CN113956045B - Preparation method of fiber composite boron carbide foam ceramic material - Google Patents

Preparation method of fiber composite boron carbide foam ceramic material Download PDF

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CN113956045B
CN113956045B CN202111476616.2A CN202111476616A CN113956045B CN 113956045 B CN113956045 B CN 113956045B CN 202111476616 A CN202111476616 A CN 202111476616A CN 113956045 B CN113956045 B CN 113956045B
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boron carbide
freezing
heating
prepared
fiber
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CN113956045A (en
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叶俊伟
张迪嘉
张守臣
宁桂玲
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Dalian University of Technology
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Abstract

The invention belongs to the technical field of inorganic material preparation, and discloses a preparation method of a fiber composite boron carbide foamed ceramic material. The process method is simple, low in energy consumption and free of pollution; the prepared boron carbide material has uniform and adjustable aperture and orientation, and the by-product helium generated by boron absorption neutrons can be discharged in time through the pore structure; the laminated structure is compact, and rays can be prevented from passing through without hindrance; the fibers are embedded in the laminates or bridge the adjacent laminates to enhance the mechanical strength and improve the heat dissipation capability of the laminates. The prepared material can be used in the fields of nuclear power industry, protective armor and the like, and has good application prospect.

Description

Preparation method of fiber composite boron carbide foam ceramic material
Technical Field
The invention belongs to the technical field of inorganic material preparation, and relates to a preparation method of a fiber composite boron carbide foam ceramic material.
Background
The boron carbide and the composite material thereof have the advantages of low density, high hardness, high temperature resistance, corrosion resistance, good chemical stability and excellent neutron absorption performance, can be used for an absorption rod, a control rod and a safety rod in a nuclear reactor core assembly, and are materials for a spent fuel container and radiation protection. The existing preparation process of boron carbide ceramics is mostly formed by hot-pressing or pressureless sintering of pure boron carbide or a small amount of sintering aid; the method needs high temperature, has high requirements on equipment and high energy consumption, and the prepared boron carbide material has high density but poor toughness and is difficult to adapt to the use requirements of light weight, easy processing and convenient replacement of shielding materials.
In order to solve the problems of high preparation cost, difficult sintering and large specific gravity of boron carbide materials, organic polymers can be used as a matrix, boron carbide powder is dispersed in the matrix, and the composite material is prepared by the processes of blending, extruding, curing and the like. The material prepared by the process has low density, but the content of boron carbide in the matrix is low, rays can easily and directly penetrate through gaps among boron carbide particles, the shielding effect is limited, and the heat conductivity, heat resistance and ageing resistance of the material are required to be improved; after long-term irradiation, the material can cause the molecular weight of the polymer to be reduced and the softening temperature to be reduced, so that the material can not be used for high-radioactivity spent fuel pool materials or transport containers.
The two types of boron carbide materials are compact block materials, and helium as a byproduct generated after the boron carbide absorbs neutrons cannot be discharged in time, so that the materials are swelled, cracked and invalid, and even safety problems are caused. With the rapid development of nuclear power industry in China, the demands of spent fuel transportation and storage container materials and nuclear shielding materials are increasing day by day, and the development of high-performance boron carbide ceramic materials is urgently needed.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a fiber composite boron carbide foam ceramic material, which improves the mechanical and heat transfer properties of the material through the design of a fiber reinforced porous structure, enables the neutron absorption byproduct helium to be discharged to provide a pore channel, effectively prevents rays from directly passing through a compact laminate stacking structure, promotes the attenuation of ray energy by utilizing the reflection and refraction between laminates, and can meet the use requirements in the fields of nuclear shielding and electromagnetic shielding.
A preparation method of a fiber composite boron carbide foam ceramic material comprises the following steps:
step 1, preparing boron carbide powder into aqueous slurry, sequentially adding an auxiliary agent, fibers and ammonium polymethacrylate according to a proportion, and mixing and ball-milling for 1-20 hours at the speed of 100-400 r/min to obtain mixed slurry; then heating the mixed slurry to 30-90 ℃, adding a binder and uniformly stirring to obtain a raw material solution;
