CN116352835A - Carbon-based composite ceramic and preparation method thereof - Google Patents
Carbon-based composite ceramic and preparation method thereofDownload PDFInfo
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- CN116352835A CN116352835ACN202310546453.3ACN202310546453ACN116352835ACN 116352835 ACN116352835 ACN 116352835ACN 202310546453 ACN202310546453 ACN 202310546453ACN 116352835 ACN116352835 ACN 116352835A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27M—WORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
- B27M1/00—Working of wood not provided for in subclasses B27B - B27L, e.g. by stretching
- B27M1/08—Working of wood not provided for in subclasses B27B - B27L, e.g. by stretching by multi-step processes
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/163—Compounds of boron
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/32—Mixtures of different inorganic impregnating agents
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/04—Combined bleaching or impregnating and drying of wood
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27M—WORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
- B27M1/00—Working of wood not provided for in subclasses B27B - B27L, e.g. by stretching
- B27M1/06—Working of wood not provided for in subclasses B27B - B27L, e.g. by stretching by burning or charring, e.g. cutting with hot wire
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Abstract
Description
Translated fromChinese技术领域technical field
本发明属于碳基复合陶瓷制备技术领域，尤其是一种碳基复合陶瓷及其制备方法。The invention belongs to the technical field of carbon-based composite ceramic preparation, in particular to a carbon-based composite ceramic and a preparation method thereof.
背景技术Background technique
木材结构的生物碳是一种多孔材料，通过对天然木材进行高温碳化处理而获得的木材结构的生物碳具有重量轻、多级孔隙结构和各向异性等优点。木材结构的生物碳的天然三维多孔导电网络使其成为高效电磁干扰屏蔽的一个很有前途的候选材料。然而，木材结构的生物碳的单一屏蔽机制限制了其电磁干扰屏蔽应用能力。Wood-structured biochar is a porous material, and wood-structured biochar obtained by high-temperature carbonization of natural wood has the advantages of light weight, multi-level pore structure, and anisotropy. The natural three-dimensional porous conductive network of wood-structured biochar makes it a promising candidate for efficient EMI shielding. However, the single shielding mechanism of biochar for wood structures limits its ability for EMI shielding applications.
现有技术中通过将各种导电材料集成到木材结构的生物碳模板中，获得具有改进电磁干扰屏蔽材料的功能复合材料。通常是利用熔盐法制备木材结构的MAX@C复合材料，其中MXA相为Ti2AlC、V2AlC和Cr2AlC，通过在木材结构的生物碳表面原位生长MAX相涂层，制备了具有多孔结构的涂层。但是，采用熔盐法制备的涂层厚度分布不均匀，形状不可控，而且原料M位金属元素粉末即Ti、V和Cr价格昂贵，工艺繁琐，不利于其大规模产业化应用。In the prior art, functional composites with improved EMI shielding materials are obtained by integrating various conductive materials into biochar templates of wood structures. Usually, the MAX@C composites of wood structure are prepared by molten salt method, in which the MXA phases are Ti2 AlC, V2 AlC and Cr2 AlC, and the MAX phase coating is prepared by in-situ growth on the biochar surface of the wood structure. Coatings with a porous structure. However, the thickness distribution of the coating prepared by the molten salt method is uneven, the shape is uncontrollable, and the raw material M-site metal element powders, namely Ti, V and Cr, are expensive and the process is cumbersome, which is not conducive to its large-scale industrial application.
发明内容Contents of the invention
针对现有技术中存在的碳基复合材料的制备方法中导电涂层分布不均匀、工艺繁琐、原料价格昂贵导致其不适于大规模产业化的问题，本发明提供一种碳基复合陶瓷及其制备方法。Aiming at the problems existing in the prior art in the preparation method of carbon-based composite materials such as uneven distribution of conductive coating, cumbersome process and expensive raw materials, which make it unsuitable for large-scale industrialization, the present invention provides a carbon-based composite ceramic and its Preparation.
为达到上述目的，本发明采用以下技术方案予以实现：In order to achieve the above object, the present invention adopts the following technical solutions to achieve:
本发明提供一种碳基复合陶瓷的制备方法，包括以下步骤：The invention provides a method for preparing carbon-based composite ceramics, comprising the following steps:
将天然木材进行首次干燥并高温碳化处理，得到木材结构的生物碳；The natural wood is dried for the first time and then carbonized at high temperature to obtain the biochar of the wood structure;
配制浸渍液，所述浸渍液为稀土硝酸盐和B4C粉末的混合悬浮液；其中，稀土硝酸盐为Re(NO3)3·6H2O或Re(NO3)3·5H2O，其中Re为镧系元素；preparing an impregnating solution, which is a mixed suspension of rare earth nitrate and B4 C powder; wherein, the rare earth nitrate is Re(NO3 )3 ·6H2 O or Re(NO3 )3 ·5H2 O, Wherein Re is lanthanide;
将木材结构的生物碳浸入浸渍液中浸渍并二次干燥，得到含有稀土硝酸盐及B4C粉末的木材结构的生物碳；Immersing the biochar of the wood structure in the impregnating solution and drying it for the second time to obtain the biochar of the wood structure containing rare earth nitrate and B4 C powder;
将含有稀土硝酸盐及B4C粉末的木材结构的生物碳进行硼/碳热还原处理，得到碳基复合陶瓷。The wood-structured biochar containing rare earth nitrate and B4 C powder is subjected to boron/carbothermal reduction treatment to obtain carbon-based composite ceramics.
优选地，首次干燥的温度为80～120℃。Preferably, the temperature of the first drying is 80-120°C.
优选地，高温碳化处理的条件为：惰性气体保护下800～1000℃保温2～6h。Preferably, the conditions for the high-temperature carbonization treatment are: under the protection of an inert gas, keep the temperature at 800-1000°C for 2-6 hours.
进一步地，配制浸渍液的方法为：将稀土硝酸盐、B4C粉末、分散剂和表面改性剂溶于离子水和乙醇的混合溶液中，得到浸渍液；所述分散剂添加量为B4C粉末质量的0.2～1.0％，改性剂的添加量为B4C粉末质量的2～5％，稀土硝酸盐与B4C粉末的摩尔比为2:1，去离子水和乙醇的体积比为9:1；浸渍液中稀土硝酸盐的浓度为0.36～2.64mol/L，B4C粉末的浓度为0.18～1.32mol/L。Further, the method for preparing the impregnation solution is as follows: dissolving the rare earth nitrate, B4 C powder, dispersant and surface modifier in the mixed solution of ionized water and ethanol to obtain the impregnation solution; the added amount of the dispersant is B 0.2-1.0% of the mass of4 C powder, the amount of modifier added is 2-5% of the mass of B4 C powder, the molar ratio of rare earth nitrate to B4 C powder is 2:1, the amount of deionized water and ethanol The volume ratio is 9:1; the concentration of rare earth nitrate in the impregnation solution is 0.36-2.64mol/L, and the concentration of B4 C powder is 0.18-1.32mol/L.
