CN105734385B - A kind of iron-based ferrous acid dysprosium material and its application - Google Patents
A kind of iron-based ferrous acid dysprosium material and its application Download PDFInfo
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- CN105734385B CN105734385B CN201610217061.2A CN201610217061A CN105734385B CN 105734385 B CN105734385 B CN 105734385B CN 201610217061 A CN201610217061 A CN 201610217061A CN 105734385 B CN105734385 B CN 105734385B
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
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- C22C1/00—Making non-ferrous alloys
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- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
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Abstract
The invention discloses a kind of iron-based ferrous acid dysprosium material and its application, under inert gas shielding, by dysprosia powder and iron powder according to mass percent Fe (8~38%) Dy2O3Mixed after being weighed；By above-mentioned mixed-powder in ratio of grinding media to material 0.8~52:1st, under conditions of packing factor 0.15~0.85,80~550rpm of rotational speed of ball-mill, 2~98h of ball milling in the way of 50~60min of ball milling -4~6min of stopping；Then by the mixed-powder after ball milling under conditions of 80~480MPa of pressure 0.15~3.5h of isostatic cool pressing to be pressed into base substrate；Base substrate is placed under inert gas shielding again and sinters 5~50h at 750~1250 DEG C, iron-based ferrous acid dysprosium pellet is produced, can be as the excellent neutron absorber in command bundle rods for nuclear reactors, and equipment, technique are simple, easy to operate, controllability is superior, prepares low cost.
Description
Technical field
The present invention relates to belong to nuclear power plant reactor technical field, and in particular to a kind of iron-based ferrous acid dysprosium material and its should
With.
Background technology
In nuclear power station running, typically reactor Steam Generator in Load Follow is realized by adjusting control rod and changing boric acid concentration
Control.Control rod is neutron absorber, and its translational speed is fast, and operation is reliable, using flexible, controls the degree of accuracy of reactivity
It is high.And changing boric acid concentration can realize that the slow change to reactivity is controlled.
The opening of nuclear power plant reactor, stop main by control rod control with power adjusting.Once generation Nuclear Power Accident, control rod
It can automatically hurtle down, stop the chain reaction of nuclear fission in reactor, to ensure safety.The conventional neutron-absorbing material of control rod
Material has boron carbide (B4C), Ag-In-Cd, boron steel and combinations thereof body etc..And with B4C and the neutron that boron steel material is representative
Absorbing material easily under arms during there is more serious irradiation damage, this is mainly due to B10(n, α) reaction produced by
Caused by helium and swelling.The strongly exothermic property of steam generation that such material can be under the conditions of reactor disaster with HTHP in addition
Oxidation reaction, produces hydrogen, hydrogen occurs when serious quick-fried.Ag-In-Cd belongs to strong neutron absorber, during military service, and its is small
Movement can bring the change by a relatively large margin of reactivity, generally require change boric acid concentration to coordinate it to move.But utilize and change cold
But the boric acid concentration in water can produce a large amount of waste water come the method for following load, so as to increase entreprise cost, while using the party
Method is long to the time of reactivity regulation.Therefore, design is used in control rod using weak neutron absorber pellet in nuclear reactor
Instead of being realized with adjusting boric acid concentration method to the micro control of nuclear reactivity and regulation.
