 hours each time. The thermally cured 3D print containing ethanol was then placed in CO2Drying in supercritical drying fluid to obtain initial 3D printed silicon-aluminum oxide aerogel;
the certain temperature is 25-80 ℃;
the CO is2The supercritical drying condition is that the temperature is 35-70 ℃ and the pressure is 8-15 MPa.
Fifthly, carrying out high-temperature heat treatment to obtain the 3D printed silicon-aluminum oxide ceramic aerogel, wherein the method comprises the following steps:
and (3) carrying out heat treatment on the initial 3D printed silicon-aluminum oxide aerogel prepared in the fourth step in a muffle furnace controlled by a certain program at a constant temperature for 2 hours, and naturally cooling to obtain the 3D printed silicon-aluminum oxide ceramic aerogel. The high-temperature heat treatment aims at realizing the conversion of boehmite in the initial 3D-printed silicon-aluminum oxide aerogel into gamma-phase alumina, and removing a small amount of organic polyvinyl alcohol, dry residual ethanol and a small amount of adsorbed water in the heat treatment process to obtain the 3D-printed silicon-aluminum oxide ceramic aerogel with the porous ceramic structure.
The certain program control means that the temperature rise rate of the muffle furnace is controlled to be 1-10 ℃/min;
the constant temperature refers to a steady-state heat treatment temperature reached by the muffle furnace after temperature rise through program control, and the selection range of the constant temperature is controlled to be 600-1100 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the urea in the first step of the invention serves as a temperature induction catalyst of the heat-curable silicon-aluminum oxide ceramic ink, when the temperature is close to or higher than 60 ℃, the urea can be automatically decomposed and release alkaline ammonia, and under the catalytic action of the alkaline ammonia, condensation polymerization reaction occurs between silica sol particles and boehmite particles in the ink, so that the heat curing molding of the silicon-aluminum oxide ceramic ink is realized. In the first step, urea is uniformly mixed in the silicon-aluminum oxide ceramic ink, when the external temperature meets the urea decomposition condition, the 3D printing piece with no matter the volume can be completely thermally cured theoretically, and the additive manufacturing of the silicon-aluminum oxide ceramic aerogel is not limited by the size requirement. Further, urea has a property of not decomposing at room temperature, and according to this property, storage of ink in a room temperature environment can be realized.
(2) In the first step of the invention, the nano silicon oxide powder and polyvinyl alcohol are added into the silicon-aluminum oxide ceramic ink to realize the adjustment of the rheological property of the ink, because the nano silicon oxide powder and the polyvinyl alcohol tend to form a stable and reversible hydrogen bond crosslinking network in the ink. Under the action of external force, the silicon-aluminum oxide ceramic ink shows a flow behavior of shear thinning, which ensures that the ink can be smoothly extruded out of a nozzle; after the external force action is removed, the ink has the solid characteristic, self-supporting forming can be realized after printing, and structural damage caused by gravity collapse is avoided.
(3) The 3D printing silicon-aluminum oxide ceramic aerogel prepared by the method has relatively low density and thermal conductivity. The third step of the thermosetting 3D print may be by supercritical CO2Drying to obtain the low-density 3D printing silicon-aluminum oxide ceramic aerogel with the density distribution range of 0.14-0.62 g-cm-3(ii) a The low density means that the interior of the 3D printed silicon-aluminum oxide ceramic aerogel has rich pore structures, so that the 3D printed silicon-aluminum oxide ceramic aerogel has low thermal conductivity, and the thermal conductivity ranges from 0.029 to 0.104 W.m-1·K-1The low density and low thermal conductivity further demonstrate that the inventive method can be used for additive manufacturing of silica alumina ceramic aerogels.