step 2, pouring the raw material liquid prepared in the step 1 into a pre-prepared freezing container, placing the container on the top of a metal heat conduction column of a pre-prepared freezing device, injecting liquid nitrogen serving as a cold source into a barrel of the freezing device, and directionally freezing the raw material liquid placed in the freezing container on the top of the barrel; after completely freezing, placing the mixture in a freeze drying box for further drying to obtain a freeze-dried blank;
and 3, sintering the freeze-dried blank obtained in the step 2 at a certain temperature in an argon flow atmosphere, and cooling to room temperature to obtain the fiber composite boron carbide foamed ceramic material.
According to the scheme, the boron carbide in the step 1 is industrial boron carbide powder with the grain size of 0.2-10 microns.
According to the scheme, the adding amount of the boron carbide in the step 1 is 10-45% of the mass of the water.
According to the scheme, the auxiliary agent in the step 1 is one or more of sodium carboxymethylcellulose, gelatin and polyvinyl alcohol.
According to the scheme, the addition amount of the auxiliary agent in the step 1 is 0.5-20% of the mass of the solid component.
According to the scheme, the fiber in the step 1 is one or more of silicon carbide fiber, carbon fiber and carbon nano tube.
According to the scheme, the adding amount of the fibers in the step 1 is 0.5-10% of the mass of the solid components.
According to the scheme, the adding amount of the ammonium polymethacrylate in the step 1 is 0.1-5% of the mass of the solid components.
According to the scheme, the binder in the step 1 is silicon powder or aluminum powder, and any one of the silicon powder and the aluminum powder is selected.
According to the scheme, the addition amount of the binder in the step 1 is 1-15% of the mass of the boron carbide powder.
According to the scheme, the refrigerating device in the step 2 comprises a round barrel with a metal lining and an attached thermal insulation material, and a metal column is vertically placed in the barrel to serve as a metal heat conduction column.
According to the scheme, the sintering conditions in the step 3 are that the temperature is increased to 1000 ℃ at the speed of 10 ℃/min, the temperature is increased to 1400 ℃ at the speed of 5 ℃/min, the temperature is increased to 1500-1700 ℃ at the speed of 2 ℃/min, and the temperature is kept for 1-10h.
Compared with the prior art, the invention has the advantages that the fiber composite boron carbide foamed ceramic material is prepared by adopting a water dispersion system through freezing and pressureless sintering, the process method is simple, the energy consumption is lower, and no pollution is caused; the prepared boron carbide material has uniform and adjustable aperture and orientation, the hole structure can discharge helium as a byproduct of boron absorption neutrons in time, the material has good thermal stress, the laminated structure is compact, rays can be prevented from passing through the laminated structure without obstruction, and meanwhile, the ordered stacking of the laminated plates can enable the rays to be reflected and refracted for multiple times between the plate layers, so that the energy of the rays is enabled to be attenuated quickly; the added fibers are embedded in the laminates or bridge the adjacent laminates to enhance the mechanical strength and improve the heat dissipation capability of the laminates. The prepared material can be used in the fields of nuclear power industry, protective armor and the like, and has good application prospect.
Drawings
FIG. 1 is an electron scanning electron microscope image of a fiber composite boron carbide foam ceramic material of the present invention.
Detailed Description
The following detailed description of the invention refers to the accompanying drawings.
Example 1
24g of water is taken as a dispersing agent, 6.80g of boron carbide powder with the average grain diameter of 0.5 mu m is added to prepare slurry, and then 0.05g of silicon powder, 0.51g of aluminum powder, 0.64g of silicon carbide fiber and 0.08g of ammonium polymethacrylate are added. Mixing and ball milling for 2h at 180r/min to obtain a mixed solution I. And heating the mixed solution I to 80 ℃, adding 0.98g of gelatin, and uniformly mixing to obtain a mixed solution II. And pouring the obtained mixed solution II into a freezing container, placing the container on the top of a metal heat conducting column of a pre-prepared freezing device, and injecting the container into a barrel of the freezing device by taking liquid nitrogen as a cold source. And taking down the freezing container after the mixed solution is completely frozen, and putting the freezing container in a freeze drying box for freeze drying to obtain a blank. Taking the freeze-dried blank out of the freezing container, placing the blank in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon flow atmosphere, heating to 1400 ℃ at a speed of 5 ℃/min, heating to 1600 ℃ at a speed of 2 ℃/min, keeping the temperature for 2h, cooling to room temperature, and taking out to obtain the fiber composite boron carbide foamed ceramic material, wherein the structure is shown in figure 1. Tests show that: the density of the prepared fiber composite boron carbide material is 0.34g/cm 3 The compressive strength is 5.5Mpa.
Example 2
