CN109592982A - A kind of boron carbide neutrons in nuclei absorbing material and preparation method - Google Patents
A kind of boron carbide neutrons in nuclei absorbing material and preparation method Download PDFInfo
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Abstract
The present invention relates to boron carbide neutrons in nuclei absorbing materials of a kind of structure-function integration and preparation method thereof, the following steps are included: being boron carbide powder (nuclear leve powder) 85~98.5wt% by weight percent, 1~5wt% of solid-phase sintering auxiliary agent, liquid-phase sintering auxiliary agent 0.5~10wt% three classes raw material is put into ball mill mixing container, addition high molecular material is soft template, and ball milling slurrying is carried out after deionized water is added, gained slurry solid concentration is 40~70wt%；Gained slurry obtains pelletizing with spray drying granulation mechanism；Pelletizing is depressed into green compact in 50-300MPa using dry-pressing formed or cold isostatic compaction technique；It puts the green body into vacuum drying oven, using vacuum or normal pressure-sintered mode, 0.5~5h completion sintering is kept the temperature at a temperature of 2000~2300 DEG C and obtains boron carbide ceramics.The present invention is using boron carbide nuclear leve powder as raw material, using high molecular material as soft template, it is prepared for porous silicon carbide boron neutrons in nuclei absorbing material, with it is at low cost, can mass production, free carbon content is low, neutron absorption effectiveness is high, suitable for preparing the advantages such as big-size complicated shape protecting component, small cores outer reactor protection and other types of nuclear reactor shieldings in have good application prospect.
Description
Technical field:
The present invention relates to a kind of boron carbide neutrons in nuclei absorbing material technical methods of structure-function integration, belong to advanced pottery
Porcelain field.
Technical background:
Boron carbide ceramics has good absorption neutron ability, this is because isotope in natural boron10The thermal capture of B
Section reaches 3850/b.Therefore, in nuclear industry, boron carbide ceramics is very important neutron absorber material.With nuclear industry
Fast development, boron carbide neutron absorption ball, control rod, storage nuke rubbish and the products such as boron carbide-based barricade in laboratory
Large-scale promotion application has been obtained in all types of nuclear reaction systems.The beginning of this century, the U.S. propose the advanced nuclear energy of forth generation
Reaction system, developing goal include sustainability, safety and reliability and economy, wherein miniaturization and safety are
The revolutionary of forth generation nuclear reactor is improved.It is reported that the protective layer outside the advanced nuclear reactor of external forth generation is big absolutely
Majority uses boron carbide protective materials, and to replace traditional lead base protective layer, boron carbide has lower density (2.52g/
cm3), reactor overall weight can be substantially reduced, miniaturization, the light-weight design of reactor are conducive to.In addition, boron carbide is made pottery
The good neutron absorption capability of porcelain can greatly improve the safety of nuclear reactor.
As the neutron absorber material and component of outer reactor nuclear defence, to the main body of the performance requirement of boron carbide ceramics
Present two aspects: first requirement boron carbide ceramics has certain porosity, because porous structure can increase to neutron
Sorbent surface product, improves absorption efficiency and protection effect；Second is the supporting member as outer layer, it is desirable that boron carbide ceramics has
Certain intensity and rigidity.For technique, at present, it can be achieved that the boron carbide neutrons in nuclei of industrialization absorbs the preparation of ceramic material
Method mainly has two kinds of techniques of hot pressed sintering and pressureless sintering.Since boron carbide ceramics covalent bond score is greater than 90% or more, from
Diffusion coefficient is very low, and the mechanism of mass transmission of the elimination of stomata, crystal boundary and bulk diffusion needs high temperature, simple boron carbide
Ceramic post sintering is extremely difficult, realizes that sintering densification is usually required by pressure or sintering aid etc..Heat pressing process is in high temperature
Apply certain pressure while sintering to boron carbide sintered body, promotes the densification of boron carbide ceramics, but heat pressing process list furnace
Limits throughput, and the infrastructure product that size is smaller, shape is relatively simple can only be prepared, therefore hot pressing boron carbide ceramics price ten
Divide valuableness.Non-pressure sintering technology advantage is to be suitble to large-scale production, can be first by the boron carbide green compact preprocessing after compression moulding
Molding is sintered again, is avoided high rigidity boron carbide sintered body processing bring increased costs, is particularly suitable for preparing big ruler
Very little, complicated shape structure member.In addition, nuclear reactor outer protective usually requires that neutron absorber material has certain hole
Rate, be conducive to neutron it is quick absorption and reaction, high-densit boron carbide ceramics to outer layer neutrons in nuclei protection be instead it is unfavorable,
Non-pressure sintering technology can regulate and control porosity, the crystallite dimension of boron carbide ceramics by addition sintering aid, optimization sintering temperature
Etc. microstructures, to guarantee the neutron absorption effectiveness of boron carbide ceramics.