(4) By adopting the method, the 3D printing silicon-aluminum oxide ceramic aerogel with stable structure and high temperature resistance can be obtained. The fifth step of heat treatment of the initial 3D-printed silicon-aluminum oxide aerogel can realize partial sintering of silicon oxide in the aerogel and transformation of boehmite to gamma-phase alumina, so that the 3D-printed silicon-aluminum oxide ceramic aerogel presents a stable structureAnd (4) characteristics. The gas-phase silicon oxide has good sintering resistance, can effectively avoid collapse of an internal pore structure of the aerogel in the heat treatment process, which is the reason why the aerogel can keep high specific surface area after heat treatment, and after heat treatment, the specific surface area distribution range of the 3D printing silicon-aluminum oxide ceramic aerogel with different formulas is 172-308 m2·g-1The high-temperature specific surface area retention rate is 55-99%, and the relatively high specific surface area and specific surface area retention rate mean that the 3D printing silicon-aluminum oxide ceramic aerogel disclosed by the invention has excellent high-temperature resistance, and experiments prove that the 3D printing silicon-aluminum oxide ceramic aerogel disclosed by the invention can still keep a hollow porous structure after being calcined at 1100 ℃, and the structure and the shape of the aerogel are not damaged.
(5) By adopting the method, the 3D printed silicon-aluminum oxide ceramic aerogel with different surface precisions can be obtained. The 3D prints silicon-aluminum oxide ceramic aerogel and as thermal-insulated component, and accurate and closely assemble between the component just can reach high-efficient thermal-insulated effect. In the process of printing the silicon-aluminum oxide ceramic ink in the 3D mode in the second step, the surface precision of a 3D printing piece is directly influenced by the caliber of nozzles of different printers, and the smaller the caliber of the nozzles is, the more favorable the 3D printing silicon-aluminum oxide ceramic aerogel with high surface precision can be obtained. According to the invention, different printer nozzles within the range of 0.1-3 mm are selected for printing, so that 3D printing silicon-aluminum oxide ceramic aerogel with different surface accuracies can be obtained.
(6) The 3D printing silicon-aluminum oxide ceramic aerogel disclosed by the invention is rich in raw material source, low in price, simple in 3D printing method and strong in implementation, and urea serving as a temperature induction catalyst has the advantages of no toxicity and harmlessness.
Drawings
Fig. 1 is a flow chart of a preparation method of the 3D-printed silicon-aluminum oxide ceramic aerogel according to the invention.
FIG. 2 is a primary 3D-printed silica-alumina aerogel prepared in the fourth step of example 1. The additive manufacturing of the silicon-aluminum oxide aerogel printed in the initial state 3D adopts a nozzle with the diameter of 1.2mm to deposit ink, and a scaffold structure stacked layer by layer is formed by overlapping the ink.
Fig. 3 is a 3D printed silica alumina ceramic aerogel prepared in the fifth step of example 1 of the present invention. The 3D printed silicon-aluminum oxide ceramic aerogel can still keep a hollow porous scaffold structure after being subjected to heat treatment at 1100 ℃ for 2 hours.
Detailed Description
The invention is further illustrated by the following figures and examples. In the examples, the 3D printed silicon-aluminum oxide ceramic aerogel concerned by the present invention was mainly studied for density, thermal conductivity, specific surface area and high-temperature specific surface area retention. In the embodiment, the density of the 3D-printed silicon-aluminum oxide ceramic aerogel is obtained by calculating a volume and a mass, the thermal conductivity is tested by using a thermal conductivity constant instrument (Hotdisk), the specific surface area is obtained by calculating a nitrogen adsorption-desorption isotherm collected by a nitrogen adsorption device (Quantachrome) by using a BET theory, and the high-temperature specific surface area retention rate is obtained by calculating a ratio of the specific surface area of a sample with the same formula at different heat treatment temperatures to the specific surface area of the initial 3D-printed silicon-aluminum oxide aerogel.
