CN115504804A - Method for manufacturing SiOC porous heat insulation structure through continuous additive manufacturing - Google Patents
Method for manufacturing SiOC porous heat insulation structure through continuous additive manufacturing Download PDFInfo
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Abstract
The invention relates to a method for continuously and additively manufacturing an SiOC porous heat insulation structure, wherein the method for continuously and additively manufacturing the SiOC porous heat insulation structure comprises the following steps: mixing acrylate-based polysiloxane, a photoinitiator, a light blocking agent or an ultraviolet absorber to obtain photosensitive ceramic precursor slurry; placing the photosensitive ceramic precursor slurry in continuous photocuring equipment, and performing continuous photocuring treatment to obtain a ceramic precursor blank; and carrying out pyrolysis treatment on the ceramic precursor body to obtain the SiOC porous heat insulation structure. In addition, the invention also provides an SiOC porous heat insulation structure which is a bionic structure of the wall of the shell of the armored beetle and is prepared by adopting the continuous additive manufacturing method. The invention is mainly used for efficiently and quickly preparing the light high-efficiency heat-insulating device with the bionic structure.
Description
Technical Field
The invention relates to the technical field of porous materials, in particular to a method for continuously manufacturing an SiOC porous heat insulation structure in an additive mode.
Background
With the rapid development of machining technology and the increasing demand of light and efficient materials in the fields of aerospace, ship construction and the like, light porous materials become the key direction for the application of the materials in the fields. The porous material has good bearing capacity, energy absorption performance and buckling resistance, and can still maintain good strength when being subjected to strong compression load, thereby being widely applied.
The porous material has various forms, wherein the bionic porous material has the unique advantage that the structural performance can be accurately regulated and controlled, and the mechanical performance of the bionic porous material can be accurately regulated and controlled in modes of finite element simulation, prototype part trial production and the like. Typical bionic porous materials such as honeycomb structures are widely applied to positions such as doors and panels of landing gears of airplanes. However, the honeycomb structure has the problems of insufficient lateral pressure resistance and easy slippage and collapse of a honeycomb interlayer, and has a great optimization space. Even if the honeycomb structure has obvious defects, the honeycomb structure is still widely applied and is mainly limited by the processing mode, and the traditional lightweight design is mainly realized by bending, brazing and the like, so that the bionic structure with a complex shape is difficult to prepare. With the continuous development of additive manufacturing technology, a plurality of high-efficiency bionic structures such as a dot matrix structure, a coleoptera structure, a cuttlefish bone structure and the like are continuously and practically applied, and the superiority of various bionic structures is also proved.
However, most of the conventional additive manufacturing techniques adopt a layer-by-layer solidification method. After each layer is solidified, the material is refilled by lifting, powder spreading and other modes, and is solidified again to form connection with the last solidified layer. The process of repeatedly lifting or spreading the powder greatly reduces the preparation efficiency, so that the practical application of the light and efficient bionic structure is greatly limited.
At present, for a bionic structure with good heat insulation performance and excellent light weight and high efficiency, the traditional processing technology is difficult to realize the complex structure, and the traditional additive manufacturing technology has the problem of low preparation efficiency.
Disclosure of Invention
In view of the above, the present invention provides a method for continuously additive manufacturing a SiOC porous thermal insulation structure, and mainly aims to efficiently and rapidly prepare a biomimetic structure having good thermal insulation performance and excellent lightweight and high efficiency characteristics.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a method for continuously additive manufacturing an SiOC porous thermal insulation structure, including the following steps:
preparing photosensitive ceramic precursor slurry: mixing acrylate-based polysiloxane, a photoinitiator, a light blocking agent or an ultraviolet absorber to obtain photosensitive ceramic precursor slurry; wherein the content of the first and second substances, the content of the photoinitiator in the photosensitive ceramic precursor slurry is 0.1-5wt%, and the content of the light blocking agent or ultraviolet absorber is 0.1-5wt%; preferably, the acrylate-based polysiloxane has 2 or more acrylate functional groups, preferably 5 or more functional groups; preferably, the molecular weight of the acrylate-based polysiloxane is 100-30000, preferably 200-10000; preferably, the viscosity of the acrylate-based polysiloxane is 20 to 5000cps, preferably 20 to 2000cps; preferably, the viscosity of the photosensitive ceramic precursor slurry is 20 to 5000cps, preferably 20 to 2000cps;
the method comprises the following steps of: placing the photosensitive ceramic precursor slurry in continuous photocuring equipment, and performing continuous photocuring treatment to obtain a ceramic precursor blank;
pyrolysis treatment: and carrying out pyrolysis treatment on the ceramic precursor body to obtain the SiOC porous heat insulation structure.
Preferably, before the preparation of the photosensitive ceramic precursor slurry, the method further comprises:
preparation of acrylate-based polysiloxane: under an alkaline environment, carrying out a ring-opening reaction on epoxy siloxane and acrylic acid to obtain acrylate-based polysiloxane;
preferably, after the epoxy siloxane and the acrylic acid are mixed, the organic base and the polymerization inhibitor are added into the mixture, and the mixture is obtained after uniform mixing treatment; reacting the mixture at a set temperature for a set time to obtain acrylate-based polysiloxane;
preferably, in said mixture: the content of the organic alkali is 1 to 5 weight percent, and the content of the polymerization inhibitor is 0.5 to 3 weight percent;
further preferably, the set temperature is 60-120 ℃, and the set time is 6-24h.
Further preferably, the molar ratio of the epoxy siloxane to acrylic acid is (10n; wherein n is the number of functional groups of the epoxy siloxane;
further preferably, the uniformly mixing treatment mode is one or more of a magnetic stirring mode of 300-900rpm, an ultrasonic dispersion mode of 10-100kHz and a heating and stirring mode of 50-200 ℃;
further preferably, the mixture is placed in a reaction vessel, and a condensing device is arranged on the reaction vessel; and (3) placing the reaction vessel on a heating device, and reacting the mixture at a set temperature for a set time to obtain the acrylate-based polysiloxane.
Preferably, the epoxy siloxane is multifunctional epoxy siloxane or its composition, wherein the average functionality is greater than or equal to 2, preferably greater than or equal to 5.
Preferably, the organic base is one or more of diisopropylethylamine, triethylenediamine, tetramethylethylenediamine, triethylamine, diazabicyclo and the like.