优选地，分散剂为四甲基氢氧化铵或聚乙烯亚胺；表面改性剂为3-氨基丙基三乙氧基硅烷。Preferably, the dispersant is tetramethylammonium hydroxide or polyethyleneimine; the surface modifier is 3-aminopropyltriethoxysilane.
优选地，B4C粉末的粒径为45～55nm。Preferably, the particle diameter of the B4 C powder is 45-55 nm.
优选地，浸渍的条件为真空浸渍4～8h；二次干燥的条件为40～60℃。Preferably, the impregnation condition is vacuum impregnation for 4-8 hours; the secondary drying condition is 40-60°C.
优选地，硼/碳热还原处理的条件为：氩气气氛下在1800～2000℃保温1～6h。Preferably, the conditions for the boron/carbothermal reduction treatment are: keeping the temperature at 1800-2000° C. for 1-6 hours under an argon atmosphere.
优选地，所述天然木材为杉木、杨木、松木、梓木、香木、梧桐木和巴沙木中的一种或多种。Preferably, the natural wood is one or more of fir, poplar, pine, catalpa, fragrant wood, sycamore and balsa wood.
本发明还提供一种利用上述的制备方法制备的碳基复合陶瓷，该复合陶瓷的气孔率为63％～82％，电导率为80.1～250.4S/cm,热导率为4.38～23.14W·m-1·K-1，电磁干扰屏蔽效能为27～65dB，抗弯强度为6～38MPa。The present invention also provides a carbon-based composite ceramic prepared by the above preparation method, the composite ceramic has a porosity of 63% to 82%, an electrical conductivity of 80.1 to 250.4S/cm, and a thermal conductivity of 4.38 to 23.14W. m-1 ·K-1 , the electromagnetic interference shielding effectiveness is 27~65dB, and the bending strength is 6~38MPa.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明一种碳基复合陶瓷的制备方法，选用天然木材原料，并对其依次进行首次干燥、高温处理、浸渍处理、二次干燥处理和硼/碳热还原处理，得到类蜂窝结构碳和稀土二硼二碳复合陶瓷。以天然木材和稀土硝酸盐为原料成本低廉，需要的原始材料为木材，形状可控，极大地节省了成本；另外，木材具有精细的分级多孔结构，包括毫米级、微米级、纳米级的孔隙结构，是一般多孔陶瓷达不到的，制备过程简单，可以精确的控制材料的尺寸、形状，实现材料合成与组装一体化，避免了熔盐法制备过程中对厚度的控制，适宜工业化生产。A method for preparing carbon-based composite ceramics in the present invention, selects natural wood raw materials, and performs first drying, high temperature treatment, dipping treatment, secondary drying treatment and boron/carbon thermal reduction treatment on it in order to obtain honeycomb-like structure carbon and rare earth Diboron and carbon composite ceramics. Using natural wood and rare earth nitrates as raw materials is low in cost, and the original material required is wood, which has a controllable shape and greatly saves costs; in addition, wood has a fine hierarchical porous structure, including millimeter-scale, micron-scale, and nano-scale pores The structure is beyond the reach of general porous ceramics, the preparation process is simple, the size and shape of the material can be precisely controlled, and the integration of material synthesis and assembly can be realized, which avoids the thickness control during the preparation process of the molten salt method, and is suitable for industrial production.
本发明还提供一种利用上述方法制备的碳基复合陶瓷，该陶瓷电导率与热导率高，电导率为80.1～350.4S/cm，热导率为4.38～23.14W·m-1·K-1，电磁干扰屏蔽效能为27～65dB，抗弯强度为6～38Mpa，克服了一般多孔陶瓷复合材料不能兼具高气孔率和较好电导率、热导率、电磁干扰屏蔽效能与抗弯强度的缺陷。The present invention also provides a carbon-based composite ceramic prepared by the above method, the ceramic has high electrical conductivity and thermal conductivity, the electrical conductivity is 80.1-350.4S/cm, and the thermal conductivity is 4.38-23.14W·m-1 ·K-1 , the electromagnetic interference shielding effectiveness is 27~65dB, and the bending strength is 6~38Mpa, which overcomes the fact that general porous ceramic composite materials cannot have both high porosity and good electrical conductivity, thermal conductivity, electromagnetic interference shielding effectiveness and bending resistance Strength flaws.
附图说明Description of drawings
图1为本发明的一种碳基复合陶瓷制备过程的示意图。Fig. 1 is a schematic diagram of the preparation process of a carbon-based composite ceramic of the present invention.
图2为本发明的实施例硼/碳热还原反应后试样的XRD图。Fig. 2 is the XRD pattern of the sample after the boron/carbothermal reduction reaction of the embodiment of the present invention.
图3为实施例硼/碳热还原反应后试样的SEM图。Fig. 3 is the SEM image of the sample after the boron/carbothermal reduction reaction of the embodiment.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。通常在此处附图中描述和示出的本发明实施例的组件可以以各种不同的配置来布置和设计。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments It is a part of embodiments of the present invention, but not all embodiments. The components of the embodiments of the invention generally described and illustrated in the figures herein may be arranged and designed in a variety of different configurations.
因此，以下对在附图中提供的本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。Accordingly, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.
应注意到：相似的标号和字母在下面的附图中表示类似项，因此，一旦某一项在一个附图中被定义，则在随后的附图中不需要对其进行进一步定义和解释。It should be noted that like numerals and letters denote similar items in the following figures, therefore, once an item is defined in one figure, it does not require further definition and explanation in subsequent figures.
在本发明实施例的描述中，需要说明的是，若出现术语“上”、“下”、“水平”、“内”等指示的方位或位置关系为基于附图所示的方位或位置关系，或者是该发明产品使用时惯常摆放的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二”等仅用于区分描述，而不能理解为指示或暗示相对重要性。In the description of the embodiments of the present invention, it should be noted that the orientation or positional relationship indicated by the terms "upper", "lower", "horizontal", "inside" etc. is based on the orientation or positional relationship shown in the drawings , or the orientation or positional relationship that the product of the invention is usually placed in use is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation or be constructed in a specific orientation and operation, and therefore should not be construed as limiting the invention. In addition, the terms "first", "second", etc. are only used for distinguishing descriptions, and should not be construed as indicating or implying relative importance.