In conclusion preparing a kind of porosity and having both the boron carbide neutron absorber material of some strength and rigidity to development
The nuclear energy reaction system of a new generation has important application value.Meanwhile no pressure preparation process has at low cost, microstructure can
It controls, be suitble to the advantages that preparing big-size complicated shape protecting component, there is huge application potential in nuclear reactor protection.
Summary of the invention:
The present invention especially minimizes forth generation nuclear reactor outer layer NEUTRON PROTECTION to boron carbide ceramics for nuclear reactor
Materials demand, using nuclear leve boron carbide powder as raw material, using high molecular material as soft template, in solid liquid phase sintering aid under the conditions of system
For the boron carbide neutrons in nuclei absorbing material containing certain porosity, low free carbon content.
The technical solution adopted by the present invention are as follows: a kind of boron carbide neutrons in nuclei absorbing material and preparation method, including following step
It is rapid:
(1) various raw materials are put into mixing container according to certain formula rate, the various raw materials include following heavy
Measure each component of percentage: boron carbide nuclear leve 85~98.5wt% of powder, solid-phase sintering 1~5wt% of auxiliary agent, liquid-phase sintering auxiliary agent
0.5~10wt%；Then ball milling slurrying additionally incorporates a certain amount of deionized water and polymer soft-template material before ball milling slurrying
Material, makes 40~70wt% of solid concentration of resulting slurry.
(2) by slurry obtained by step (1), granulation powder is made using spray drying granulation technique, specifically: use slurry
The slurry prepared in step (1) is sent into the prilling spry of spray drying granulation machine and is atomized by pump, and mashing pump conveys the pressure of slurry
Power is 0.02~0.4Mpa；Or it will be formed in the centrifugal turntable spray head of slurry feeding spray drying granulation machine using peristaltic pump micro-
Small droplet, centrifugal turntable revolving speed are 2000~20000 revs/min, and the inlet temperature of spray drying granulation machine is 120~250 DEG C,
100~150 DEG C of outlet temperature.
(3) pelletizing obtained by step (2) is pressed into green compact using dry pressure formed or cold isostatic compaction technique,
Briquetting pressure is 50~300MPa.
(4) green compact obtained by step (3) are put into vacuum sintering furnace, are sintered using non-pressure sintering technology.Tool
Body are as follows: vacuum degree is 10~1000Pa in control furnace before 1400~1600 DEG C, and 1400~1600 DEG C are passed through argon gas or helium is lazy
Property protective gas, or after evacuation heat before be passed through inert protective gas to normal pressure.Certain heating rate is set, 2000
0.5~5h completion sintering is kept the temperature at a temperature of~2300 DEG C obtains boron carbide ceramics.
Pulping equipment in above-mentioned steps (1) of the present invention is the mixing equipments such as ball mill, sand mill, planetary mills.
Ball milling slurrying in above-mentioned steps (1) of the present invention, by controlling ratio of grinding media to material, drum's speed of rotation, ball mill mixing time,
The slurry for being suitable for spray drying granulation is made, specially uses the medium ball of resin, zirconium oxide or silicon carbide as ball milling when,
Sphere diameter is 1~10mm, the ratio of the sum of ratio of grinding media to material, that is, medium ball weight and three kinds of boron carbide, carbon dust, carborundum powder raw material weights
Value is (0.5~5): 1, mixing time is 1~40h, and drum's speed of rotation is 50~900 revs/min.
The above-mentioned boron carbide powder of the present invention is nuclear leve powder, purity >=97%, total boron aggregation carbon >=98%, isotope10B content
>=19%, partial size D50: 7~50 μm.
The above-mentioned solid-phase sintering auxiliary agent of the present invention is mainly carbon, can be graphite powder, gas grain method carbon black, coke, stone
Oil coke is also possible to organic conversion carbon (i.e. organic carbon obtained organic conversion carbon), purity >=99wt%, and partial size is 5 μm
Below.
The above-mentioned liquid-phase sintering auxiliary agent of the present invention can be SiC, Y2O3、AlN、ZrO2、Al、WC、TiB2Deng one of or
It is several, purity >=95%, partial size D50It is 10 μm or less.