Dysprosium has the relatively large stable isotope in five kinds of neutron absorption cross-sections, and neutron absorption is cut after nuclear reaction is carried out
Face will not undergo mutation, beneficial to stability contorting nuclear reactivity.The gamma activity of the transmutation product of dysprosium is low, and half-life short is set to reactor core
Standby infringement is small.Dy2TiO5Block is applied as the neutron absorber material of control rod in some nuclear power stations, its core
The heart is the superior nucleon characteristic using dysprosium element.Dy can be learnt from equilbrium phase diagram2TiO5With three kinds of crystal structures, including just
Hand over crystal structure (0~1350 DEG C), hexagonal crystallographic texture (1350 DEG C~1680 DEG C) and cubic crystal structure (fluorite structure)
(1680 DEG C~1870 DEG C).The anti-radiation performance of the block materials of fluorite structure is best, its void swelling under identical radiation parameter
Rate and irradiation growth rate are minimum, and radiation stabilized is good, the transformation that crystal structure will not occur in irradiation process.And in radiation parameter
The Dy of lower orthorhombic crystal structure2TiO5Crystal transfer can occur before decrystallized, fluorite knot is changed into by orthorhombic crystal structure
Structure, the change of crystal structure can cause the change of the volume, thermal conductivity and thermal coefficient of expansion of block materials.Therefore researchers cause
Power is in the Dy for obtaining fluorite structure2TiO5Block materials, but because fluorite structure belongs to high-temperature-phase, and control rod long service
Temperature is less than 1000 DEG C, even if therefore preparing the Dy of high temperature fluorite structure2TiO5Block, under arms during will certainly turn
It is changed into low temperature orthorhombic crystal structure, this is unfavorable for the stability and security of nuclear reaction.Command bundle rods for nuclear reactors neutron-absorbing
Another key property requirement of material pellet is that the heat conductivity of pellet is superior, so as to during under arms because neutron is anti-
The heat that should be generated in pellet can be conducted in time, it is ensured that the security of nuclear reaction, and Dy2TiO5The heat biography of ceramic pellet
The property led is relatively poor.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art part there is provided a kind of iron-based ferrous acid dysprosium material and its answer
Can be as excellent in command bundle rods for nuclear reactors with, the iron-based ferrous acid dysprosium pellet prepared by the use of the iron-based ferrous acid dysprosium material
Neutron absorber, and equipment, technique are simple, easy to operate, controllability is superior, prepares low cost.
One of the technical solution adopted for the present invention to solve the technical problems is：
A kind of iron-based ferrous acid dysprosium material, ferrous acid dysprosium of the iron-based ferrous acid dysprosium material by iron-based and disperse in iron-based
(DyFeO3) composition, and the mass ratio of ferrous acid dysprosium and iron-based is 1:0.8~1:6.2.Ferrous acid dysprosium of the disperse in iron-based can
To be p-type ferrous acid dysprosium.
The two of the technical solution adopted for the present invention to solve the technical problems are：
A kind of iron-based ferrous acid dysprosium pellet being made up of above-mentioned material.
The three of the technical solution adopted for the present invention to solve the technical problems are：
A kind of method for preparing above-mentioned iron-based ferrous acid dysprosium pellet, including：
Under inert gas shielding, by the drying dysprosia powder of 4.5~5.5 μm of particle mean size, purity more than 99.5%
With the mesh of particle mean size 350~450, the drying iron powder of purity more than 99.8%, according to mass percent Fe- (8~38%)
Dy2O3Mixed after being weighed, add process control agent and its whole mass concentration is no more than 1%, obtain mixed-powder；Will
Above-mentioned mixed-powder is in ratio of grinding media to material 0.8~52:1st, under conditions of packing factor 0.15~0.85,80~550rpm of rotational speed of ball-mill,
2~98h of ball milling in the way of 50~60min of ball milling -4~6min of stopping；Then by the mixed-powder after ball milling in pressure 80
0.15~3.5h of isostatic cool pressing is to be pressed into base substrate under conditions of~480MPa；Base substrate is placed under inert gas shielding again
750~1250 DEG C of 5~50h of sintering, produce described iron-based ferrous acid dysprosium pellet.Wherein, increase with the amount of dysprosia, correspondingly
Sintering temperature needs are higher, and ball milling, isostatic cool pressing, the time sintered need longer.
In one embodiment：The mass percent is Fe- (9~33%) Dy2O3；The parameter of mechanical milling process be ratio of grinding media to material 9~
11:1, packing factor 0.48~0.52,370~390rpm of rotational speed of ball-mill, 2.5~49h of Ball-milling Time；The ginseng of isostatic cool pressing process
Number is 0.4~0.6h of isostatic cool pressing under 250~270MPa；The parameter of sintering process is 11~17h of sintering at 780~920 DEG C.