In the process of preparing the 3D printing silicon-aluminum oxide ceramic aerogel, the density, the thermal conductivity, the specific surface area and the high-temperature specific surface area retention rate of the 3D printing silicon-aluminum oxide ceramic aerogel are obviously influenced by the using amounts of the aqueous silica sol and the aqueous aluminum sol in the first step and the heat treatment temperature in the fifth step, and other factors hardly influence the density, the thermal conductivity, the specific surface area and the high-temperature specific surface area retention rate of the 3D printing silicon-aluminum oxide ceramic aerogel concerned by the invention. The following discussion about the influence of 3 critical parameters of the amount of the aqueous silica sol, the amount of the aqueous alumina sol and the heat treatment temperature on the density, the thermal conductivity, the specific surface area and the high-temperature specific surface area retention rate of the 3D-printed silica-alumina oxide ceramic aerogel, and further illustrate the present invention by examples, and the scope of the present invention should not be construed as being limited to these examples.
As shown in fig. 1, preparative example 1 included the following steps:
firstly, preparing the heat-curable silicon-aluminum oxide ceramic ink, which comprises the following steps:
1.1 specific surface area of 400m2·g-1The gas-phase silica powder, 40 wt% of aqueous silica sol, 20 wt% of aqueous aluminum sol, polyvinyl alcohol, urea and water are mixed and stirred uniformly to prepare the primary mixed slurry. In the ink composition, the mass fractions of the gas-phase silica powder, the aqueous silica sol, the aqueous alumina sol, the polyvinyl alcohol, the urea and the water in the silicon-aluminum oxide ceramic ink are respectively 10, 30, 36, 1, 3 and 20.
1.2, placing the primarily mixed slurry in a centrifugal defoaming stirrer to stir for 3 minutes to obtain the silicon-aluminum oxide ceramic ink which is bubble-free, can be thermally cured and can be molded in a self-supporting way. In the preparation process, the revolution speed of the stirrer is controlled at 800rpm, and the rotation speed is controlled at 400 rpm;
and secondly, extruding the silicon-aluminum oxide ceramic ink for 3D printing to obtain a 3D printed piece, wherein the method comprises the following steps:
the method comprises the steps of packaging thermocurable silicon-aluminum oxide ceramic ink into a 3D printer bin, designing the structural shape of silicon-aluminum oxide ceramic aerogel by means of three-dimensional modeling software, selecting a nozzle with the caliber of 1.2mm, controlling the nozzle of a 3D printer to print on a two-dimensional plane at the movement speed of 15mm/s according to a printing path planned by a G code language, and after printing one layer of ink, automatically lifting the nozzle of the printer upwards according to the programming path, and printing the next layer until a 3D printed part is obtained;
thirdly, controlling temperature and performing thermocuring, wherein the method comprises the following steps:
placing the 3D printed part prepared in the second step into a closed container, heating the 3D printed part in a water bath kettle with the constant temperature of 60 ℃, and completely curing the 3D printed part in a gel manner after 6-8 hours to obtain a thermocured 3D printed part;
and fourthly, supercritical drying to obtain the initial 3D printed silicon-aluminum oxide aerogel, wherein the method comprises the following steps:
and (3) soaking the thermocuring 3D printing piece prepared in the third step in absolute ethyl alcohol (the concentration is more than or equal to 99.5%) at 50 ℃ for solvent replacement, and removing impurities by replacing for 5 times, wherein the replacement time is 24 hours each time. The impurity-removed thermally cured 3D print was then cured at 55 ℃ and 13MPa in CO2Drying in supercritical drying fluidAnd obtaining the initial 3D printing silicon-aluminum oxide aerogel. Fig. 2 is a primary 3D-printed silica-alumina aerogel with a complex scaffold structure, which is a hollowed-out porous structure formed by stacking ink tows, and has good structural integrity and shape fidelity, and the feasibility of obtaining the silica-alumina aerogel with a complex structural shape by using a 3D printing technology is proved.