此外，若出现术语“水平”，并不表示要求部件绝对水平，而是可以稍微倾斜。如“水平”仅仅是指其方向相对“竖直”而言更加水平，并不是表示该结构一定要完全水平，而是可以稍微倾斜。In addition, when the term "horizontal" appears, it does not mean that the part is required to be absolutely horizontal, but may be slightly inclined. For example, "horizontal" only means that its direction is more horizontal than "vertical", and it does not mean that the structure must be completely horizontal, but can be slightly inclined.
在本发明实施例的描述中，还需要说明的是，除非另有明确的规定和限定，若出现术语“设置”、“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。In the description of the embodiments of the present invention, it should also be noted that, unless otherwise specified and limited, the terms "setting", "installation", "connection" and "connection" should be interpreted in a broad sense, for example, It can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediary, and it can be the internal communication of two components. Those of ordinary skill in the art can understand the specific meanings of the above terms in the present invention according to specific situations.
下面结合具体的实施例对本发明做进一步的详细说明，所述是对本发明的解释而不是限定。The present invention will be further described in detail below in conjunction with specific embodiments, which are explanations of the present invention rather than limitations.
本发明公开了一种碳基复合陶瓷的制备方法，参照图1，包括以下步骤：The invention discloses a method for preparing carbon-based composite ceramics, referring to Figure 1, comprising the following steps:
S1：将天然木材进行首次干燥并高温碳化处理，得到木材结构的生物碳；首次干燥的温度为80～120℃，干燥时间48～96h；高温碳化处理的条件为：惰性气体保护下800～1000℃保温2～6h；所述天然木材为杉木、杨木、松木、梓木、香木、梧桐木和巴沙木中的一种或多种。S1: Dry natural wood for the first time and perform high-temperature carbonization treatment to obtain biochar of wood structure; the temperature for the first drying is 80-120°C, and the drying time is 48-96 hours; the conditions for high-temperature carbonization treatment are: 800-1000 °C under the protection of inert gas Insulate at ℃ for 2-6 hours; the natural wood is one or more of fir, poplar, pine, catalpa, fragrant wood, sycamore wood and balsa wood.
S2：配制浸渍液；具体操作为：将稀土硝酸盐、B4C粉末、分散剂和表面改性剂溶于离子水和乙醇的混合溶液中，得到稀土硝酸盐和B4C粉末的混合悬浮液即浸渍液；所述分散剂添加量为B4C粉末质量的0.2～1.0％，改性剂的添加量为B4C粉末质量的2～5％，稀土硝酸盐与B4C粉末的摩尔比为2:1，去离子水和乙醇的体积比为9:1；浸渍液中稀土硝酸盐的浓度为0.36～2.64mol/L，B4C粉末的浓度为0.18～1.32mol/L；所述分散剂为四甲基氢氧化铵或聚乙烯亚胺；表面改性剂为3-氨基丙基三乙氧基硅烷；B4C粉末的粒径为45～55nm；稀土硝酸盐为Re(NO3)3·6H2O或Re(NO3)3·5H2O，其中Re为镧系元素，Re优选为Y、Gd、Lu或Yb。S2: Preparation of impregnation solution; the specific operation is: dissolving rare earth nitrate, B4 C powder, dispersant and surface modifier in a mixed solution of ionized water and ethanol to obtain a mixed suspension of rare earth nitrate and B4 C powder The liquid is the impregnating liquid; the added amount of the dispersant is 0.2-1.0% of the mass of the B4 C powder, the added amount of the modifier is 2-5% of the mass of the B4 C powder, and the amount of the rare earth nitrate and the B4 C powder is The molar ratio is 2:1, the volume ratio of deionized water and ethanol is 9:1; the concentration of rare earth nitrate in the impregnation solution is 0.36-2.64mol/L, and the concentration of B4 C powder is 0.18-1.32mol/L; The dispersant is tetramethylammonium hydroxide or polyethyleneimine; the surface modifier is 3-aminopropyltriethoxysilane; the particle size ofB4C powder is 45-55nm; the rare earth nitrate is Re (NO3 )3 ·6H2 O or Re(NO3 )3 ·5H2 O, wherein Re is a lanthanide element, and Re is preferably Y, Gd, Lu or Yb.
S3：将木材结构的生物碳浸入浸渍液中浸渍并二次干燥，得到含有稀土硝酸盐及B4C粉末的木材结构的生物碳；浸渍的条件为真空浸渍4～8h；二次干燥的条件为40～60℃，48～96h。S3: Immerse the biochar of the wood structure in the impregnation solution and dry it again to obtain the biochar of the wood structure containing rare earth nitrate and B4 C powder; the impregnation condition is vacuum impregnation for 4-8 hours; the condition of the second drying It is 40～60℃, 48～96h.
S4：将含有稀土硝酸盐及B4C粉末的木材结构的生物碳进行硼/碳热还原处理，得到碳基复合陶瓷；硼/碳热还原处理的条件为：氩气气氛下在1800～2000℃保温1～6h。S4: Boron/carbothermal reduction treatment is performed on wood-structured biochar containing rare earth nitrates and B4 C powder to obtain carbon-based composite ceramics; the conditions for boron/carbothermal reduction treatment are: under an argon atmosphere at 1800-2000 ℃ insulation 1 ~ 6h.
实施例1Example 1
以天然杉木为原料，将天然木材切割成便于打磨的小块，放入鼓风干燥箱中在100℃下干燥24h。将干燥后的木材置于管式气氛炉中，通入流动氩气气氛保护，以0.5℃/min的升温速率加热至500℃，再以1℃/min的升温速率加热至1000℃，保温处理4h，随炉冷却至室温，得到木材结构的生物碳。Using natural fir as raw material, cut the natural wood into small pieces that are easy to polish, and put it into a blast drying oven to dry at 100°C for 24 hours. The dried wood is placed in a tube-type atmosphere furnace, protected by a flowing argon atmosphere, heated to 500°C at a heating rate of 0.5°C/min, and then heated to 1000°C at a heating rate of 1°C/min. After 4 hours, cool down to room temperature with the furnace to obtain wood-structured biochar.