In one embodiment：The mass percent is Fe- (9~11%) %Dy2O3；The parameter of mechanical milling process is ratio of grinding media to material
0.9~1.1:1, packing factor 0.18~0.22,90~110rpm of rotational speed of ball-mill, 95~97h of Ball-milling Time；Isostatic cool pressing process
Parameter be 90~110MPa under 2.8~3.2h of isostatic cool pressing；The parameter of sintering process be 1180~1220 DEG C at sintering 47~
49h。
In one embodiment：The mass percent is Fe- (9~38%) Dy2O3；The parameter of mechanical milling process be ratio of grinding media to material 9~
11:1, packing factor 0.48~0.52,370~390rpm of rotational speed of ball-mill, 47~49h of Ball-milling Time；The ginseng of isostatic cool pressing process
Number is 0.4~0.6h of isostatic cool pressing under 250~270MPa；The parameter of sintering process is 7~49h of sintering at 1180~1220 DEG C.
In one embodiment：The mass percent is Fe- (36~38%) Dy2O3；The parameter of mechanical milling process is ratio of grinding media to material 49
~51:1, packing factor 0.78~0.82,490~510rpm of rotational speed of ball-mill, 47~49h of Ball-milling Time；Isostatic cool pressing process
Parameter is 0.18~0.22h of isostatic cool pressing under 440~460MPa；The parameter of sintering process be 1180~1220 DEG C at sintering 23~
25h。
In one embodiment：The mass percent is Fe- (18~26%) Dy2O3；The parameter of mechanical milling process is ratio of grinding media to material 9
~11:1, packing factor 0.48~0.52,370~390rpm of rotational speed of ball-mill, 2.5~3.5h of Ball-milling Time；Isostatic cool pressing process
Parameter be 250~270MPa under 0.4~0.6h of isostatic cool pressing；The parameter of sintering process be 1180~1220 DEG C at sintering 23~
25h。
The four of the technical solution adopted for the present invention to solve the technical problems are：
A kind of above-mentioned iron-based ferrous acid dysprosium pellet is used for the purposes for preparing command bundle rods for nuclear reactors.
The five of the technical solution adopted for the present invention to solve the technical problems are：
Above-mentioned iron-based ferrous acid dysprosium pellet is provided with a kind of command bundle rods for nuclear reactors, including involucrum, the involucrum.
Method for expressing Fe- (8~38%) Dy of the mass percent of the present invention2O3Refer to dysprosia (Dy2O3) powder with
In the mixture of iron (Fe) powder, the mass fraction of dysprosia powder is 8~38%；Similarly, Fe-10%Dy2O3, Fe-19%
Dy2O3, Fe-25.68%Dy2O3, Fe-32%Dy2O3, Fe-37%Dy2O3Refer respectively to the mixed of dysprosia powder and iron powder
In compound, the mass fraction of dysprosia powder is 10%, 19%, 25.68%, 32%, 37%.
Its " inert gas " of the present invention can be nitrogen, argon gas, hydrogen, helium, carbon dioxide etc., or above-mentioned gas
One or more mixing, it, which is acted on, is starvation and keeps certain pressure intensity, while gas is not involved in reaction in itself.
The technical program is compared with background technology, and it has the following advantages that：
The invention provides a kind of iron-based ferrous acid dysprosium material and its application, joined using powder metallurgical technique in specific technique
Under several, by high-energy ball milling method so that Fe powder and Dy2O3Powder is uniformly mixed, then obtained after isostatic cool pressing and sintering
Iron-based ferrous acid dysprosium material has excellent heat-conductive characteristic, mechanical property and low thermal coefficient of expansion, gives full play to dysprosium element
Superior nucleon characteristic, moreover it is possible to avoid Dy2TiO5Ceramic material is used as the crystal structure diversity present in control rod pellet, spoke
According to the deficiency of unstability and heat-conductive characteristic difference etc., so as to be used as the excellent neutron-absorbing in command bundle rods for nuclear reactors
Body.The equipment of the present invention, technique are simple, and easy to operate, controllability is superior, low cost, meanwhile, than being prepared using powder metallurgical technique
Dy2TiO5The sintering temperature of fluorite structure pellet is low, is conducive to further reduction to prepare cost.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 be the embodiment of the present invention 1 according to mass percent Fe-32%Dy2O3Mixed-powder after weighing is by different
The X ray diffracting spectrum of Ball-milling Time.