The above-mentioned polymer soft-template material of the present invention can for polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone,
One or more of phenolic resin, polyvinyl butyral, methylcellulose etc..
Raw material in above-mentioned steps (1) of the present invention can also include 0.5~5wt% of dispersing agent.Polymer soft-template is added
Each raw material proportioning after dispersing agent, in step (1) are as follows: boron carbide nuclear leve 85~98.5wt% of powder, solid-phase sintering auxiliary agent 1~
5wt%, liquid-phase sintering 0.5~10wt% of auxiliary agent, 5~20wt% of polymer soft-template, 0.5~5wt% of dispersing agent；Ball mill mixing
It is preceding that a certain amount of deionized water is added, so that the solid concentration of gained slurry is 40~70wt%.
Solid concentration is 40~70wt% after deionized water is added in above-mentioned steps (1) of the present invention, and solid concentration refers to
The solid state component total weight that boron carbide powder, solid-phase sintering auxiliary agent, liquid-phase sintering auxiliary agent are formed in raw material.
In above-mentioned steps (1) of the present invention the ratio of polymer soft-template and dispersing agent refer to two kinds of ingredients and boron carbide powder,
The ratio of solid-phase sintering auxiliary agent, liquid-phase sintering auxiliary agent solid state component.
The above-mentioned dispersing agent of the present invention is one of ammonium polyacrylate, ammonium citrate, tetramethylammonium hydroxide or one kind
More than.
The advantages of the present invention:
1. the present invention, using high molecular material as soft template, is prepared for a kind of porous carbon using nuclear leve boron carbide powder as raw material
Change boron neutron absorber material.Using the bridge linking effect of soft template, by solid phase under atomizing granulating technology and certain briquetting pressure
Grain is reunited and is connected, and removes soft template under high temperature, should so as to form the boron carbide ceramics for remaining certain porosity
Material is conducive to the sorbent surface product for increasing boron carbide ceramics to neutrons in nuclei in terms of functionality, improves neutron absorption effectiveness.
2. in practical applications, boron carbide absorbing material will have structure function simultaneously, usually it is prepared into having both one
Determine large scale, the complicated shape neutrons in nuclei protecting component of intensity, the support for reactor shielding layer.And 7 μm or more coarse granules
Boron carbide powder sintering activity is lower, and pure boron carbide powder sintering character is lower.Present invention employs solid-liquid phase sintering aids
The sintering of synergistic effect mechanism promotion boron carbide powder.Solid-phase sintering auxiliary agent is mainly carbon, can remove carbonization boron surface
Oxide layer be conducive to improve sintering activity, and carbon is present in boron carbide in sintering process to increase carbonization boron surface energy
Grain boundaries can prevent diffusion into the surface and evaporation, control grain boundary.Liquid-phase sintering promoter effect is to be formed under certain temperature
Low melting point liquid phase intermediate reduces sintering temperature, improves mass transfer rate.The deoxidation that the use of composite assistant can play carbon simultaneously is imitated
It should be acted on the liquid-phase sintering of Liquid Additive, promote boron carbide sintering densification, improve sintering character.
Detailed description of the invention:
Fig. 1 is boron carbide material of the invention.
Specific embodiment:
The present invention is described in further detail below by specific embodiment, but the present invention is not limited solely to following implementation
Example.
Raw material in the following embodiments of the present invention is commercial product, and equipment is industry conventional equipment.
Embodiment 1:
By 920 grams of (D of boron carbide nuclear leve powder50>=7 μm), 60 grams of carbon dust, 20 grams of carborundum powder, 1000 grams of deionized water, add
Enter in ball mill mixing container, 130g phenolic resin, 50 grams of polyvinyl alcohol and 30 grams of dispersing agents (ammonium polyacrylate) are added and carry out
Ball milling slurrying.Ball mill mixing time, drum's speed of rotation, ratio of grinding media to material are controlled, the slurry of suitable spray drying granulation is made, specifically
Are as follows: medium ball when using polyurethane ball as ball milling, bulb diameter 10mm, ratio of grinding media to material, that is, medium ball weight and boron carbide,
The ratio of the sum of three kinds of carbon dust, carborundum powder raw materials is 3:1, and the ball mill mixing time is 12 hours, and drum's speed of rotation is 80 revs/min
Clock.Then, pelletizing is obtained by mist projection granulating, specifically: after sieving with 100 mesh sieve slurry, slurry is sent into peristaltic pump and is sprayed
The centrifugal turntable spray head of mist drying-granulating machine, the revolving speed of centrifugal turntable are 5000 revs/min, form mist droplet, spray drying
The inlet temperature of pelletizer is 150 DEG C, and outlet temperature is 110 DEG C.Resulting pelletizing is dry-pressing formed under 150MPa pressure to be obtained
To green compact；It puts the green body into and carries out pressureless sintering in vacuum sintering furnace, 1h is kept the temperature at a temperature of 2180 DEG C, after natural cooling
To boron carbide ceramics.