Adding 6.96g of boron carbide powder with the average grain diameter of 0.5 mu m into 24g of water serving as a dispersing agent to prepare slurry, and then adding0.10g of silicon powder, 0.40g of aluminum powder and 0.48g of silicon carbide fiber are added, and 0.10g of ammonium polymethacrylate is added. Mixing and ball milling at 200r/min for 1.5h to obtain a mixed solution I. And heating the mixed solution I to 60 ℃, adding 0.85g of gelatin, and uniformly mixing to obtain a mixed solution II. And pouring the obtained mixed solution II into a freezing container, placing the container on the top of a metal heat conducting column of a pre-prepared freezing device, and injecting the container into a barrel of the freezing device by taking liquid nitrogen as a cold source. And taking down the freezing container after the mixed solution is completely frozen, and putting the freezing container in a freeze drying box for freeze drying to obtain a blank. Taking the freeze-dried blank out of the freezing container, placing the blank in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon flow atmosphere, heating to 1400 ℃ at a speed of 5 ℃/min, heating to 1500 ℃ at a speed of 2 ℃/min, preserving heat for 3h, cooling to room temperature, and taking out to obtain the fiber composite boron carbide foamed ceramic material. Tests show that: the density of the prepared fiber composite boron carbide material is 0.32g/cm 3 The compressive strength is 4.8MPa.
Example 3
24g of water is taken as a dispersing agent, 7.20g of boron carbide powder with the average grain diameter of 0.5 mu m is added, 0.13g of silicon powder, 0.48g of aluminum powder, 0.20g of carbon fiber and 0.12g of ammonium polymethacrylate are added. Mixing and ball milling at 160r/min for 1.5h to obtain a mixed solution I. And heating the mixed solution I to 60 ℃, adding 0.75g of polyvinyl alcohol, and uniformly mixing to obtain a mixed solution II. And pouring the obtained mixed solution II into a freezing container, placing the container on the top of a metal heat conducting column of a pre-prepared freezing device, and injecting the container into a barrel of the freezing device by taking liquid nitrogen as a cold source. And taking down the freezing container after the mixed solution is completely frozen, and putting the freezing container in a freeze drying box for freeze drying to obtain a blank. Taking the freeze-dried blank out of the freezing container, placing the blank in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon flow atmosphere, heating to 1400 ℃ at a speed of 5 ℃/min, heating to 1550 ℃ at a speed of 2 ℃/min, preserving heat for 2.5h, cooling to room temperature, and taking out to obtain the fiber composite boron carbide foamed ceramic material. Tests show that: the density of the prepared fiber composite boron carbide material is 0.31g/cm 3 The compressive strength is 3.2MPa.
Example 4
24g of water is taken as a dispersant, 7.02g of boron carbide powder with the average grain diameter of 0.5 mu m is added, and 0.45g of aluminum powder is added0.06g ammonium polymethacrylate was added to 0.17g carbon nanotubes. 170r/min for 2 hours to obtain a mixed solution I. And heating the mixed solution I to 60 ℃, adding 0.79g of sodium carboxymethylcellulose, and uniformly mixing to obtain a mixed solution II. And pouring the obtained mixed solution II into a freezing container, placing the container on the top of a metal heat conducting column of a pre-prepared freezing device, and injecting the container into a barrel of the freezing device by taking liquid nitrogen as a cold source. And taking down the freezing container after the mixed solution is completely frozen, and putting the freezing container in a freeze drying box for freeze drying. Taking the freeze-dried blank out of the freezing container, placing the blank in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon flow atmosphere, heating to 1400 ℃ at a speed of 5 ℃/min, heating to 1550 ℃ at a speed of 2 ℃/min, keeping the temperature for 3h, cooling to room temperature, and taking out to obtain the fiber composite boron carbide foamed ceramic material. Tests show that: the density of the prepared fiber composite boron carbide material is 0.32g/cm 3 The compressive strength is 2.7MPa.
Example 5
24g of water is taken as a dispersing agent, 6.50g of boron carbide powder with the average grain diameter of 0.5 mu m is added, 0.25g of silicon powder, 0.10g of carbon nano tube and 0.07g of ammonium polymethacrylate are added. 170r/min, and ball milling for 2h to obtain a mixed solution I. And heating the mixed solution I to 60 ℃, adding 0.60g of sodium carboxymethylcellulose, and uniformly mixing to obtain a mixed solution II. Pouring the obtained mixed solution II into a freezing container, placing the container on the top of a metal heat conducting column of a pre-prepared freezing device, and injecting the container into a barrel of the freezing device by taking liquid nitrogen as a cold source. And taking down the freezing container after the mixed solution is completely frozen, and putting the freezing container in a freeze drying box for freeze drying. Taking the freeze-dried blank out of the freezing container, placing the blank in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon flow atmosphere, heating to 1400 ℃ at a speed of 5 ℃/min, heating to 1550 ℃ at a speed of 2 ℃/min, preserving heat for 2.5h, cooling to room temperature, and taking out to obtain the fiber composite boron carbide foamed ceramic material. The test shows that: the density of the prepared fiber composite boron carbide material is 0.33g/cm 3 The compressive strength is 2.0MPa.