Preferably, the polymerization inhibitor component is one or more of 2,6-tert-butyl-p-cresol, tea polyphenol, tert-butyl-p-hydroxyanisole, tert-butyl hydroquinone and other compounds.
Preferably, the acrylate-based polysiloxane is multifunctional acrylate-based polysiloxane or a composition thereof, wherein the average functionality is more than or equal to 2, preferably more than or equal to 5.
Preferably, the photoinitiator is one or more of TPO free radical type initiator, 819 free radical type initiator and TPO-L free radical type initiator.
Preferably, the ultraviolet absorbent is one or more of Sudan I ultraviolet absorbent, methyl red ultraviolet absorbent, methyl orange ultraviolet absorbent and carotene ultraviolet absorbent.
Preferably, the light blocking agent is OB + light blocking agent, and the components are as follows: 5-bis- (5-tert-butyl-2-benzoxazolyl) thiophene.
Preferably, the acrylate-based polysiloxane is selected from any one or more of the following: hyperbranched polysiloxanes TEGO RC 706, TEGO RC 711, TEGO RC 715, TEGO RC 722 from Germany British chemical company; x-62-7661, X-62-7989, KF2005 of Japan shin-Etsu chemical Co; acrylate-based polysiloxanes, TEGO RC 902, TEGO RC 922 from British chemical, germany; x-62-7662 and X-62-7629 of Japan shin-Etsu chemical Co.
Preferably, in the continuous additive manufacturing step: and placing the photosensitive ceramic precursor slurry in a slurry tank of continuous photocuring equipment, and introducing oxygen to the bottom of the slurry tank to ensure that the oxygen pressure in the photosensitive ceramic precursor slurry is 0.005-0.02bar in the continuous photocuring treatment.
Preferably, in the continuous additive manufacturing step: the light curing equipment is continuous light curing ceramic additive manufacturing equipment; preferably, the parameter settings are as follows: the thickness of the layer is set to 1-300 μm, and the exposure intensity is set to 1-100mW/cm 2 The exposure time is set to 0.5-30s, and the speed is set to 0.1-300mm/min.
Preferably, in the step of pyrolysis treatment: and heating the ceramic precursor body to 800-1200 ℃ in an inert atmosphere, preserving the heat for 0.5-10h at the temperature of 800-1200 ℃, and then cooling to room temperature to obtain the SiOC porous heat insulation structure.
Preferably, the inert atmosphere is argon.
Preferably, the heating rate of the ceramic precursor body when the temperature is increased to 800-1200 ℃ is 1-10 ℃/min.
On the other hand, the embodiment of the invention provides an SiOC porous heat insulation structure, wherein the SiOC porous heat insulation structure is a bionic structure imitating the wall of a deilidium ferrugineum shell; wherein the SiOC porous heat insulation structure is prepared by the continuous additive manufacturing method of the SiOC porous heat insulation structure. The bionic structure of the shell of the imitated siderite beetle has relatively higher mechanical strength. The SiOC ceramics used have a relatively low thermal conductivity, which, in combination, result in a lighter, more excellent thermal insulation and a final part with sufficient mechanical properties.
Preferably, the bionic structure of the shell wall of the deilidoxime pseudosiderobinii is an integrated structure; wherein, the bionic structure of imitative indisputable beetle shell wall includes:
a first panel;
the second panel is opposite to the first panel;
the core structure comprises a plurality of hollow cylindrical structures, wherein the hollow cylindrical structures are arranged between the first panel and the second panel, and any two adjacent hollow cylindrical structures are connected; the two ends of the hollow cylindrical structure are open, and the cylindrical outer wall of the hollow cylindrical structure is provided with a first part and a second part which are oppositely arranged; wherein the first portion meets the first panel and the second portion meets the second panel;
preferably, the outer wall of the hollow cylindrical structure further comprises a third part and a fourth part which are oppositely arranged; the third part and the fourth part are both provided with connecting plates, and the connecting plates are parallel to the first panel and the second panel; wherein any two adjacent hollow cylindrical structures are connected through a connecting plate.
Preferably, the thickness H of the first panel is 1-10mm, the maximum length a of the opening of the hollow cylindrical structure in the direction parallel to the first panel is 3-30mm, the maximum length H of the opening of the hollow cylindrical structure in the direction perpendicular to the first panel is 3-50mm, and the shortest distance B between the outer walls of two adjacent hollow cylindrical structures is 1-10mm. Preferably, the total length and width of the SiOC porous heat insulation structure is 20-300mm, and the thickness is 5-50mm.
Compared with the prior art, the method for manufacturing the SiOC porous heat insulation structure by the continuous additive has the following beneficial effects:
on one hand, the embodiment of the invention provides a method for continuously manufacturing an SiOC porous heat insulation structure in an additive manner, which firstly provides that acrylate-based polysiloxane is used as a main raw material and is mixed with a photoinitiator and an ultraviolet absorber (the ultraviolet absorber can also be replaced by a photo-blocker) to prepare special photosensitive ceramic precursor slurry, and the special photosensitive ceramic precursor slurry has the advantages of fast curing, high curing depth, low critical exposure intensity and good fluidity, can be quickly backfilled in the continuous photo-curing process, and thus realizes the continuous additive manufacturing of ultra-fast sample pieces with the thickness of more than 10 mm/min; meanwhile, due to the use of the photosensitive ceramic precursor slurry, the finally prepared SiOC porous heat-insulating structure belongs to polymer derived ceramic, and the polymer derived ceramic has excellent performance. In summary, the continuous additive manufacturing method of the SiOC porous thermal insulation structure provided by the embodiment of the invention can efficiently and rapidly prepare the biomimetic structure with good thermal insulation performance and excellent light weight and high efficiency characteristics.
On the other hand, the embodiment of the invention provides an SiOC porous heat insulation structure, which belongs to a light porous structure, is inspired by a deironium siderite beetle shell, mainly comprises a core structure similar to a phi shape and an upper panel and a lower panel, and is called as a bionic structure of the wall of the deironium siderite beetle shell, and the structure has good mechanical strength and simultaneously ensures high porosity of more than 80 percent. On the basis, the SiOC porous heat insulation structure is prepared by the continuous additive manufacturing method of the SiOC porous heat insulation structure, so that the embodiment of the invention realizes the rapid and efficient preparation of the bionic structure of the shell wall of the armored beetle, solves the problems of difficult preparation, low preparation efficiency and low strength of a sample piece of complex bionic porous ceramic, has good mechanical property and heat insulation property, greatly improves the precision of the sample piece, reduces the surface roughness and has larger practical application value.