The density of the boron carbide ceramics is 2.25g/cm3, relative density 89.0%.
Embodiment 2:
By 910 grams of (D of boron carbide nuclear leve powder98>=41 μm), 40 grams of carbon dust, oxidation 50 grams of yttrium powder, 1000 grams of deionized water, add
Enter in ball mill mixing container, be added 50g phenolic resin, 50 grams of polyvinyl butyrals and 20 grams of dispersing agents (ammonium citrate) into
Row ball milling slurrying (ball milling pulping process such as embodiment 1).Then, pelletizing is obtained by mist projection granulating, specifically: by slurry mistake
After 100 meshes, slurry is sent into the centrifugal turntable spray head of spray drying granulation machine with peristaltic pump, the revolving speed of centrifugal turntable is 6000
Rev/min, mist droplet is formed, the inlet temperature of spray drying granulation machine is 160 DEG C, and outlet temperature is 110 DEG C.It is resulting to make
Powder is dry-pressing formed under 150MPa pressure obtains green compact for grain；It puts the green body into and carries out pressureless sintering in vacuum sintering furnace,
1h is kept the temperature at a temperature of 2170 DEG C, obtains boron carbide ceramics after natural cooling.
The density of the boron carbide ceramics is 2.18g/cm3, consistency 86.2%.
Embodiment 3:
By 930 grams of (D of boron carbide nuclear leve powder50>=23 μm), 60 grams of carbon dust, 10 grams of zirconia powder, 1500 grams of deionized water, add
Enter in ball mill mixing container, 60g polyvinylpyrrolidone, 40 grams of polyethylene glycol oxides and 20 grams of dispersing agent (polyacrylic acid are added
Ammonium) carry out ball milling slurrying (ball milling pulping process such as embodiment 1).Then, pelletizing is obtained by mist projection granulating, specifically: it will
After slurry crosses 60 meshes, slurry is sent into the centrifugal turntable spray head of spray drying granulation machine, the revolving speed of centrifugal turntable with peristaltic pump
It is 6000 revs/min, forms mist droplet, the inlet temperature of spray drying granulation machine is 150 DEG C, and outlet temperature is 110 DEG C.Institute
The pelletizing obtained is dry-pressing formed under 150MPa pressure to obtain green compact；It puts the green body into and carries out pressureless sintering in vacuum sintering furnace,
1h is kept the temperature at a temperature of 2200 DEG C, obtains boron carbide ceramics after natural cooling.
The density of the boron carbide ceramics is 2.26g/cm3, consistency 90.1%.
Through the foregoing embodiment to the analysis of raw material composition and consistency, the boron carbide powder and soft mode of different-grain diameter are found
Plate/boron carbide mass ratio should keep certain relationship, be just able to achieve preferable porosity, intensity, rigid nature index it is comprehensive
It closes, by digital simulation and experimental verification, it is found that following relationship can achieve preferable effect:
In formula, D50For boron carbide powder partial size, m0For boron carbide powder quality, m1For soft template quality of materials.I.e. for partial size
Biggish boron carbide powder should increase boron carbide powder and soft template/boron carbide mass ratio according to above-mentioned formula, can guarantee hole
Soft template material utilization amount, economical environment-protective are reduced while gap rate, intensity, rigid nature index.
Claims (9)
1. a kind of boron carbide neutrons in nuclei absorbing material and preparation method, it is characterised in that: the following steps are included:
(1) various raw materials are put into mixing container according to certain formula rate, the various raw materials include following weight hundred
The each component of point ratio: boron carbide nuclear leve 85~98.5wt% of powder, solid-phase sintering 1~5wt% of auxiliary agent, liquid-phase sintering auxiliary agent 0.5~
10wt%；Then ball milling slurrying additionally incorporates a certain amount of deionized water and polymer soft-template material before ball milling slurrying, make institute
The solid concentration of the slurry obtained is 40~70wt%.