Fig. 2 is the X ray diffracting spectrum of the three kinds of iron-based ferrous acid dysprosium pellets obtained in the embodiment of the present invention 1.
Fig. 3 is the X ray diffracting spectrum of the three kinds of iron-based ferrous acid dysprosium pellets obtained in the embodiment of the present invention 4.
Fig. 4 is that the elongation of iron-based ferrous acid dysprosium pellet and thermal coefficient of expansion obtained in the embodiment of the present invention 7 becomes with temperature
Change schematic diagram, wherein solid line represents that elongation varies with temperature schematic diagram, and dotted line represents that thermal coefficient of expansion varies with temperature signal
Figure.
Fig. 5 is the final pellet signal of obtained iron-based ferrous acid dysprosium pellet after over mechanical processing in the embodiment of the present invention 7
Figure.
Fig. 6 is the scanning electron microscope (SEM) photograph on the iron-based ferrous acid dysprosium pellet surface obtained in the embodiment of the present invention 8.
Embodiment
Present disclosure is illustrated below by embodiment：
Embodiment 1
Take average 5 μm of granularity, the drying Dy of purity 99.6%2O3Starting powder and the mesh of particle mean size 400, purity 99.9%
Drying atomization iron starting powder, in glove box under inert gas shielding, respectively according to mass percent Fe-10%Dy2O3、
Fe-25.68%Dy2O3, Fe-32%Dy2O3Mixed respectively after being weighed, operations described below is carried out respectively：Load planetary high energy
In ball mill, further according to needing to be suitably added process control agent such as stearic acid and its whole mass concentration is no more than 1%, mixed
Close powder；By above-mentioned mixed-powder in ratio of grinding media to material 10:1st, under conditions of packing factor 0.5, rotational speed of ball-mill 380rpm, according to ball milling
55min-stopping 5min mode 3~48h of ball milling, intermittent duty can prevent that ball grinder temperature is too high.
Fig. 1 is according to mass percent Fe-32%Dy2O3Mixed-powder after weighing passes through the X-ray of different Ball-milling Times
Diffracting spectrum.It can be seen that with the increase of Ball-milling Time, Dy2O3Mutually and Fe phases diffraction maximum gradually wideization, intensity
Gradually reduce.Wideization of diffraction maximum is main as caused by two aspect factors, includes the production of refinement and the distortion of lattice of crystal particle scale
It is raw.From Fig. 1, it is observed that with the increase Dy of Ball-milling Time2O3The diffraction peak intensity of phase is reduction, after 48h ball millings
It is wholly absent, shows that destruction and constituent element of the perfection of crystal by ball milling there occurs continuous solid solution, this make it that participation is spread out
The number of die penetrated reduces to cause peak gradually to decrease up to disappearance.High-energy ball milling makes Dy2O3While particle and the refinement of Fe particles
A large amount of new surfaces and lattice defect are generated, crystallite dimension reduces diffusion length while reduction, is conducive to the diffusion of atom
And rearrangement, it is active very high, be conducive to the progress of sintering reaction.
Take above-mentioned according to mass percent Fe-10%Dy2O3, Fe-25.68%Dy2O3, Fe-32%Dy2O3Weigh, mix,
Mixed-powder after ball milling 3h carries out operations described below respectively：Load rubber package set in glove box, then by the rubber package set tightened
It is placed in the hydraulic cylinder in isostatic cool pressing instrument, isostatic cool pressing 0.5h is to be pressed into column base under conditions of pressure 260MPa
Body；Base substrate is placed in Ar-sintering stove again and sinters 16h at 900 DEG C, the iron-based iron of three kinds of different ferrous acid dysprosium contents is produced
The mass ratio of sour dysprosium pellet, ferrous acid dysprosium and iron-based is respectively 1:6.10,1:1.82,1:1.28.