准备200mL烧杯，量取90mL去离子水和10mL无水乙醇，称取0.036mol的硝酸钇，配制0.36mol/L浓度的硝酸钇溶液；再称取0.018mol的B4C粉体，加入B4C粉体质量0.2％的四甲基氢氧化铵，加入B4C粉体质量2.0％的3-氨基丙基三乙氧基硅烷，加入磁力搅拌转子，室温下电磁搅拌24h，之后在80℃的油浴锅内电磁搅拌改性3h，冷却至室温后，将浸渍液与木材结构的生物碳放入250mL抽滤瓶中，使用真空水泵抽至真空状态，并用超声仪超声分散浸渍6h。最后在超声分散的条件下使用机械真空泵抽20min，保证悬浮液充分均匀地渗透到木材结构的生物碳中。将浸渍后的木材结构的生物碳放入100ml烧杯中，放入鼓风干燥箱，在40℃下干燥48h。Prepare a 200mL beaker, measure 90mL of deionized water and 10mL of absolute ethanol, weigh 0.036mol of yttrium nitrate, and prepare a 0.36mol/L concentration of yttrium nitrate solution; then weigh 0.018mol of B4 C powder, add B4 C powder with 0.2% tetramethylammonium hydroxide, add B4 C powder with 2.0% 3-aminopropyltriethoxysilane, add a magnetic stirring rotor, electromagnetically stir at room temperature for 24 hours, and then at 80°C After cooling to room temperature, put the impregnating liquid and wood-structured biochar into a 250mL suction filter bottle, pump it to a vacuum state with a vacuum pump, and ultrasonically disperse and impregnate it for 6 hours. Finally, under the condition of ultrasonic dispersion, use a mechanical vacuum pump for 20 minutes to ensure that the suspension fully and evenly penetrates into the biochar of the wood structure. Put the impregnated wood-structured biochar into a 100ml beaker, put it in a blast drying oven, and dry it at 40°C for 48h.
将干燥后的样品装于BN坩埚内，将BN坩埚置于多功能炉中，通入氩气，以10℃/min从室温升至1200℃后，再以5℃/min从1200℃升至1850℃，并保温2h。得到的类蜂窝结构碳基复合陶瓷记为C@YB2C2，经测试该复合陶瓷的气孔率为73.7％，电导率为80.1S/cm，热导率为4.38W·m-1·K-1，电磁干扰屏蔽效能为27dB，抗弯强度为6.1Mpa。Put the dried sample in a BN crucible, place the BN crucible in a multi-functional furnace, pass in argon gas, rise from room temperature to 1200°C at 10°C/min, and then rise from 1200°C at 5°C/min to 1850°C, and keep warm for 2h. The obtained carbon-based composite ceramics with a honeycomb structure is denoted as C@YB2 C2 . The porosity of the composite ceramics is 73.7%, the electrical conductivity is 80.1S/cm, and the thermal conductivity is 4.38W·m-1 ·K-1 , the electromagnetic interference shielding effectiveness is 27dB, and the bending strength is 6.1Mpa.
实施例2Example 2
以天然梧桐木为原料，将天然木材切割成便于打磨的小块，放入鼓风干燥箱中在120℃下干燥36h。将干燥后的木材置于管式气氛炉中，通入流动氮气气氛保护，以0.5℃/min的升温速率加热至500℃，再以1℃/min的升温速率加热至800℃，保温处理4h，随炉冷却至室温，得到木材结构的生物碳。Using natural sycamore wood as raw material, cut the natural wood into small pieces that are easy to polish, put it in a blast drying oven and dry it at 120°C for 36h. The dried wood was placed in a tubular atmosphere furnace, protected by a flowing nitrogen atmosphere, heated to 500°C at a heating rate of 0.5°C/min, and then heated to 800°C at a heating rate of 1°C/min, and kept for 4 hours. , and cool down to room temperature with the furnace to obtain wood-structured biochar.
准备200mL烧杯，量取90mL去离子水和10mL无水乙醇，称取0.12mol的硝酸钇，配制1.2mol/L浓度的硝酸钇溶液。再称取0.06mol的B4C粉体，加入B4C粉体质量1.0％的聚乙烯亚胺，加入B4C粉体质量5.0％的3-氨基丙基三乙氧基硅烷，加入磁力搅拌转子，室温下电磁搅拌24h,之后在80℃的油浴锅内电磁搅拌改性3h。冷却至室温后与木材结构的生物碳一同放入250mL抽滤瓶中，使用真空水泵抽至真空状态，并用超声仪超声分散浸渍4h。最后在超声分散的条件下使用机械真空泵抽20min，保证悬浮液充分均匀地渗透到样品中。Prepare a 200mL beaker, measure 90mL of deionized water and 10mL of absolute ethanol, weigh 0.12mol of yttrium nitrate, and prepare a 1.2mol/L concentration of yttrium nitrate solution. Then weigh 0.06 mol of B4 C powder, add polyethyleneimine with 1.0% mass of B4 C powder, add 3-aminopropyltriethoxysilane with 5.0% mass of B4 C powder, add magnetic Stir the rotor, electromagnetically stir at room temperature for 24 hours, and then modify by electromagnetically stirring in an oil bath at 80°C for 3 hours. After cooling to room temperature, put it into a 250mL suction filter bottle together with the biochar of the wood structure, use a vacuum water pump to vacuum, and use an ultrasonic instrument to ultrasonically disperse and impregnate for 4 hours. Finally, under the condition of ultrasonic dispersion, use a mechanical vacuum pump for 20 minutes to ensure that the suspension fully and evenly penetrates into the sample.
将浸渍后的样品放入100ml烧杯中，放入鼓风干燥箱，在50℃下干燥72h。Put the impregnated sample into a 100ml beaker, put it into a blast drying oven, and dry it at 50°C for 72h.
将干燥后的样品装于BN坩埚内，将BN坩埚置于多功能炉中，通入氩气，以10℃/min从室温升至1200℃后，再以5℃/min从1200℃升至1900℃，并保温1h，得到的类蜂窝结构碳基复合陶瓷C@YB2C2，经测试该复合陶瓷的气孔率为69.9％，电导率为165.4S/cm，热导率为4.98W·m-1·K-1，电磁干扰屏蔽效能为34dB，抗弯强度为16.6Mpa。Put the dried sample in a BN crucible, place the BN crucible in a multi-functional furnace, pass in argon gas, rise from room temperature to 1200°C at 10°C/min, and then rise from 1200°C at 5°C/min To 1900 ℃, and keep warm for 1h, the obtained honeycomb structure carbon-based composite ceramic C@YB2 C2 , the porosity of the composite ceramic is 69.9%, the electrical conductivity is 165.4S/cm, and the thermal conductivity is 4.98W. ·m-1 ·K-1 , the electromagnetic interference shielding effectiveness is 34dB, and the bending strength is 16.6Mpa.