In summary, the method for continuously additive manufacturing the SiOC porous heat insulation structure provided by the embodiment of the present invention has the following advantages: the SiOC porous heat insulation structure (bionic structure of the shell wall of the armored beetle) has excellent mechanical strength, good heat insulation performance and extremely high porosity, and the used material has low density, so that the SiOC porous heat insulation structure has very low structural density and has very positive effects in the application fields of aerospace, ship transportation, vehicle engineering and the like. In addition, the continuous additive manufacturing method of the SiOC porous heat insulation structure can (1) control the surface appearance and the surface roughness of a sample piece by controlling the layering thickness of software; (2) The preparation speed and precision of the sample piece can be controlled by regulating and controlling parameters; (3) By controlling the types of raw materials, the polysiloxane material modified by the same acrylate group with various functionalities can be synthesized. Acrylate-based polysiloxane materials with different functionalities are matched with each other, so that ceramic precursor blanks with different hardness after curing can be obtained; (4) The adopted continuous additive manufacturing method has the advantages of low price of raw materials, easy acquisition and high localization degree, and is beneficial to large-scale synthesis and sample piece production.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic view of a SiOC porous thermal insulation structure;
FIG. 2 is a schematic size diagram of an SiOC porous thermal insulation structure;
FIG. 3 is a diagram of a ceramic precursor body prepared according to an embodiment of the present invention;
FIG. 4 is a schematic representation of a SiOC porous thermal insulation structure prepared in accordance with an embodiment of the present invention;
FIG. 5 is a graph showing the results of the thermal insulation performance of the SiOC porous thermal insulation structure of example 1;
FIG. 6 is a graph showing the results of mechanical properties of the SiOC porous heat insulating structure in example 1.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The polymer-derived ceramic has low density and lower thermal conductivity, and can be rapidly manufactured by the DLP photocuring technology, which can perfectly solve the problems in the background art. In addition, ultra-high precision material molding can be achieved by a more efficient continuous photo-curing manufacturing technique. The ceramic precursor material has the unique advantages of quick curing, good fluidity, high manufacturing precision and the like, and meanwhile, after the ceramic precursor material is pyrolyzed into ceramic, the ceramic precursor material has excellent mechanical strength and heat-insulating property, and has wide application prospect as a light and high-efficiency porous heat-insulating material.
For a bionic structure with good heat insulation performance and excellent light weight and high efficiency, the traditional processing technology is difficult to realize the complex structure, and the efficiency of the common additive manufacturing technology is too low. Based on the technical problem, the invention provides a continuous additive manufacturing technology, which can improve the preparation efficiency by more than 10 times so as to realize the efficient and rapid preparation of a complex porous heat-insulation bionic structure. However, there is a technical problem in that a special paste needs to be prepared, and the functional groups of the components of such a paste need to have a certain oxygen inhibition effect, thereby realizing a continuous photo-curing process.
To sum up, the embodiment of the invention provides a method for continuously manufacturing an SiOC porous heat insulation structure in an additive manner, and the specific scheme is as follows:
on one hand, the embodiment of the invention provides a continuous additive manufacturing method of an SiOC porous heat insulation structure, which mainly comprises the following steps:
preparing photosensitive ceramic precursor slurry: mixing acrylate-based polysiloxane, a photoinitiator and an ultraviolet absorber (or replacing the ultraviolet absorber with a photo-blocker) to obtain photosensitive ceramic precursor slurry; wherein, the content of the photoinitiator in the photosensitive ceramic precursor slurry is 0.1-5wt%, and the content of the ultraviolet light absorber (or light blocking agent) is 0.1-5wt%.
The invention firstly provides the preparation of photosensitive ceramic precursor slurry by using acrylate-based polysiloxane as a raw material, which is a key for realizing continuous photocuring preparation. The acrylate-based polysiloxane is characterized by not polymerizing when the oxygen concentration is less than a certain value. Therefore, in the subsequent continuous additive manufacturing steps, only oxygen needs to be introduced to the bottom of the tank filled with the slurry, so that the oxygen pressure in the photosensitive ceramic precursor slurry is 0.005-0.02bar, and the continuous polymerization of the slurry is ensured to be carried out by taking the interface of the oxygen concentration threshold as a limit.
Wherein, the acrylate-based polysiloxane is prepared by the ring-opening reaction of epoxy polysiloxane and acrylic acid in an alkaline environment. Preferably, the acrylate-based polysiloxane is prepared by ring-opening epoxy polysiloxane and acrylic acid with different functional groups to obtain acrylate-based polysiloxane with different functionalities.
Preferably, the invention also provides a simple synthesis method for obtaining the acrylate-based polysiloxane with different functionalities, which comprises the following steps:
1) The epoxysiloxane was mixed thoroughly with acrylic acid to give a solution. Wherein the ratio of epoxysilicone to acrylic acid is related to the number of functional groups of the epoxysilicone. When the number of functional groups of the epoxysiloxane is n, the molar ratio of mixing with acrylic acid is 10n.
The epoxysilicone is a multifunctional epoxysilicone or a combination thereof, wherein the average functionality is more than or equal to 2, preferably more than or equal to 5.
2) Adding organic alkali and polymerization inhibitor into the solution, and fully and uniformly mixing to obtain a mixture. Preferably, the mixing mode is one or more of magnetic stirring at 300-900rpm, ultrasonic dispersion at 10-100kHz and heating and stirring at 50-200 ℃.
Preferably, the organic base is one or more of diisopropylethylamine, triethylenediamine, tetramethylethylenediamine, triethylamine, diazabicyclo and the like. Preferably, the polymerization inhibitor component is one or more of 2,6-tert-butyl-p-cresol, tea polyphenol, tert-butyl-p-hydroxyanisole, tert-butyl hydroquinone and other compounds.
3) The mixture was placed in an erlenmeyer flask equipped with a condensing unit. And (3) putting the whole device into a water bath kettle, heating for a period of time at a specific temperature, taking out, and cooling at room temperature to obtain the acrylate-based polysiloxane. Preferably, the reaction device can be a large reaction kettle from a 250ml conical flask to more than 20L. Preferably, the condensing means is water cooled.