Fig. 2 is the X ray diffracting spectrum of above-mentioned three kinds of iron-baseds ferrous acid dysprosium pellet.As can be seen that after 900 DEG C sinter 16h,
Do not detect Dy2O3Diffraction maximum, do not detect the diffraction maximum of Fe oxide yet, only detected Fe and DyFeO3's
Diffraction maximum, illustrates Dy2O3DyFeO has been completely reformed into Fe reactions3, form iron-based ferrous acid dysprosium block.
Above-mentioned iron-based ferrous acid dysprosium pellet can obtain the final pellet of regular shape after over mechanical processing, and this is final
Pellet is placed in command bundle rods for nuclear reactors involucrum, and a kind of command bundle rods for nuclear reactors is constituted together with other parts, available for controlling
The operation of nuclear power plant reactor processed.
Embodiment 2
Take average 5 μm of granularity, the drying Dy of purity 99.6%2O3Starting powder and the mesh of particle mean size 400, purity 99.9%
Drying atomization iron starting powder, in glove box under inert gas shielding, according to mass percent Fe-10%Dy2O3Claimed
Mix, be fitted into planetary high-energy ball mill after amount, further according to needing to be suitably added process control agent such as stearic acid and make its end
Mass concentration is no more than 1%, obtains mixed-powder；By above-mentioned mixed-powder in ratio of grinding media to material 10:1st, packing factor 0.5, ball milling turn
Under conditions of fast 380rpm, the ball milling 3h in the way of ball milling 55min-stopping 5min, intermittent duty can prevent ball grinder temperature
Spend height；Then the mixed-powder after ball milling is loaded into rubber package set in glove box, then the rubber package set tightened is placed in cold
In hydraulic cylinder in isostatic pressed instrument, isostatic cool pressing 0.5h is to be pressed into column base substrate under conditions of pressure 260MPa；Again will
Base substrate is placed in Ar-sintering stove sinters 12h at 800 DEG C, produces the quality of iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium and iron-based
Than for 1:6.10.
Above-mentioned iron-based ferrous acid dysprosium pellet can obtain the final pellet of regular shape after over mechanical processing, and this is final
Pellet is placed in command bundle rods for nuclear reactors involucrum, a kind of command bundle rods for nuclear reactors is constituted together with other parts, and can be used for
Control the operation of nuclear power plant reactor.
Embodiment 3
Take average 5 μm of granularity, the drying Dy of purity 99.6%2O3Starting powder and the mesh of particle mean size 400, purity 99.9%
Drying atomization iron starting powder, in glove box under inert gas shielding, according to mass percent Fe-10%Dy2O3Claimed
Mix, be fitted into planetary high-energy ball mill after amount, further according to needing to be suitably added process control agent such as stearic acid and make its end
Mass concentration is no more than 1%, obtains mixed-powder；By above-mentioned mixed-powder in ratio of grinding media to material 1:1st, packing factor 0.2, rotational speed of ball-mill
Under conditions of 100rpm, the ball milling 96h in the way of ball milling 55min-stopping 5min, intermittent duty can prevent ball grinder temperature
Spend height；Then the mixed-powder after ball milling is loaded into rubber package set in glove box, then the rubber package set tightened is placed in cold
In hydraulic cylinder in isostatic pressed instrument, isostatic cool pressing 3h is to be pressed into column base substrate under conditions of pressure 100MPa；Again by base
Body is placed in Ar-sintering stove sinters 48h at 1200 DEG C, produces the mass ratio of iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium and iron-based
For 1:6.10.
Above-mentioned iron-based ferrous acid dysprosium pellet can obtain the final pellet of regular shape after over mechanical processing, and this is final
Pellet is placed in command bundle rods for nuclear reactors involucrum, a kind of command bundle rods for nuclear reactors is constituted together with other parts, and can be used for
Control the operation of nuclear power plant reactor.