实施例3Example 3
以天然香木为原料，将天然木材切割成便于打磨的小块，放入鼓风干燥箱中在80℃下干燥72h。将干燥后的木材置于管式气氛炉中，通入流动氩气气氛保护，以0.5℃/min的升温速率加热至500℃，再以1℃/min的升温速率加热至900℃，保温处理6h，随炉冷却至室温，得到木材结构的生物碳材料。Using natural fragrant wood as raw material, cut the natural wood into small pieces that are easy to polish, put it into a blast drying oven and dry it at 80°C for 72h. The dried wood is placed in a tube-type atmosphere furnace, protected by a flowing argon atmosphere, heated to 500°C at a heating rate of 0.5°C/min, and then heated to 900°C at a heating rate of 1°C/min. After 6 hours, cool down to room temperature with the furnace to obtain a wood-structured biochar material.
准备200mL烧杯，量取90mL去离子水和10mL无水乙醇，称取0.10mol的硝酸镥，配制1.0mol/L浓度的硝酸钇溶液。再称取0.05mol的B4C粉体，加入B4C粉体质量0.5％的分散剂四甲基氢氧化铵，加入B4C粉体质量3.0％的3-氨基丙基三乙氧基硅烷，加入磁力搅拌转子，室温下电磁搅拌24h，之后在80℃的油浴锅内电磁搅拌改性3h。冷却后与木材结构的生物碳一同放入250mL抽滤瓶中，使用真空水泵抽至真空状态，并用超声仪超声分散浸渍6h。最后在超声分散的条件下使用机械真空泵抽20min，保证悬浮液充分均匀地渗透到木材结构的生物碳中。Prepare a 200mL beaker, measure 90mL of deionized water and 10mL of absolute ethanol, weigh 0.10mol of lutetium nitrate, and prepare a 1.0mol/L concentration of yttrium nitrate solution. Then weigh 0.05mol of B4 C powder, add 0.5% of B4 C powder mass dispersant tetramethylammonium hydroxide, add B4 C powder mass of 3.0% 3-aminopropyltriethoxy For silane, add a magnetic stirring rotor, stir electromagnetically at room temperature for 24 hours, and then modify it by electromagnetic stirring in an oil bath at 80°C for 3 hours. After cooling, put it into a 250mL suction filter bottle together with the biochar of the wood structure, use a vacuum water pump to vacuum, and use an ultrasonic instrument to ultrasonically disperse and impregnate for 6 hours. Finally, under the condition of ultrasonic dispersion, use a mechanical vacuum pump for 20 minutes to ensure that the suspension fully and evenly penetrates into the biochar of the wood structure.
将浸渍后的样品放入100ml烧杯中，放入鼓风干燥箱，在60℃下干燥48h。Put the impregnated sample into a 100ml beaker, put it into a blast drying oven, and dry it at 60°C for 48h.
将干燥后的样品装于BN坩埚内，将BN坩埚置于多功能炉中，通入氩气，以10℃/min从室温升至1200℃后，再以5℃/min从1200℃升至1950℃，并保温2h，得到的类蜂窝结构碳基复合材料记C@LuB2C2，经测试气孔率为82.1％，电导率为215.6S/cm，热导率为23.14W·m-1·K-1，电磁干扰屏蔽效能为48dB，抗弯强度为28.1Mpa。Put the dried sample in a BN crucible, place the BN crucible in a multi-functional furnace, pass in argon gas, rise from room temperature to 1200°C at 10°C/min, and then rise from 1200°C at 5°C/min to 1950°C and keep it warm for 2 hours, the obtained carbon-based composite material with honeycomb structure is recorded as C@LuB2 C2 , the porosity is 82.1%, the electrical conductivity is 215.6S/cm, and the thermal conductivity is 23.14W·m- 1 ·K-1 , the electromagnetic interference shielding effectiveness is 48dB, and the bending strength is 28.1Mpa.
实施例4Example 4
以天然杉木为原料，将天然木材切割成便于打磨的小块，放入鼓风干燥箱中在90℃下干燥96h；将干燥后的木材置于管式气氛炉中，通入流动氮气气氛保护，以0.5℃/min的升温速率加热至500℃，再以1℃/min的升温速率加热至1000℃，保温处理2h，随炉冷却至室温，得到木材结构的生物碳材料。Using natural fir as raw material, cut the natural wood into small pieces that are easy to polish, put it in a blast drying oven and dry it at 90°C for 96 hours; put the dried wood in a tube-type atmosphere furnace, and pass it into a flowing nitrogen atmosphere for protection , heated to 500°C at a heating rate of 0.5°C/min, then heated to 1000°C at a heating rate of 1°C/min, held for 2 hours, and cooled to room temperature with the furnace to obtain a wood-structured biochar material.
准备200mL烧杯，量取90mL去离子水和10mL无水乙醇，称取0.264mol的硝酸钇，配制2.64mol/L浓度的硝酸钇溶液。再称取0.132mol的B4C粉体，加入B4C粉体质量0.5％的四甲基氢氧化铵，加入B4C粉体质量3.5％的3-氨基丙基三乙氧基硅烷，加入磁力搅拌转子，室温下电磁搅拌24h，之后在80℃的油浴锅内电磁搅拌改性3h。冷却后与木材结构的生物碳材料一同放入250mL抽滤瓶中，使用真空水泵抽至真空状态，并用超声仪超声分散浸渍8h。最后在超声分散的条件下使用机械真空泵抽20min，保证悬浮液充分均匀地渗透到样品中。Prepare a 200mL beaker, measure 90mL of deionized water and 10mL of absolute ethanol, weigh 0.264mol of yttrium nitrate, and prepare a 2.64mol/L concentration of yttrium nitrate solution. Then weigh 0.132mol of B4 C powder, add 0.5% tetramethylammonium hydroxide of B4 C powder mass, add 3-aminopropyltriethoxysilane of 3.5% of B4 C powder mass, A magnetic stirring rotor was added, electromagnetic stirring was performed at room temperature for 24 hours, and then modified by electromagnetic stirring in an oil bath at 80° C. for 3 hours. After cooling, put it into a 250mL suction filter bottle together with the biochar material of wood structure, use a vacuum water pump to vacuum, and use an ultrasonic instrument to ultrasonically disperse and impregnate for 8 hours. Finally, under the condition of ultrasonic dispersion, use a mechanical vacuum pump for 20 minutes to ensure that the suspension fully and evenly penetrates into the sample.
将浸渍后的样品放入100ml烧杯中，放入鼓风干燥箱，在55℃下干燥72h。Put the impregnated sample into a 100ml beaker, put it into a blast drying oven, and dry it at 55°C for 72h.