And (3) fully and uniformly mixing the synthesized acrylate-based polysiloxane with a certain proportion of photoinitiator and ultraviolet absorber to obtain the ceramic precursor slurry. Preferably, the photoinitiator is one or more of free radical initiators such as TPO, 819, TPO-L and the like. Preferably, the ultraviolet absorbent is one or more of Sudan I, methyl red, methyl orange, carotene, etc.
The acrylate-based polysiloxane has more than 2 acrylate functional groups, preferably acrylate-based polysiloxane with more than 5 or 5 functional groups; preferably, the molecular weight of the acrylate-based polysiloxane is 100-30000, preferably 200-10000; preferably, the viscosity of the acrylate-based polysiloxane is 20 to 5000cps, preferably 20 to 2000cps.
The acrylate-based polysiloxane is multifunctional acrylate-based polysiloxane or a composition thereof, wherein the average functionality is more than or equal to 2, preferably more than or equal to 5.
In addition, the acrylate-based polysiloxane can be prepared by self-made method, and can also be selected from any one or more of the following grades: hyperbranched polysiloxane TEGO RC 706, TEGO RC 711, TEGO RC 715 and TEGO RC 722 from British chemical Co, germany; x-62-7661, X-62-7989, KF2005 of Japan shin-Etsu chemical Co; acrylate-based polysiloxanes, TEGO RC 902, TEGO RC 922 from British chemical, germany; x-62-7662 and X-62-7629 of Japan shin-Etsu chemical Co.
The method comprises the following steps of: and placing the photosensitive ceramic precursor slurry in continuous photocuring equipment, and performing continuous photocuring treatment to obtain a ceramic precursor blank.
In this step: and placing the ceramic precursor slurry in continuous photocuring equipment, and performing continuous photocuring to obtain a ceramic precursor blank. Preferably, the continuous light curing apparatus is an off-the-market continuous additive manufacturing apparatus, numbered IMR-Xinglab. Preferably, the parameters are: the layer thickness is set to 0.1-300 μm, and the exposure intensity is set to 1-100mW/cm 2 The exposure time is set to 0.5-30s, and the speed is set to 0.1-300mm/min.
In addition, in the step, oxygen is introduced to the bottom of the tank for containing the photosensitive ceramic precursor slurry, and the oxygen forms a concentration gradient towards the inside of the photosensitive ceramic precursor slurry, so that the photosensitive ceramic precursor slurry can be continuously polymerized by taking the interface of the oxygen concentration threshold as a limit.
And (3) pyrolysis treatment: and carrying out pyrolysis treatment on the ceramic precursor body to obtain the SiOC porous heat insulation structure.
In the step, the ceramic precursor body is placed in an atmosphere furnace, and the SiOC light porous heat insulation structure is prepared in an inert atmosphere. Preferably, the pyrolysis atmosphere is argon. Preferably, the heating rate during pyrolysis is 1-10 ℃/min, the pyrolysis temperature is 800-1200 ℃, and the heat preservation time is 0.5-10h.
The continuous additive manufacturing method of the SiOC porous heat insulation structure provided by the embodiment of the invention can realize continuous photocuring preparation of the SiOC porous heat insulation structure, so that a complex porous heat insulation bionic structure can be efficiently and quickly prepared.
On the other hand, the embodiment of the invention provides an SiOC porous heat insulation structure, wherein the SiOC porous heat insulation structure is a bionic structure of a wall of an armored beetle shell (the specific structure is shown in figures 1-4); the SiOC porous heat insulation structure is prepared by the method for manufacturing the SiOC porous heat insulation structure by continuous additive manufacturing.
As shown in fig. 1. The bionic structure of the shell wall of the armored rope beetle is composed of a core structure of the armored rope beetle shell, a first panel 1 and a second panel 2. Wherein the core structure is similar to a phi shape, which is similar to the shell structure of the Dendrolimus punctatus.
Specifically, referring to fig. 1, the bionic structure of the shell wall of the deilidoxime pseudosidestoides proposed in this embodiment is an integrated structure; the bionic structure of the wall of the armored beetle shell comprises a first panel 1, a second panel 2 and a core structure. Wherein the first panel 1 and the second panel 2 are oppositely arranged. The core structure comprises a plurality of hollow cylindrical structures 3, wherein the hollow cylindrical structures 3 are arranged between the first panel 1 and the second panel 2, and any two adjacent hollow cylindrical structures 3 are connected; wherein, two ends of the hollow cylindrical structure 3 are open, and the cylindrical outer wall of the hollow cylindrical structure 3 is provided with a first part and a second part which are oppositely arranged; wherein a first portion meets the first panel 1 and a second portion meets the second panel 2. The outer wall of the hollow cylindrical structure 3 also comprises a third part and a fourth part which are oppositely arranged; the third part and the fourth part are both provided with connecting plates 31, and the connecting plates 31 are parallel to the first panel 1 and the second panel 2; any two adjacent hollow cylindrical structures are connected through a connecting plate 31.
Preferably, as shown in fig. 2, the thickness H of the first panel 1 is 1-10mm, the maximum length a of the opening of the hollow cylindrical structure 3 in the direction parallel to the first panel 1 is 3-30mm, the maximum length H of the opening of the hollow cylindrical structure 3 in the direction perpendicular to the first panel 1 is 3-50mm, and the shortest distance B between the cylinder outer walls of two adjacent hollow cylindrical structures 3 is 1-10mm.
In summary, the SiOC lightweight porous thermal insulation structure provided in the embodiments of the present invention has the advantages of lightweight, high efficiency, high thermal insulation performance, high temperature resistance, and thermal shock resistance, and is mainly applied to thermal insulation materials in special environments such as high temperature resistance and acid corrosion resistance. The preparation method has the characteristics of high efficiency, high precision and low surface roughness, and is mainly applied to the field of continuous photocuring ceramic materials.
The invention is further illustrated below by way of examples:
example 1
The preparation of an SiOC porous thermal insulation structure in this embodiment mainly includes the following steps:
1) Establishing an SiOC porous heat insulation structure model: the characteristic size of the shell of the Dendrolimus punctatus is obtained according to an optical photograph and an SEM microscopic photograph of the shell of the Dendrolimus punctatus, and a model is drawn in Solidworks drawing software (the model is shown in figures 1 and 2). Where, a =10mm, b =5mm, h =1mm.