Fifthly, carrying out high-temperature heat treatment to obtain the 3D printed silicon-aluminum oxide ceramic aerogel, wherein the method comprises the following steps:
and (3) heating the initial 3D printing silicon-aluminum oxide aerogel prepared in the fourth step to 1100 ℃ in a muffle furnace at the speed of 10 ℃/min, carrying out heat treatment at the constant 1100 ℃ for 2 hours, and naturally cooling along with the furnace to obtain the 3D printing silicon-aluminum oxide ceramic aerogel. The density of the 3D printed silicon-aluminum oxide ceramic aerogel is 0.35 g-cm-3The thermal conductivity is 0.083 W.m-1·K-1A specific surface area of 183m2·g-1. Fig. 3 is a 3D printed silicon-aluminum oxide ceramic aerogel obtained by subjecting the initial 3D printed silicon-aluminum oxide aerogel with a complex scaffold structure in fig. 2 to heat treatment at 1100 ℃ for 2 hours, and after the heat treatment, the aerogel still can keep a good hollow porous structure without structural and shape damage, thereby proving that the 3D printed silicon-aluminum oxide ceramic aerogel has good high temperature resistance.
In the first step of the invention, the density, the thermal conductivity, the specific surface area and the high-temperature specific surface area retention rate of the 3D printing silicon-aluminum oxide ceramic aerogel concerned by the invention are not influenced by regulating and controlling the dosage of the polyvinyl alcohol, the urea and the water within the required range; the use amount of polyvinyl alcohol and water only influences the self-supporting formability of a 3D printing piece, the use amount of urea only influences the curing rate of the silicon-aluminum oxide ceramic ink, the stirring time and the stirring rate of a centrifugal defoaming stirrer do not influence the density, the thermal conductivity, the specific surface area and the high-temperature specific surface area retention rate of the 3D printing silicon-aluminum oxide ceramic aerogel concerned by the invention, and the stirring time and the stirring rate only influence the defoaming degree of the silicon-aluminum oxide ceramic ink; in addition, the nano silicon oxide powders with different specific surface areas have almost no influence on the density and the thermal conductivity of the 3D printing silicon-aluminum oxide ceramic aerogel concerned by the invention, and the influences on the specific surface area and the high-temperature specific surface area retention rate are small and can be basically ignored. In the second step, the caliber size of the nozzle of the 3D printer only affects the surface precision of the 3D printing silicon-aluminum oxide ceramic aerogel, the movement speed of the nozzle of the 3D printer only affects the speed of the 3D printing process, and the density, the thermal conductivity, the specific surface area and the high-temperature specific surface area retention rate of the 3D printing silicon-aluminum oxide ceramic aerogel concerned by the invention are not affected. In the fourth step, the solvent replacement and drying conditions have no influence on the density, thermal conductivity, specific surface area and high-temperature specific surface area retention of the 3D printed silicon-aluminum oxide ceramic aerogel concerned by the present invention. In the fifth step, the muffle furnace temperature rise rate, solvent replacement and drying conditions have no influence on the density, thermal conductivity, specific surface area and high-temperature specific surface area retention rate of the 3D printing silicon-aluminum oxide ceramic aerogel concerned by the invention. Therefore, the above conditions have no influence on the density, the thermal conductivity, the specific surface area and the high-temperature specific surface area retention rate of the 3D-printed silicon-aluminum oxide ceramic, and the 3D-printed silicon-aluminum oxide ceramic aerogel with good performance can be obtained as long as the conditions are selected within the range described in the invention. The main factors influencing the density, the thermal conductivity, the specific surface area and the high-temperature specific surface area retention rate of the 3D printed silicon-aluminum oxide ceramic aerogel are the water-based silica sol and the water-based aluminum sol in the first step of the invention and the high-temperature heat treatment temperature in the fifth step of the invention.