Claims (2)

1. The preparation method of the fiber composite boron carbide foam ceramic material is characterized by comprising the following steps:
step 1, preparing boron carbide powder into water slurry, sequentially adding an auxiliary agent, fibers and ammonium polymethacrylate according to a proportion, and mixing and ball-milling for 1-20h at the speed of 100-400r/min to obtain mixed slurry; then heating the mixed slurry to 30-90 ℃, adding a binder, and uniformly stirring to obtain a raw material solution; wherein the auxiliary agent is one or a combination of more than two of sodium carboxymethylcellulose, gelatin and polyvinyl alcohol;
wherein, the adding amount of the boron carbide is 10-45% of the mass of the water; the addition amount of the auxiliary agent is 0.5-20% of the mass of the solid component; the adding amount of the fiber is 0.5-10% of the mass of the solid component; the addition amount of the ammonium polymethacrylate is 0.1-5% of the mass of the solid components; the addition amount of the binder is 1-15% of the mass of the boron carbide powder;
step 2, pouring the raw material liquid prepared in the step 1 into a pre-prepared freezing container, placing the freezing container on the top of a metal heat conduction column of a pre-prepared freezing device, injecting liquid nitrogen serving as a cold source into a barrel of the freezing device, and directionally freezing the raw material liquid placed in the freezing container on the top of the freezing container; after completely freezing, placing the mixture in a freeze drying box for further drying to obtain a freeze-dried blank;
step 3, sintering the freeze-dried blank obtained in the step 2 at a certain temperature in an argon flow atmosphere, and cooling to room temperature to obtain a fiber composite boron carbide foam ceramic material; the sintering process comprises the following steps: heating to 1000 deg.C at 10 deg.C/min, heating to 1400 deg.C at 5 deg.C/min, heating to 1500-1700 deg.C at 2 deg.C/min, and maintaining for 1-10 hr;
the boron carbide is boron carbide powder with the grain size of 0.2-10 mu m;
the fiber is one or the combination of more than two of silicon carbide fiber, carbon fiber and carbon nano tube;
the binder is silicon powder or aluminum powder.
2. The method of claim 1, wherein the freezing device comprises a barrel with a metal liner and a thermal insulation material attached to the inner liner, and a metal column is vertically arranged in the barrel to serve as the metal heat-conducting column.
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