Embodiment 4
Take average 5 μm of granularity, the drying Dy of purity 99.6%2O3Starting powder and the mesh of particle mean size 400, purity 99.9%
Drying atomization iron starting powder, in glove box under inert gas shielding, respectively according to mass percent Fe-10%Dy2O3、
Fe-19%Dy2O3, Fe-25.68%Dy2O3, Fe-32%Dy2O3Mixed respectively after being weighed, operations described below is carried out respectively：Dress
Enter in planetary high-energy ball mill, further according to needing to be suitably added process control agent such as stearic acid and its whole mass concentration is not surpassed
1% is crossed, mixed-powder is obtained；By above-mentioned mixed-powder in ratio of grinding media to material 10:1st, packing factor 0.5, rotational speed of ball-mill 380rpm bar
Under part, the ball milling 48h in the way of ball milling 55min-stopping 5min, intermittent duty can prevent that ball grinder temperature is too high；Then
Mixed-powder after ball milling is loaded into rubber package set in glove box, then the rubber package set tightened is placed in isostatic cool pressing instrument
Hydraulic cylinder in, isostatic cool pressing 0.5h is to be pressed into column base substrate under conditions of pressure 260MPa；Base substrate is placed in argon gas again
Protect in sintering furnace and sinter 8h at 1200 DEG C, produce the iron-based ferrous acid dysprosium pellet of three kinds of different ferrous acid dysprosium contents, ferrous acid dysprosium and iron
The mass ratio of base is respectively 1:6.10,1:2.78,1:1.82,1:1.28.
Fig. 3 is the X ray diffracting spectrum of above-mentioned three kinds of iron-baseds ferrous acid dysprosium pellet.As can be seen that after 1200 DEG C sinter 8h,
Do not detect Dy2O3Diffraction maximum, do not detect the diffraction maximum of Fe oxide yet, only detected Fe and DyFeO3's
Diffraction maximum, illustrates Dy2O3DyFeO has been completely reformed into Fe reactions3, form iron-based ferrous acid dysprosium block.
Above-mentioned iron-based ferrous acid dysprosium pellet can obtain the final pellet of regular shape after over mechanical processing, and this is final
Pellet is placed in command bundle rods for nuclear reactors involucrum, a kind of command bundle rods for nuclear reactors is constituted together with other parts, and can be used for
Control the operation of nuclear power plant reactor.
Embodiment 5
Take average 5 μm of granularity, the drying Dy of purity 99.6%2O3Starting powder and the mesh of particle mean size 400, purity 99.9%
Drying atomization iron starting powder, in glove box under inert gas shielding, according to mass percent Fe-37%Dy2O3Claimed
Mix, be fitted into planetary high-energy ball mill after amount, further according to needing to be suitably added process control agent such as stearic acid and make its end
Mass concentration is no more than 1%, obtains mixed-powder；By above-mentioned mixed-powder in ratio of grinding media to material 10:1st, packing factor 0.5, ball milling turn
Under conditions of fast 380rpm, the ball milling 48h in the way of ball milling 55min-stopping 5min, intermittent duty can prevent ball grinder
Temperature is too high；Then the mixed-powder after ball milling is loaded into rubber package set in glove box, then the rubber package set tightened is placed in
In hydraulic cylinder in isostatic cool pressing instrument, isostatic cool pressing 0.5h is to be pressed into column base substrate under conditions of pressure 260MPa；Again
Base substrate is placed in Ar-sintering stove and sinters 48h at 1200 DEG C, the matter of iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium and iron-based is produced
Amount is than being 1:1.
Above-mentioned iron-based ferrous acid dysprosium pellet can obtain the final pellet of regular shape after over mechanical processing, and this is final
Pellet is placed in command bundle rods for nuclear reactors involucrum, a kind of command bundle rods for nuclear reactors is constituted together with other parts, and can be used for
Control the operation of nuclear power plant reactor.