The process parameters used in examples 2-27 are shown in Table 1. Observing the data in the table 1, the density range of the 3D printed silicon-aluminum oxide ceramic aerogel is 0.14-0.62 g-cm-3The thermal conductivity is 0.029-0.104 W.m-1·K-1The specific surface area is 172-308 m2·g-1The high-temperature specific surface area retention ratio is 55-99%, which indicates that the 3D printing silicon-aluminum oxide aerogel can still maintain the porous structure of the aerogel without being completely sintered in a high-temperature environment. The density of the 3D printed silicon-aluminum oxide ceramic aerogel is increased along with the increase of the use amount of the aqueous silica sol and the aqueous aluminum sol, so that the thermal conductivity shows similar change rules; with the rise of the heat treatment temperature, 3D printing of the silicon-aluminum oxide ceramic aerogelThe specific surface area and the high-temperature specific surface area retention rate tend to decrease slowly and then decrease rapidly.
According to the result of the embodiment of the invention, the 3D printing silicon-aluminum oxide ceramic aerogel prepared by the method has relatively single component, is non-toxic and harmless, has low density and low thermal conductivity, and can realize complex structure design and high-precision shape. In addition, the temperature-controlled thermal curing scheme can realize the macro additive manufacturing of the silicon-aluminum oxide ceramic aerogel, which has important significance for the industrial production of the silicon-aluminum oxide ceramic aerogel material.
The above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, but all changes that can be made by applying the principles of the present invention and performing non-inventive work on the basis of the principles shall fall within the scope of the present invention.
Table 13D preparation process parameters and related properties of printed silicon aluminum oxide ceramic aerogels
Claims (12)
1. A preparation method of an extruded 3D printed silicon-aluminum oxide ceramic aerogel is characterized by comprising the following steps:
firstly, preparing the heat-curable silicon-aluminum oxide ceramic ink, which comprises the following steps:
1.1 mixing nano silicon oxide powder, aqueous silica sol, aqueous aluminum sol, polyvinyl alcohol, urea and water, and uniformly stirring to prepare a primary mixed slurry; wherein, the nano silicon oxide powder is used as an ink thickener to adjust the rheological property of the ink; the polyvinyl alcohol is used as an ink cross-linking agent to assist the nano silicon oxide powder to adjust the rheological property of the ink; urea is used as a temperature induction catalyst, is decomposed to release alkaline ammonia, promotes the water-based silica sol and the water-based aluminum sol to perform polycondensation reaction, and realizes the thermal curing of the silicon-aluminum oxide ceramic ink; in the ink composition, the mass fractions of nano silicon oxide powder, aqueous silica sol, aqueous aluminum sol, polyvinyl alcohol, urea and water in the silicon-aluminum oxide ceramic ink are respectively 10, 15-55, 0-50, 0-5, 1-5 and 1-40;
1.2, placing the primarily mixed slurry in a centrifugal defoaming stirrer to be stirred to obtain the silicon-aluminum oxide ceramic ink which is bubble-free, can be thermally cured and can be molded in a self-supporting way;
and secondly, extruding the silicon-aluminum oxide ceramic ink for 3D printing to obtain a 3D printed piece, wherein the method comprises the following steps:
packaging silicon-aluminum oxide ceramic ink in a 3D printer bin, designing the structural shape of silicon-aluminum oxide ceramic aerogel by means of three-dimensional modeling software, selecting a 3D printer nozzle with a corresponding discharge port diameter according to the surface precision requirement, planning a printing path according to a numerical control programming language (namely G code), controlling the 3D printer nozzle to print on a two-dimensional plane, and after printing one layer of ink, automatically lifting the printer nozzle upwards according to the programming path, and printing the next layer until a 3D printed part is obtained;
thirdly, controlling temperature and performing thermocuring, wherein the method comprises the following steps:
placing the 3D printing piece prepared in the second step into a closed container, heating the 3D printing piece in a water bath kettle with constant temperature to decompose urea contained in the 3D printing piece and release alkaline ammonia, carrying out polycondensation reaction between nano silica particles and boehmite particles in the 3D printing piece under the catalysis of the alkaline ammonia, and carrying out gel curing on the 3D printing piece to obtain a thermocured 3D printing piece;