将干燥后的样品装于BN坩埚内，将BN坩埚置于多功能炉中，通入氩气，以10℃/min从室温升至1200℃后，再以5℃/min从1200℃升至1900℃，并保温4h，得到的类蜂窝结构C@YB2C2复合陶瓷的气孔率为77.3％，电导率为186.9S/cm，热导率为5.34W·m-1·K-1，电磁干扰屏蔽效能为39dB，抗弯强度为18.1Mpa。Put the dried sample in a BN crucible, place the BN crucible in a multi-functional furnace, pass in argon gas, rise from room temperature to 1200°C at 10°C/min, and then rise from 1200°C at 5°C/min To 1900 ℃, and keep warm for 4h, the porosity of the obtained honeycomb structure C@YB2 C2 composite ceramics is 77.3%, the electrical conductivity is 186.9S/cm, and the thermal conductivity is 5.34W·m-1 ·K-1 , EMI shielding effectiveness is 39dB, bending strength is 18.1Mpa.
实施例5Example 5
以天然杨木为原料，将天然木材切割成便于打磨的小块，放入烘箱中干燥72h。将干燥后的木材置于管式气氛炉中，通入流动氩气气氛保护，以0.5℃/min的升温速率加热至500℃，再以1℃/min的升温速率加热至1000℃，保温处理6h，随炉冷却至室温，得到木材结构的生物碳材料。Using natural poplar as raw material, cut the natural wood into small pieces that are easy to polish, and put it in an oven to dry for 72 hours. The dried wood is placed in a tube-type atmosphere furnace, protected by a flowing argon atmosphere, heated to 500°C at a heating rate of 0.5°C/min, and then heated to 1000°C at a heating rate of 1°C/min. After 6 hours, cool down to room temperature with the furnace to obtain a wood-structured biochar material.
准备200mL烧杯，量取90mL去离子水和10mL无水乙醇，称取0.15mol的硝酸钆，配制1.5mol/L浓度的硝酸钆溶液。再称取0.075mol的B4C粉体，加入B4C粉体质量0.4％的分散剂聚乙烯亚胺，加入B4C粉体质量3.5％的3-氨基丙基三乙氧基硅烷，加入磁力搅拌转子，室温下电磁搅拌24h，之后在80℃的油浴锅内电磁搅拌改性3h。冷却后与木材结构的生物碳材料一同放入250mL抽滤瓶中，使用真空水泵抽至真空状态，并用超声仪超声分散浸渍4h。最后在超声分散的条件下使用机械真空泵抽20min，保证悬浮液充分均匀地渗透到样品中。Prepare a 200mL beaker, measure 90mL of deionized water and 10mL of absolute ethanol, weigh 0.15mol of gadolinium nitrate, and prepare a 1.5mol/L concentration of gadolinium nitrate solution. Then weigh 0.075 mol of B4 C powder, add 0.4% of B4 C powder mass dispersant polyethyleneimine, add 3.5% of B4 C powder mass 3-aminopropyltriethoxysilane, A magnetic stirring rotor was added, electromagnetic stirring was performed at room temperature for 24 hours, and then modified by electromagnetic stirring in an oil bath at 80° C. for 3 hours. After cooling, put it into a 250mL suction filter bottle together with the biochar material of wood structure, use a vacuum water pump to vacuum, and use an ultrasonic instrument to ultrasonically disperse and impregnate for 4 hours. Finally, under the condition of ultrasonic dispersion, use a mechanical vacuum pump for 20 minutes to ensure that the suspension fully and evenly penetrates into the sample.
将浸渍后的样品放入100ml烧杯中，放入鼓风干燥箱，在50℃下干燥96h。Put the impregnated sample into a 100ml beaker, put it into a blast drying oven, and dry it at 50°C for 96h.
将干燥后的样品装于BN坩埚内，将BN坩埚置于多功能炉中，通入氩气，以10℃/min从室温升至1200℃后，再以5℃/min从1200℃升至2000℃，并保温1h，得到的类蜂窝结构C@GdB2C2复合陶瓷的气孔率为77.3％，电导率为178.9S/cm，热导率为10.51W·m-1·K-1，电磁干扰屏蔽效能为42dB，抗弯强度为26.6Mpa。Put the dried sample in a BN crucible, place the BN crucible in a multi-functional furnace, pass in argon gas, rise from room temperature to 1200°C at 10°C/min, and then rise from 1200°C at 5°C/min To 2000 ℃, and keep it warm for 1h, the porosity of the obtained honeycomb structure C@GdB2 C2 composite ceramics is 77.3%, the electrical conductivity is 178.9S/cm, and the thermal conductivity is 10.51W·m-1 ·K-1 , EMI shielding effectiveness is 42dB, bending strength is 26.6Mpa.
实施例6Example 6
以天然梓木为原料，将天然木材切割成便于打磨的小块，放入鼓风干燥箱中在100℃下干燥48h。将干燥后的木材置于管式气氛炉中，通入流动氩气气氛保护，以0.5℃/min的升温速率加热至500℃，再以1℃/min的升温速率加热至900℃，保温处理3h，随炉冷却至室温，得到多孔结构的炭材料。Using natural catalpa as raw material, cut the natural wood into small pieces that are easy to polish, put it in a blast drying oven and dry it at 100°C for 48 hours. The dried wood is placed in a tube-type atmosphere furnace, protected by a flowing argon atmosphere, heated to 500°C at a heating rate of 0.5°C/min, and then heated to 900°C at a heating rate of 1°C/min. After 3 hours, cool down to room temperature with the furnace to obtain a carbon material with a porous structure.
准备200mL烧杯，量取90mL去离子水和10mL无水乙醇，称取0.18mol的硝酸镱，配制1.80mol/L浓度的硝酸镱溶液。再称取0.09mol的B4C粉体，加入B4C粉体质量0.7％的四甲基氢氧化铵，加入B4C粉体质量2.5％的3-氨基丙基三乙氧基硅烷，加入磁力搅拌转子，室温下电磁搅拌24h，之后在80℃的油浴锅内电磁搅拌改性3h。冷却后与木材结构的生物碳一同放入250mL抽滤瓶中，使用真空水泵抽至真空状态，并用超声仪超声分散浸渍8h。最后在超声分散的条件下使用机械真空泵抽20min，保证悬浮液充分均匀地渗透到样品中。Prepare a 200mL beaker, measure 90mL of deionized water and 10mL of absolute ethanol, weigh 0.18mol of ytterbium nitrate, and prepare a 1.80mol/L concentration of ytterbium nitrate solution. Then weigh 0.09 mol of B4 C powder, add 0.7% tetramethylammonium hydroxide of B4 C powder mass, add 2.5% of B4 C powder mass 3-aminopropyltriethoxysilane, A magnetic stirring rotor was added, electromagnetic stirring was performed at room temperature for 24 hours, and then modified by electromagnetic stirring in an oil bath at 80° C. for 3 hours. After cooling, put it into a 250mL suction filter bottle together with the biochar of the wood structure, use a vacuum water pump to vacuum, and use an ultrasonic instrument to ultrasonically disperse and impregnate for 8 hours. Finally, under the condition of ultrasonic dispersion, use a mechanical vacuum pump for 20 minutes to ensure that the suspension fully and evenly penetrates into the sample.