2) Synthesizing and preparing photosensitive ceramic precursor slurry: 100g of trifunctional epoxy siloxane (IOTA 105-3) and 10g of acrylic acid are weighed and mixed evenly by ultrasound for 30 min. Subsequently, 3g of triethylamine and 1g of tert-butylhydroquinone were added thereto, and mixed by sonication for 30min to obtain a mixture. The mixture was placed in a 250mL Erlenmeyer flask, a condenser tube was inserted, and a water pump was connected to the condenser tube to form a loop. Putting the conical flask into a water bath kettle, heating at the temperature of 90 ℃ for 24h, and then taking out and cooling to room temperature to obtain the acrylate-based polysiloxane. The viscosity of the resulting acrylate-based polysiloxane was 186cps.
3) Adding 1.5g of TPO-L and 0.3g of light blocking agent OB + into acrylate polysiloxane, and uniformly mixing by ultrasonic treatment for 30min to obtain photosensitive ceramic precursor slurry. Wherein, in the photosensitive ceramic precursor slurry, the mass fraction of TPO-L is 3.75wt%, and the mass fraction of the light blocker OB + is 0.75wt%. The viscosity of the obtained photosensitive ceramic precursor slurry was 181cps.
4) Continuous additive manufacturing: and placing the slurry into a slurry tank of continuous additive manufacturing equipment, and introducing oxygen into the bottom of the slurry tank to ensure that the oxygen pressure in the photosensitive ceramic precursor slurry is 0.005-0.02bar in the continuous photocuring treatment. The setting parameters are as follows: the thickness of the layer was set to 50 μm, and the exposure intensity was set to 20mW/cm 2 The exposure time was set to 3s and the speed was set to 5mm/min. After the preparation is completed, the residual solution on the surface is dried by an air gun, then the mixture is placed into isopropanol for ultrasonic cleaning for 5min, and after air drying, a ceramic precursor body (namely, a ceramic precursor body) of the shell of the Trypanosoma ferrugineum is obtained, and the figure 3 is shown.
5) And (3) pyrolyzing into porcelain: putting the ceramic precursor body (namely the ceramic precursor body) of the shell of the armored beetle into an atmosphere furnace, heating to 1000 ℃ at 1 ℃/min under the flowing argon atmosphere, then preserving the temperature for 1h, and then cooling to room temperature at 5 ℃/min to obtain the SiOC porous heat insulation structure, wherein the surface of the SiOC porous heat insulation structure is black (see figure 4).
The thermal insulation performance test was performed on the SiOC porous thermal insulation structure prepared in this example: the sample was placed in a through-hole refractory brick, the gap was tightly filled with heat-insulating cotton, and then the refractory brick was placed in a muffle furnace having a furnace temperature of 800 ℃ with the sample piece side facing the inside of the muffle furnace and the sample piece side facing the outside of the muffle furnace. And measuring the outside temperature of the sample piece by using an infrared temperature measuring gun, drawing a curve and calculating the heat conductivity coefficient of the curve. The surface appearance of the sample is not changed before and after the heat insulation performance test. The thermal insulation performance curve is shown in fig. 5. As can be seen from fig. 5, the SiOC porous thermal insulation structure prepared in this example has excellent thermal insulation properties.
The mechanical property test of the SiOC porous heat insulation structure prepared in this example was performed: the sample was placed in a universal tester and a displacement load was applied at a rate of 0.5mm/min to obtain a stress-strain curve, as shown in fig. 6. As can be seen from fig. 6, the SiOC porous thermal insulation structure prepared in this example has excellent mechanical properties.
Example 2
The preparation of an SiOC porous thermal insulation structure in this embodiment mainly includes the following steps:
1) Establishing an SiOC porous heat insulation structure model: and (3) acquiring the characteristic size of the shell of the Dendrolimus punctatus according to the optical picture and the SEM microscopic picture of the shell of the Dendrolimus punctatus, and drawing a model in Solidworks drawing software. Wherein, A =30mm, B =2mm, H =30mm, h =1mm.
2) Synthesizing and preparing photosensitive ceramic precursor slurry: 100g of trifunctional epoxy siloxane (IOTA 105-3) and 10g of acrylic acid are weighed and mixed evenly by ultrasound for 30 min. Subsequently, 3g of triethylamine and 1g of tert-butylhydroquinone were added thereto, and mixed by sonication for 30min to obtain a mixture. The mixture was placed in a 250mL conical flask, a condenser tube was inserted, and a water pump was connected to the condenser tube to form a loop. Putting the conical flask into a water bath kettle, heating at the temperature of 90 ℃ for 24h, and then taking out and cooling to room temperature to obtain the acrylate-based polysiloxane. The viscosity of the resulting acrylate-based polysiloxane was 1121cps.
3) To the acrylate-based polysiloxane was added 1.5g of TPO-L,0.3g of a light blocker OB + (ingredient: 2.5-bis- (5-tert-butyl-2-benzoxazolyl) thiophene), and uniformly mixing by ultrasonic for 30min to obtain photosensitive ceramic precursor slurry. Wherein, in the photosensitive ceramic precursor slurry, the mass fraction of TPO-L is 3.75wt%, and the mass fraction of the light blocker OB + is 0.75wt%. The viscosity of the photosensitive ceramic precursor slurry was 1081cps.
4) Continuous additive manufacturing: and placing the slurry into a slurry tank in continuous additive manufacturing equipment, and introducing oxygen into the bottom of the slurry tank to ensure that the oxygen pressure in the photosensitive ceramic precursor slurry is 0.005-0.02bar in the continuous photocuring treatment. The set parameters are as follows: the thickness of the layer was set to 50 μm, and the exposure intensity was set to 20mW/cm 2 The exposure time was set to 3s and the speed was set to 5mm/min. And after the preparation is finished, blowing the residual solution on the surface by using an air gun, then putting the blow-dried solution into isopropanol for ultrasonic cleaning for 5min, and airing to obtain the ceramic precursor body (namely the ceramic precursor body) of the shell of the Trypanosoma ferrugineum.
5) And (3) pyrolyzing into porcelain: putting the ceramic precursor body (namely the ceramic precursor body) of the shell of the armored beetle into an atmosphere furnace, heating to 1000 ℃ at 1 ℃/min under the flowing argon atmosphere, then preserving the heat for 1h, and then cooling to room temperature at 5 ℃/min to obtain the SiOC porous heat insulation structure, wherein the surface of the SiOC porous heat insulation structure is black.