(2) by slurry obtained by step (1), granulation powder is made using spray drying granulation technique, specifically: it will using shurry pump
The slurry prepared in step (1) is sent into the prilling spry of spray drying granulation machine and is atomized, and the pressure of mashing pump conveying slurry is
0.02~0.4Mpa；Or slurry is sent into the centrifugal turntable spray head of spray drying granulation machine using peristaltic pump and forms small mist
Drop, centrifugal turntable revolving speed are 2000~20000 revs/min, and the inlet temperature of spray drying granulation machine is 120~250 DEG C, outlet
100~150 DEG C of temperature.
(3) pelletizing obtained by step (2) is pressed into green compact using dry pressure formed or cold isostatic compaction technique, formed
Pressure is 50~300MPa.
(4) green compact obtained by step (3) are put into vacuum sintering furnace, are sintered using non-pressure sintering technology.Specifically:
Vacuum degree is 10~1000Pa in control furnace before 1400~1600 DEG C, and 1400~1600 DEG C are passed through argon gas or the protection of helium inertia
Gas, or inert protective gas is passed through to normal pressure before heating after evacuation.Certain heating rate is set, 2000~2300
0.5~5h completion sintering is kept the temperature at a temperature of DEG C obtains boron carbide ceramics.
2. a kind of boron carbide neutrons in nuclei absorbing material according to claim 1 and preparation method, it is characterised in that: step
(1) pulping equipment in is the mixing equipments such as ball mill, sand mill, planetary mills.
3. a kind of boron carbide neutrons in nuclei absorbing material according to claim 1 and preparation method, it is characterised in that: step
(1) the ball milling slurrying in is made by controlling ratio of grinding media to material, drum's speed of rotation, ball mill mixing time and is suitable for spray drying granulation
Slurry, medium ball when specially using resin, zirconium oxide or silicon carbide as ball milling, sphere diameter is 1~10mm, and ratio of grinding media to material is
The weight of medium ball and the ratio of the sum of boron carbide, carbon dust, three kinds of raw material weights of carborundum powder are (0.5~5): 1, mixing time
For 1~40h, drum's speed of rotation is 50~900 revs/min.
4. a kind of boron carbide neutrons in nuclei absorbing material according to claim 1 and preparation method, it is characterised in that: described
Boron carbide powder is nuclear leve powder, purity >=97%, total boron aggregation carbon >=98%, isotope10B content >=19%, partial size D50: 7~
50μm。
5. a kind of boron carbide neutrons in nuclei absorbing material according to claim 1 and preparation method, it is characterised in that: described
Solid-phase sintering auxiliary agent is mainly carbon, can be graphite powder, gas grain method carbon black, coke, petroleum coke, is also possible to organic conversion
Carbon (i.e. organic carbon obtained organic conversion carbon), purity >=99wt%, partial size are 5 μm or less.
6. a kind of boron carbide neutrons in nuclei absorbing material according to claim 1 and preparation method, it is characterised in that: described
Liquid-phase sintering auxiliary agent can be SiC, Y2O3、AlN、ZrO2、Al、WC、TiB2One or more of Deng, purity >=95%, partial size
D50It is 10 μm or less.
7. a kind of boron carbide neutrons in nuclei absorbing material according to claim 1 and preparation method, it is characterised in that: described
Polymer soft-template material can be polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone, phenolic resin, polyvinyl alcohol contracting
One or more of butyraldehyde, methylcellulose etc..
8. a kind of boron carbide neutrons in nuclei absorbing material according to claim 1 and preparation method, it is characterised in that step (1)
In raw material can also include 0.5~5wt% of dispersing agent.After polymer soft-template and dispersing agent is added, each original in step (1)
Material proportion are as follows: boron carbide nuclear leve 85~98.5wt% of powder, solid-phase sintering 1~5wt% of auxiliary agent, liquid-phase sintering auxiliary agent 0.5~
10wt%, 5~20wt% of polymer soft-template, 0.5~5wt% of dispersing agent；A certain amount of deionized water is added before ball mill mixing,
So that the solid concentration of gained slurry is 40~70wt%.Solid concentration refers to boron carbide powder in raw material, solid-phase sintering auxiliary agent, liquid
The solid state component total weight that phase sintering auxiliary agent is formed.The ratio of polymer soft-template and dispersing agent refers to two kinds of ingredients and boron carbides
The ratio of powder, solid-phase sintering auxiliary agent, liquid-phase sintering auxiliary agent solid state component.
9. a kind of boron carbide neutrons in nuclei absorbing material according to claim 7 and preparation method, it is characterised in that: described
Dispersing agent be one of ammonium polyacrylate, ammonium citrate, tetramethylammonium hydroxide or more than one.
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