将浸渍后的样品放入100ml烧杯中，放入鼓风干燥箱，在40℃下干燥72h。Put the impregnated sample into a 100ml beaker, put it into a blast drying oven, and dry it at 40°C for 72h.
将干燥后的样品装于BN坩埚内，将BN坩埚置于多功能炉中，通入氩气，以10℃/min从室温升至1200℃后，再以5℃/min从1200℃升至2000℃，并保温2h，得到的类蜂窝结构C@YbB2C2复合陶瓷的气孔率为82.1％，电导率为143.9S/cm，热导率为11.69W·m-1·K-1，电磁干扰屏蔽效能为58dB，抗弯强度为38.1Mpa。Put the dried sample in a BN crucible, place the BN crucible in a multi-functional furnace, pass in argon gas, rise from room temperature to 1200°C at 10°C/min, and then rise from 1200°C at 5°C/min to 2000°C and keep it warm for 2 hours, the porosity of the obtained honeycomb-like C@YbB2 C2 composite ceramics is 82.1%, the electrical conductivity is 143.9S/cm, and the thermal conductivity is 11.69W·m-1 ·K-1 , EMI shielding effectiveness is 58dB, bending strength is 38.1Mpa.
实施例7Example 7
以天然松木为原料，将天然木材切割成便于打磨的小块，放入鼓风干燥箱中在120℃下干燥48h。将干燥后的木材置于管式气氛炉中，通入流动氩气气氛保护，以0.5℃/min的升温速率加热至500℃，再以1℃/min的升温速率加热至1000℃，保温处理2h，随炉冷却至室温，得到木材结构的生物碳材料。Using natural pine as raw material, cut the natural wood into small pieces that are easy to polish, put it into a blast drying oven and dry it at 120°C for 48 hours. The dried wood is placed in a tube-type atmosphere furnace, protected by a flowing argon atmosphere, heated to 500°C at a heating rate of 0.5°C/min, and then heated to 1000°C at a heating rate of 1°C/min. After 2 hours, cool down to room temperature with the furnace to obtain a wood-structured biochar material.
准备200mL烧杯，量取90mL去离子水和10mL无水乙醇，称取0.24mol的硝酸镱，配制2.40mol/L浓度的硝酸镱溶液。再称取0.12mol的B4C粉体，加入B4C粉体质量0.6％的聚乙烯亚胺,加入B4C粉体质量3.5％的3-氨基丙基三乙氧基硅烷，加入磁力搅拌转子，室温下电磁搅拌24h，之后在80℃的油浴锅内电磁搅拌改性3h。冷却后与木材结构的生物碳一同放入250mL抽滤瓶中，使用真空水泵抽至真空状态，并用超声仪超声分散8h。最后在超声分散的条件下使用机械真空泵抽20min，保证悬浮液充分均匀地渗透到样品中。Prepare a 200mL beaker, measure 90mL of deionized water and 10mL of absolute ethanol, weigh 0.24mol of ytterbium nitrate, and prepare a 2.40mol/L concentration of ytterbium nitrate solution. Then weigh 0.12 mol of B4 C powder, add polyethyleneimine with 0.6% mass of B4 C powder, add 3-aminopropyltriethoxysilane with 3.5% mass of B4 C powder, add magnetic The rotor was stirred, electromagnetically stirred at room temperature for 24 hours, and then modified by electromagnetically stirring in an oil bath at 80° C. for 3 hours. After cooling, put it into a 250mL suction filter bottle together with the biochar of the wood structure, use a vacuum water pump to vacuum, and use an ultrasonic instrument to ultrasonically disperse for 8 hours. Finally, under the condition of ultrasonic dispersion, use a mechanical vacuum pump for 20 minutes to ensure that the suspension fully and evenly penetrates into the sample.
将浸渍后的样品放入100ml烧杯中，放入鼓风干燥箱，在40℃下干燥72h。Put the impregnated sample into a 100ml beaker, put it into a blast drying oven, and dry it at 40°C for 72h.
将干燥后的样品装于BN坩埚内，将BN坩埚置于多功能炉中，通入氩气，以10℃/min从室温升至1200℃后，再以5℃/min从1200℃升至2000℃，并保温1h，得到的类蜂窝结构C@YbB2C2复合陶瓷的气孔率为74.6％，电导率为165.6S/cm，热导率为16.32W·m-1·K-1，电磁干扰屏蔽效能为65dB，抗弯强度为30.6Mpa。Put the dried sample in a BN crucible, place the BN crucible in a multi-functional furnace, pass in argon gas, rise from room temperature to 1200°C at 10°C/min, and then rise from 1200°C at 5°C/min to 2000°C and keep it warm for 1h, the obtained honeycomb structure C@YbB2 C2 composite ceramics has a porosity of 74.6%, an electrical conductivity of 165.6S/cm, and a thermal conductivity of 16.32W·m-1 ·K-1 , EMI shielding effectiveness is 65dB, bending strength is 30.6Mpa.
实施例8Example 8
以天然巴沙木为原料，将天然木材切割成便于打磨的小块，放入鼓风干燥箱中在100℃下干燥96h。将干燥后的木材置于管式气氛炉中，通入流动氩气气氛保护，以0.5℃/min的升温速率加热至500℃，再以1℃/min的升温速率加热至1000℃，保温处理4h，随炉冷却至室温，得到木材结构的生物碳材料。Using natural balsa wood as raw material, cut the natural wood into small pieces that are easy to polish, and put it into a blast drying oven for 96 hours at 100°C. The dried wood is placed in a tube-type atmosphere furnace, protected by a flowing argon atmosphere, heated to 500°C at a heating rate of 0.5°C/min, and then heated to 1000°C at a heating rate of 1°C/min. After 4 hours, cool down to room temperature with the furnace to obtain a biochar material with a wood structure.