Through tests, the continuous and efficient additive manufacturing of the SiOC porous heat insulation structure can be realized, the preparation speed of the SiOC porous heat insulation structure is far higher than that of the traditional ultraviolet light projection forming process in the comparative example 1, and the performance of the porous heat insulation structure obtained through pyrolysis is excellent.
Example 3
The preparation of an SiOC porous thermal insulation structure in this embodiment mainly includes the following steps:
1) Establishing an SiOC porous heat insulation structure model: and (3) acquiring the characteristic dimension of the shell of the Dendrolimus punctatus according to the optical picture and the SEM microscopic picture of the shell of the Dendrolimus punctatus, and drawing a model in Solidworks drawing software (the model is shown in figures 1 and 2). Wherein, A =20mm, B =8mm, H =10mm, h =2mm.
2) Weighing hyperbranched acrylate-based polysiloxane TEGO RC-711 100g with the viscosity of 392cps, adding 3g of TPO and 1.5g of methyl red, and ultrasonically mixing for 30min to obtain the photosensitive ceramic precursor slurry. The viscosity of the photosensitive ceramic precursor slurry was 373cps.
3) Continuous additive manufacturing: and placing the slurry into a slurry tank in continuous additive manufacturing equipment, and introducing oxygen into the bottom of the slurry tank to ensure that the oxygen pressure in the photosensitive ceramic precursor slurry is 0.005-0.02bar in the continuous photocuring treatment. The set parameters are as follows: the thickness of the layer was set to 10 μm, and the exposure intensity was set to 25mW/cm 2 The exposure time was set to 1s and the speed was set to 8mm/min. After the preparation is finished, the residual solution on the surface is dried by an air gun, then the mixture is placed into isopropanol to be ultrasonically cleaned for 5min, and after the mixture is dried, a ceramic precursor body (namely a ceramic precursor body) imitating the shell of the deilidoni ferrugineum is obtained.
4) And (3) pyrolyzing into porcelain: putting the ceramic precursor body (namely the ceramic precursor body) of the shell of the armored beetle into an atmosphere furnace, heating to 1000 ℃ at 1 ℃/min under the flowing argon atmosphere, then preserving heat for 1h, and then cooling to room temperature at 1 ℃/min to obtain the SiOC porous heat insulation structure, wherein the surface of the SiOC porous heat insulation structure is black.
Tests show that the continuous and efficient additive manufacturing of the SiOC porous heat insulation structure can be realized, the preparation speed of the SiOC porous heat insulation structure is far higher than that of the traditional ultraviolet light projection forming process in the comparative example 1, and the performance of the porous heat insulation structure obtained through pyrolysis is excellent.
Example 4
The preparation of an SiOC porous thermal insulation structure in this embodiment mainly includes the following steps:
1) Establishing an SiOC porous heat insulation structure model: and (3) acquiring the characteristic dimension of the shell of the Dendrolimus punctatus according to the optical picture and the SEM microscopic picture of the shell of the Dendrolimus punctatus, and drawing a model in Solidworks drawing software (the model is shown in figures 1 and 2). Wherein, A =20mm, B =8mm, H =10mm, h =2mm.
2) Taking acrylic ester-based polysiloxane X-62-7662 100g, the viscosity is 2250cps. Adding 4.5g of TPO and 2g of methyl orange, and uniformly mixing by ultrasonic treatment for 30min to obtain photosensitive ceramic precursor slurry. The viscosity of the photosensitive ceramic precursor slurry was 2188cps.
3) Continuous additive manufacturing: and placing the slurry into a slurry tank in continuous additive manufacturing equipment, and introducing oxygen into the bottom of the slurry tank to ensure that the oxygen pressure in the photosensitive ceramic precursor slurry is 0.005-0.02bar in the continuous photocuring treatment. The setting parameters are as follows: the thickness of the layer was set to 10 μm, and the exposure intensity was set to 25mW/cm 2 The exposure time was set to 1s and the speed was set to 8mm/min. After the preparation is finished, the residual solution on the surface is dried by an air gun, then the mixture is placed into isopropanol to be ultrasonically cleaned for 5min, and after the mixture is dried, a ceramic precursor body (namely a ceramic precursor body) imitating the shell of the deilidoni ferrugineum is obtained.
4) And (3) pyrolyzing into porcelain: putting the ceramic precursor body (namely the ceramic precursor body) of the shell of the armored beetle into an atmosphere furnace, heating to 1000 ℃ at 1 ℃/min under the flowing argon atmosphere, then preserving the heat for 1h, and then cooling to room temperature at 1 ℃/min to obtain the SiOC porous heat insulation structure, wherein the surface of the SiOC porous heat insulation structure is black.
Through tests, the continuous and efficient additive manufacturing of the SiOC porous heat insulation structure can be realized, the preparation speed of the SiOC porous heat insulation structure is far higher than that of the traditional ultraviolet light projection forming process in the comparative example 1, and the performance of the porous heat insulation structure obtained through pyrolysis is excellent.
Example 5
The preparation of an SiOC porous thermal insulation structure in this embodiment mainly includes the following steps:
1) Establishing an SiOC porous heat insulation structure model: and (3) acquiring the characteristic dimension of the shell of the Dendrolimus punctatus according to the optical picture and the SEM microscopic picture of the shell of the Dendrolimus punctatus, and drawing a model in Solidworks drawing software (the model is shown in figures 1 and 2). Wherein, A =20mm, B =8mm, H =10mm, h =2mm.
2) Hyperbranched acrylate-based polysiloxane TEGO RC-711 100g was weighed out and had a viscosity of 392cps. Adding 3g of TPO and 1.5g of methyl red, and uniformly mixing by ultrasonic treatment for 30min to obtain photosensitive ceramic precursor slurry. The viscosity of the ceramic precursor slurry was 382cps.
3) Continuous additive manufacturing: placing the slurry in a slurry tank in a continuous additive manufacturing apparatus towards the bottom of the slurry tankAnd introducing oxygen to ensure that the oxygen pressure in the photosensitive ceramic precursor slurry is 0.005-0.02bar in the continuous photocuring treatment. The setting parameters are as follows: the thickness of the layer was set to 1 μm, and the exposure intensity was set to 30mW/cm 2 The exposure time was set to 1s and the speed was set to 10mm/min. After the preparation is finished, the residual solution on the surface is dried by an air gun, then the mixture is placed into isopropanol to be ultrasonically cleaned for 5min, and after the mixture is dried, a ceramic precursor body (namely a ceramic precursor body) imitating the shell of the deilidoni ferrugineum is obtained.