Embodiment 6
Take average 5 μm of granularity, the drying Dy of purity 99.6%2O3Starting powder and the mesh of particle mean size 400, purity 99.9%
Drying atomization iron starting powder, in glove box under inert gas shielding, according to mass percent Fe-37%Dy2O3Claimed
Mix, be fitted into planetary high-energy ball mill after amount, further according to needing to be suitably added process control agent such as stearic acid and make its end
Mass concentration is no more than 1%, obtains mixed-powder；By above-mentioned mixed-powder in ratio of grinding media to material 50:1st, packing factor 0.8, ball milling turn
Under conditions of fast 500rpm, the ball milling 48h in the way of ball milling 55min-stopping 5min, intermittent duty can prevent ball grinder
Temperature is too high；Then the mixed-powder after ball milling is loaded into rubber package set in glove box, then the rubber package set tightened is placed in
In hydraulic cylinder in isostatic cool pressing instrument, isostatic cool pressing 0.2h is to be pressed into column base substrate under conditions of pressure 450MPa；Again
Base substrate is placed in Ar-sintering stove and sinters 24h at 1200 DEG C, the matter of iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium and iron-based is produced
Amount is than being 1:1.
Above-mentioned iron-based ferrous acid dysprosium pellet can obtain the final pellet of regular shape after over mechanical processing, and this is final
Pellet is placed in command bundle rods for nuclear reactors involucrum, a kind of command bundle rods for nuclear reactors is constituted together with other parts, and can be used for
Control the operation of nuclear power plant reactor.
Embodiment 7
Take average 5 μm of granularity, the drying Dy of purity 99.6%2O3Starting powder and the mesh of particle mean size 400, purity 99.9%
Drying atomization iron starting powder, in glove box under inert gas shielding, according to mass percent Fe-25.68%Dy2O3Enter
Row is mixed after weighing, and is fitted into planetary high-energy ball mill, further according to needing to be suitably added process control agent such as stearic acid and make
Its whole mass concentration is no more than 1%, obtains mixed-powder；By above-mentioned mixed-powder in ratio of grinding media to material 10:1st, packing factor 0.5, ball
Grind under conditions of rotating speed 380rpm, the ball milling 3h in the way of ball milling 55min-stopping 5min, intermittent duty can prevent ball milling
Tank temperature is too high；Then the mixed-powder after ball milling is loaded into rubber package set in glove box, then the rubber bag tightened is nested with
In hydraulic cylinder in isostatic cool pressing instrument, isostatic cool pressing 0.5h is to be pressed into column base substrate under conditions of pressure 260MPa；
Base substrate is placed in Ar-sintering stove again and sinters 24h at 1200 DEG C, iron-based ferrous acid dysprosium pellet is produced, ferrous acid dysprosium and iron-based
Mass ratio is 1:1.82.
According to standard GB/T/T-5163-2006《The measure of density of sintered material, oil content and percent opening》Tested
The density of above-mentioned iron-based ferrous acid dysprosium pellet is 6.54g/cm3。
The above-mentioned iron-based ferrous acid dysprosium block tested using heat transfer analysis instrument is in room temperature, the thermal diffusion system of 500 DEG C and 800 DEG C
Number, thermal capacitance, the value of thermal conductivity are listed in Table 1 below.
The iron-based ferrous acid dysprosium of table 1 sinters the physical property test result of block
The elongation and thermal coefficient of expansion for the above-mentioned sintering block tested using thermal dilatometer are varied with temperature such as Fig. 4 institutes
Show.
Above-mentioned iron-based ferrous acid dysprosium pellet can obtain the final pellet of regular shape after over mechanical processing, such as Fig. 5 institutes
Show.The final pellet is placed in command bundle rods for nuclear reactors involucrum, a kind of nuclear reactor control is constituted together with other parts
Rod, and available for the operation of control nuclear power plant reactor.