and fourthly, supercritical drying to obtain the initial 3D printed silicon-aluminum oxide aerogel, wherein the method comprises the following steps:
soaking the thermocuring 3D printing piece prepared in the third step in absolute ethyl alcohol, and removing impurities by solvent replacement; the thermally cured 3D print containing ethanol was then placed in CO2Drying in a supercritical drying fluid,obtaining initial 3D printing silicon-aluminum oxide aerogel;
fifthly, carrying out high-temperature heat treatment to obtain the 3D printed silicon-aluminum oxide ceramic aerogel, wherein the method comprises the following steps:
carrying out heat treatment on the initial 3D printed silicon-aluminum oxide aerogel prepared in the fourth step in a muffle furnace controlled by a program at a constant temperature for 2 hours, and naturally cooling to obtain a 3D printed silicon-aluminum oxide ceramic aerogel; the transformation of boehmite in the initial 3D-printed silicon-aluminum oxide aerogel to gamma-phase alumina is realized, and a small amount of organic polyvinyl alcohol, dry residual ethanol and a small amount of adsorbed water are removed in the heat treatment process, so that the 3D-printed silicon-aluminum oxide ceramic aerogel with the porous ceramic structure is obtained.
2. The preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel according to claim 1, wherein the nano silicon oxide powder in the step 1.1 has a specific surface area of 50-1000 m2·g-1The gas-phase silicon oxide powder of (2); the water-based silica sol is nano silica colloidal particle water dispersion with the solid content of 40 wt%; the aqueous alumina sol refers to a boehmite aqueous dispersion with a solid content of 20 wt%.
3. The preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel according to claim 1, wherein 1.2 the step of placing the initial mixed slurry in a centrifugal defoaming mixer for stirring is carried out for 1-30 minutes.
4. The preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel as claimed in claim 1, wherein in the 1.2 steps, the revolution speed of the stirrer is controlled to be 400-1000 rpm, and the rotation speed is controlled to be 100-800 rpm.
5. The preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel according to claim 1, wherein the diameter of a discharge hole of a nozzle of the 3D printer in the second step is 0.1-3.0 mm.
6. The preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel according to claim 1, wherein the printing speed of the nozzle of the 3D printer in the second step is controlled to be 0.2-40 mm/s when the nozzle of the 3D printer prints on a two-dimensional plane, namely the movement speed of the direct-writing printer in the x-axis and y-axis directions.
7. The preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel according to claim 1, wherein the constant temperature range in the third step is that the external heating temperature is controlled to be 60-90 ℃.
8. The preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel according to claim 1, wherein the concentration of the absolute ethyl alcohol in the fourth step is greater than or equal to 99.5%, and the temperature range of the absolute ethyl alcohol is 25-80 ℃.
9. The preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel according to claim 1, wherein the solvent replacement in the fourth step is performed 3-8 times, and each replacement time is 6-36 hours.
10. The method for preparing the extruded 3D printed silica alumina ceramic aerogel according to claim 1, wherein the fourth step is CO2The supercritical drying condition is that the temperature is 35-70 ℃ and the pressure is 8-15 Mpa.
11. The method of making an extruded 3D printed silica alumina ceramic aerogel according to claim 1, wherein the fourth step is comprised of amorphous silica and crystalline boehmite; wherein the mass fraction of the silicon oxide in the initial 3D-printed silicon-aluminum oxide aerogel is 60-100%, and the mass fraction of the boehmite in the initial 3D-printed silicon-aluminum oxide aerogel is 0-40%.
12. The preparation method of the extruded 3D printed silicon-aluminum oxide ceramic aerogel according to claim 1, wherein in the fifth step, the program control means that the temperature rise rate of the muffle furnace is controlled to be 1-10 ℃/min, the constant temperature means the steady-state heat treatment temperature reached by the muffle furnace after the temperature rise through the program control, and the selection range of the constant temperature is controlled to be 600-1100 ℃.
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