4) And (3) pyrolyzing into porcelain: putting the ceramic precursor body (namely the ceramic precursor body) of the shell of the armored beetle into an atmosphere furnace, heating to 1000 ℃ at 1 ℃/min under the flowing argon atmosphere, then preserving the heat for 1h, and then cooling to room temperature at 1 ℃/min to obtain the SiOC porous heat insulation structure, wherein the surface of the SiOC porous heat insulation structure is black.
Through tests, the continuous and efficient additive manufacturing of the SiOC porous heat insulation structure can be realized, the preparation speed of the SiOC porous heat insulation structure is far higher than that of the traditional ultraviolet light projection forming process in the comparative example 1, and the performance of the porous heat insulation structure obtained through pyrolysis is excellent.
Example 6
The preparation of an SiOC porous thermal insulation structure in this embodiment mainly includes the following steps:
1) Establishing an SiOC porous heat insulation structure model: and (3) acquiring the characteristic dimension of the shell of the Dendrolimus punctatus according to the optical picture and the SEM microscopic picture of the shell of the Dendrolimus punctatus, and drawing a model in Solidworks drawing software (the model is shown in figures 1 and 2). Where a =20mm, b =8mm, h =10mm, h =2mm.
2) Hyperbranched acrylate-based polysiloxane TEGO RC-711 100g was weighed out and had a viscosity of 392cps. Adding 3g of TPO and 1.5g of methyl red, and uniformly mixing by ultrasonic treatment for 30min to obtain photosensitive ceramic precursor slurry. The viscosity of the photosensitive ceramic precursor slurry was 385cps.
3) Continuous additive manufacturing: and placing the slurry into a slurry tank in continuous additive manufacturing equipment, and introducing oxygen into the bottom of the slurry tank to ensure that the oxygen pressure in the photosensitive ceramic precursor slurry is 0.005-0.02bar in the continuous photocuring treatment. The set parameters are as follows: the thickness of the layer was set to 1 μm, and the exposure was strongThe degree is set to be 12mW/cm 2 The exposure time was set to 1s and the speed was set to 1mm/min. And after the preparation is finished, blowing the residual solution on the surface by using an air gun, then putting the blow-dried solution into isopropanol for ultrasonic cleaning for 5min, and airing to obtain the ceramic precursor body (namely the ceramic precursor body) of the shell of the Trypanosoma ferrugineum.
4) And (3) pyrolyzing into porcelain: putting the ceramic precursor body (namely the ceramic precursor body) of the shell of the armored beetle into an atmosphere furnace, heating to 1000 ℃ at 1 ℃/min under the flowing argon atmosphere, then preserving the heat for 1h, and then cooling to room temperature at 1 ℃/min to obtain the SiOC porous heat insulation structure, wherein the surface of the SiOC porous heat insulation structure is black.
Through tests, the continuous and efficient additive manufacturing of the SiOC porous heat insulation structure can be realized, the preparation speed of the SiOC porous heat insulation structure is far higher than that of the traditional ultraviolet light projection forming process in the comparative example 1, and the performance of the porous heat insulation structure obtained through pyrolysis is excellent.
Comparative example 1
Comparative example 1 the preparation of the sample shown in fig. 1 and 2 was carried out using conventional uv projection molding techniques, essentially comprising the following steps:
1) Preparing photosensitive precursor slurry: 100g TEGO RC 711 was weighed and had a viscosity of 392cps. Adding 3g of TPO and 1.5g of methyl red, and ultrasonically mixing uniformly until the solution is clear. The viscosity of the ceramic precursor slurry was 388cps.
2) Ultraviolet light projection molding: placing the slurry in a commercial ADMATEC photocuring 3D printer, and setting parameters as follows: the thickness of the layer was set to 50 μm, and the exposure intensity was set to 25mW/cm 2 And the exposure time was set to 3s. And after the preparation is finished, blowing the residual solution on the surface by using an air gun, then putting the blow-dried solution into isopropanol for ultrasonic cleaning for 5min, and airing to obtain the ceramic precursor body (namely the ceramic precursor body) of the shell of the Trypanosoma ferrugineum.
3. And (3) pyrolyzing into porcelain: putting the ceramic precursor body (namely, the ceramic precursor body) of the shell of the armored beetle into an atmosphere furnace, heating to 1000 ℃ at 1 ℃/min under the flowing argon atmosphere, then preserving heat for 1h, and then cooling to room temperature at 1 ℃/min; an SiOC porous thermal insulation structure is obtained, the surface of which is black.
Wherein, in comparative example 1, the speed was about 6mm/h.
In addition, the results of comparing the molding speed with time for examples 1 to 3 and comparative example 1 are shown in Table 1.
TABLE 1
As can be seen from table 1: the preparation speed of the embodiment of the invention is far higher than that of the comparative example 1, so that the embodiment of the invention realizes the high-efficiency and rapid preparation of the complex porous heat-insulating bionic structure.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. A method for manufacturing an SiOC porous heat insulation structure in a continuous additive mode is characterized by comprising the following steps:
preparing photosensitive ceramic precursor slurry: mixing acrylate-based polysiloxane, a photoinitiator, a light blocking agent or an ultraviolet absorber to obtain photosensitive ceramic precursor slurry; wherein, the content of the photoinitiator in the photosensitive ceramic precursor slurry is 0.1 to 5 weight percent, and the content of the light blocking agent or the ultraviolet absorber is 0.1 to 5 weight percent; preferably, the acrylate-based polysiloxane has 2 or more acrylate functional groups, preferably 5 or more functional groups; preferably, the molecular weight of the acrylate-based polysiloxane is 100-30000, preferably 200-10000; preferably, the viscosity of the acrylate-based polysiloxane is 20 to 5000cps, preferably 20 to 2000cps; preferably, the viscosity of the photosensitive ceramic precursor slurry is 20 to 5000cps, preferably 20 to 2000cps;
the method comprises the following steps of: placing the photosensitive ceramic precursor slurry in continuous photocuring equipment, and performing continuous photocuring treatment to obtain a ceramic precursor blank;
and (3) pyrolysis treatment: and carrying out pyrolysis treatment on the ceramic precursor body to obtain the SiOC porous heat insulation structure.