准备200mL烧杯，量取90mL去离子水和10mL无水乙醇，称取0.16mol的硝酸镥，配制1.60mol/L浓度的硝酸镥溶液。再称取0.08mol的B4C粉体，加入B4C粉体质量0.5％的分散剂四甲基氢氧化铵，加入B4C粉体质量4.0％的改性剂3-氨基丙基三乙氧基硅烷,加入磁力搅拌转子，室温下电磁搅拌24h，之后在80℃的油浴锅内电磁搅拌改性3h。冷却后与样品一同放入250mL抽滤瓶中，使用真空水泵抽至真空状态，并用超声仪超声分散浸渍6h。最后在超声分散的条件下使用机械真空泵抽20min，保证悬浮液充分均匀地渗透到样品中。Prepare a 200mL beaker, measure 90mL of deionized water and 10mL of absolute ethanol, weigh 0.16mol of lutetium nitrate, and prepare a 1.60mol/L concentration of lutetium nitrate solution. Then weigh 0.08 mol of B4 C powder, add 0.5% of the mass of B4 C powder as a dispersant tetramethylammonium hydroxide, add 4.0% of the mass of B4 C powder as a modifier 3-aminopropyltri Ethoxysilane, add a magnetic stirring rotor, electromagnetically stir at room temperature for 24h, and then modify by electromagnetically stirring in an oil bath at 80°C for 3h. After cooling, put it into a 250mL suction filter bottle together with the sample, pump it to a vacuum state with a vacuum water pump, and ultrasonically disperse and impregnate it for 6 hours. Finally, under the condition of ultrasonic dispersion, use a mechanical vacuum pump for 20 minutes to ensure that the suspension fully and evenly penetrates into the sample.
将浸渍后的样品放入100ml烧杯中，放入鼓风干燥箱，在55℃下干燥96h。Put the impregnated sample into a 100ml beaker, put it into a blast drying oven, and dry it at 55°C for 96h.
将干燥后的样品装于BN坩埚内，将BN坩埚置于多功能炉中，通入氩气，以10℃/min从室温升至1200℃后，再以5℃/min从1200℃升至1950℃，并保温3h，得到的类蜂窝结构C@LuB2C2复合陶瓷的气孔率为69.9％，电导率为250.4S/cm，热导率为22.86W·m-1·K-1，电磁干扰屏蔽效能为46dB，抗弯强度为18.2Mpa。Put the dried sample in a BN crucible, place the BN crucible in a multi-functional furnace, pass in argon gas, rise from room temperature to 1200°C at 10°C/min, and then rise from 1200°C at 5°C/min to 1950°C and keep it warm for 3 hours, the porosity of the obtained honeycomb-like C@LuB2 C2 composite ceramics is 69.9%, the electrical conductivity is 250.4S/cm, and the thermal conductivity is 22.86W·m-1 ·K-1 , EMI shielding effectiveness is 46dB, bending strength is 18.2Mpa.
参见图2，将实施例1所获得的类蜂窝结构C@YB2C2复合陶瓷进行XRD测试，结果发现经过硼/碳热还原反应后，所获得的相为单一的YB2C2。参见图3，实施例4所获得的类蜂窝结构C@YB2C2复合陶瓷的SEM结果可以看出，YB2C2层片状晶之间相互堆积，形成了类蜂窝结构C@YB2C2复合陶瓷。Referring to Fig. 2, the XRD test was carried out on the honeycomb-like structure C@YB2 C2 composite ceramics obtained in Example 1, and it was found that after the boron/carbothermal reduction reaction, the obtained phase was a single YB2 C2 . Referring to Figure 3, the SEM results of the honeycomb-like structure C@YB2 C2 composite ceramics obtained in Example 4 show that the YB2 C2 layers of flaky grains are stacked with each other to form a honeycomb-like structure C@YB2 C2 composite ceramics.
综上所述，本发明提供的一种碳基复合陶瓷的制备方法，选用天然木材原料，并对其依次进行首次干燥、高温处理、浸渍处理、二次干燥处理和硼/碳热还原处理，得到类蜂窝结构碳和稀土二硼二碳复合陶瓷。以天然木材和稀土硝酸盐为原料成本低廉，需要的原始材料为木材，形状可控，极大地节省了成本且制备的类蜂窝结构碳和稀土二硼二碳复合陶瓷加工过程简单，可以精确的控制材料的尺寸、形状，实现材料合成与组装一体化，避免了熔盐法制备过程中对厚度的控制，适宜工业化生产，可广泛应用于电磁干扰屏蔽等领域。To sum up, the preparation method of a carbon-based composite ceramic provided by the present invention selects natural wood raw materials, and performs first drying, high temperature treatment, dipping treatment, secondary drying treatment and boron/carbon thermal reduction treatment on it in sequence, A honeycomb-like structure carbon and rare earth diboron-dicarbon composite ceramics are obtained. Using natural wood and rare earth nitrates as raw materials is low in cost, and the original material required is wood with controllable shape, which greatly saves the cost and the preparation of honeycomb-like structure carbon and rare earth diboron-dicarbon composite ceramics has a simple processing process and can be precisely Control the size and shape of the material, realize the integration of material synthesis and assembly, avoid the control of thickness during the preparation process of molten salt method, suitable for industrial production, and can be widely used in fields such as electromagnetic interference shielding.
本发明还提供利用上述的制备方法制备的碳基复合陶瓷，该复合陶瓷的气孔率为63％～82％，电导率为80.1～250.4S/cm,热导率为4.38～23.14W·m-1·K-1，电磁干扰屏蔽效能为27～65dB，抗弯强度为6～38MPa。The present invention also provides a carbon-based composite ceramic prepared by the above-mentioned preparation method, the composite ceramic has a porosity of 63% to 82%, an electrical conductivity of 80.1 to 250.4S/cm, and a thermal conductivity of 4.38 to 23.14W·m- 1 ·K-1 , the electromagnetic interference shielding effectiveness is 27~65dB, and the bending strength is 6~38MPa.
以上所述的仅仅是本发明的较佳实施例，并不用以对本发明的技术方案进行任何限制，本领域技术人员应当理解的是，在不脱离本发明精神和原则的前提下，该技术方案还可以进行若干简单的修改和替换，这些修改和替换也均属于权利要求书所涵盖的保护范围之内。The above are only preferred embodiments of the present invention, and are not intended to limit the technical solutions of the present invention. Those skilled in the art should understand that, without departing from the spirit and principles of the present invention, the technical solutions Some simple modifications and substitutions can also be made, and these modifications and substitutions also fall within the scope of protection covered by the claims.
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