2. The method for continuous additive manufacturing of an SiOC porous thermal insulation structure according to claim 1, further comprising, prior to the formulating of the photosensitive ceramic precursor slurry:
preparation of acrylate-based polysiloxane: under an alkaline environment, carrying out a ring-opening reaction on epoxy siloxane and acrylic acid to obtain acrylate-based polysiloxane;
preferably, after the epoxy siloxane and the acrylic acid are mixed, the organic base and the polymerization inhibitor are added into the mixture, and the mixture is obtained after uniform mixing treatment; reacting the mixture at a set temperature for a set time to obtain acrylate-based polysiloxane;
further preferably, in the mixture: the content of the organic alkali is 1-5wt%, and the content of the polymerization inhibitor is 0.5-3wt%;
further preferably, the set temperature is 60-120 ℃, and the set time is 6-24h.
Further preferably, the molar ratio of the epoxysiloxane to acrylic acid is (10n; wherein n is the number of functional groups of the epoxysiloxane;
further preferably, the uniformly mixing treatment mode is one or more of a magnetic stirring mode of 300-900rpm, an ultrasonic dispersion mode of 10-100kHz and a heating and stirring mode of 50-200 ℃;
further preferably, the mixture is placed in a reaction vessel, and a condensing device is arranged on the reaction vessel; and (3) placing the reaction vessel on a heating device, and reacting the mixture at a set temperature for a set time to obtain the acrylate-based polysiloxane.
3. The method for continuous additive manufacturing of an SiOC porous thermal insulation structure according to claim 2,
the epoxy siloxane is multifunctional epoxy siloxane or a composition thereof, wherein the average functionality is more than or equal to 2, preferably more than or equal to 5; and/or
The organic base is one or more of diisopropylethylamine, triethylene diamine, tetramethyl ethylene diamine, triethylamine, diazabicyclo and the like; and/or
The polymerization inhibitor comprises 2,6-tert-butyl-p-cresol, tea polyphenol, tert-butyl-p-hydroxyanisole, tert-butyl hydroquinone and one or more of the compounds.
4. The method for continuous additive manufacturing of a SiOC porous thermal insulation structure according to any one of claims 1 to 3, wherein the acrylate-based polysiloxane is a multifunctional acrylate-based polysiloxane or a combination thereof, wherein the average functionality is ≥ 2, preferably ≥ 5; and/or;
the photoinitiator is one or more of TPO free radical type initiator, 819 free radical type initiator and TPO-L free radical type initiator; and/or
The ultraviolet absorbent is one or more of Sudan I ultraviolet absorbent, methyl red ultraviolet absorbent, methyl orange ultraviolet absorbent and carotene ultraviolet absorbent; and/or
The light blocking agent is OB + light blocking agent.
5. The method for continuously and additively manufacturing the SiOC porous thermal insulation structure according to claim 1, wherein the acrylate-based polysiloxane is selected from any one or more of the following:
hyperbranched polysiloxane TEGO RC 706, TEGO RC 711, TEGO RC 715 and TEGO RC 722 from British chemical Co, germany; x-62-7661, X-62-7989, KF2005 of Japan shin-Etsu chemical Co; acrylate-based polysiloxanes, TEGO RC 902, TEGO RC 922 from British chemical, germany; x-62-7662 and X-62-7629 of Japan shin-Etsu chemical Co.
6. The method of continuous additive manufacturing of a SiOC porous thermal insulation structure according to claims 1-5, wherein in the continuous additive manufacturing step:
and placing the photosensitive ceramic precursor slurry into a slurry tank of continuous photocuring equipment, and introducing oxygen to the bottom of the slurry tank to ensure that the oxygen pressure in the photosensitive ceramic precursor slurry is 0.005-0.02bar in the continuous photocuring treatment.
7. Method of continuous additive manufacturing of a SiOC porous thermal insulation structure according to any one of claims 1-6, wherein in the continuous additive manufacturing steps:
the light curing equipment is continuous light curing ceramic additive manufacturing equipment;
preferably, the parameter settings are as follows: the layer thickness is set to 1-300 μm, and the exposure intensity is set to 1-100mW/cm 2 The exposure time is set to 0.5-30s, and the speed is set to 0.1-300mm/min.
8. Method of continuous additive manufacturing of SiOC porous thermal insulation structures according to any of claims 1-7, characterized in that in the step of pyrolysis treatment:
heating the ceramic precursor body to 800-1200 ℃ in an inert atmosphere, preserving the heat for 0.5-10h at the temperature of 800-1200 ℃, and then cooling to room temperature to obtain an SiOC porous heat insulation structure;
preferably, the inert atmosphere is argon;
preferably, the heating rate of the ceramic precursor body when the temperature is increased to 800-1200 ℃ is 1-10 ℃/min.
9. An SiOC porous heat insulation structure is characterized in that the SiOC porous heat insulation structure is a bionic structure imitating the wall of an armored beetle; wherein the SiOC porous thermal insulation structure is prepared by the continuous additive manufacturing method of the SiOC porous thermal insulation structure according to any one of claims 1 to 8.
10. The SiOC porous thermal insulation structure of claim 9, wherein the biomimetic structure of the siderite beetle shell wall is a one-piece structure; wherein, the bionic structure of the shell wall of the deilidoxime pseudosidedish includes:
a first panel;
the second panel is opposite to the first panel;
the core structure comprises a plurality of hollow cylindrical structures, wherein the hollow cylindrical structures are arranged between the first panel and the second panel, and any two adjacent hollow cylindrical structures are connected; the two ends of the hollow cylindrical structure are open, and the cylindrical outer wall of the hollow cylindrical structure is provided with a first part and a second part which are oppositely arranged; wherein the first portion meets the first panel and the second portion meets the second panel;
preferably, the outer wall of the hollow cylindrical structure further comprises a third part and a fourth part which are oppositely arranged; the third part and the fourth part are both provided with connecting plates, and the connecting plates are parallel to the first panel and the second panel; any two adjacent hollow cylindrical structures are connected through a connecting plate;
preferably, the thickness H of the first panel is 1-10mm, the maximum length a of the opening of the hollow cylindrical structure in the direction parallel to the first panel is 3-30mm, the maximum length H of the opening of the hollow cylindrical structure in the direction perpendicular to the first panel is 3-50mm, and the shortest distance B between the outer walls of two adjacent hollow cylindrical structures is 1-10mm;
preferably, the total length and width of the SiOC porous heat insulation structure is 20-300mm, and the thickness is 5-50mm.
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