Embodiment 8
Take average 5 μm of granularity, the drying Dy of purity 99.6%2O3Starting powder and the mesh of particle mean size 400, purity 99.9%
Drying atomization iron starting powder, in glove box under inert gas shielding, according to mass percent Fe-19%Dy2O3Claimed
Mix, be fitted into planetary high-energy ball mill after amount, further according to needing to be suitably added process control agent such as stearic acid and make its end
Mass concentration is no more than 1%, obtains mixed-powder；By above-mentioned mixed-powder in ratio of grinding media to material 10:1st, packing factor 0.5, ball milling turn
Under conditions of fast 380rpm, the ball milling 3h in the way of ball milling 55min-stopping 5min, intermittent duty can prevent ball grinder temperature
Spend height；Then the mixed-powder after ball milling is loaded into rubber package set in glove box, then the rubber package set tightened is placed in cold
In hydraulic cylinder in isostatic pressed instrument, isostatic cool pressing 0.5h is to be pressed into column base substrate under conditions of pressure 260MPa；Again will
Base substrate is placed in Ar-sintering stove sinters 24h at 1200 DEG C, produces the quality of iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium and iron-based
Than for 1:2.78.
Fig. 6 is the scanning electron microscope (SEM) photograph on iron-based ferrous acid dysprosium pellet surface, be can see from scanning electron microscope (SEM) photograph, in sintering process
The DyFeO of middle formation3It is distributed in iron-based, DyFeO3It is in irregular shape.
Above-mentioned iron-based ferrous acid dysprosium pellet can obtain the final pellet of regular shape after over mechanical processing, and this is final
Pellet is placed in command bundle rods for nuclear reactors involucrum, a kind of command bundle rods for nuclear reactors is constituted together with other parts, and can be used for
Control the operation of nuclear power plant reactor.
Skilled person will appreciate that, when the technical parameter of the present invention changes in following scope, it is contemplated that obtain
Technique effect same as the previously described embodiments or close：
Under inert gas shielding, by the drying dysprosia powder and average grain of 5 μm of particle mean size, purity more than 99.5%
400 mesh, the drying iron powder of purity more than 99.8% are spent, according to mass percent Fe- (10~37%) Dy2O3After being weighed
Mixing, adds process control agent and its whole mass concentration is no more than 1%, obtain mixed-powder；Above-mentioned mixed-powder is existed
Ratio of grinding media to material 1~50:1st, under conditions of packing factor 0.2~0.8,100~500rpm of rotational speed of ball-mill, according to ball milling 55min-stop
Only 5min 3~96h of mode ball milling；Then by the mixed-powder after ball milling under conditions of 100~450MPa of pressure it is cold etc. quiet
0.2~3h is pressed to be pressed into base substrate；Base substrate is placed under inert gas shielding again and sinters 8~48h at 800~1200 DEG C, is produced
Iron-based ferrous acid dysprosium pellet, it is made up of the ferrous acid dysprosium of iron-based and disperse in iron-based, and the mass ratio of ferrous acid dysprosium and iron-based is 1:1
~1:6.1；Ferrous acid dysprosium of the disperse in iron-based can be p-type ferrous acid dysprosium.
The above, only present pre-ferred embodiments, therefore the scope that the present invention is implemented can not be limited according to this, i.e., according to
Equivalence changes and modification that the scope of the claims of the present invention and description are made, all should still belong in the range of the present invention covers.
Claims (10)
1. a kind of iron-based ferrous acid dysprosium material, it is characterised in that：The iron-based ferrous acid dysprosium material is by iron-based and disperse in iron-based
Ferrous acid dysprosium is constituted, and the mass ratio of ferrous acid dysprosium and iron-based is 1:0.8~1:6.2；The iron-based ferrous acid dysprosium material is in the following manner
Prepare：Under inert gas shielding, by the drying dysprosia powder of 4.5~5.5 μm of particle mean size, purity more than 99.5%
With the mesh of particle mean size 350~450, the drying iron powder of purity more than 99.8%, according to mass percent Fe- (8~38%)
Dy2O3Mixed after being weighed, add process control agent and its whole mass concentration is no more than 1%, obtain mixed-powder；Will
Above-mentioned mixed-powder is in ratio of grinding media to material 0.8~52:1st, under conditions of packing factor 0.15~0.85,80~550rpm of rotational speed of ball-mill,
2~98h of ball milling in the way of 50~60min of ball milling -4~6min of stopping；Then by the mixed-powder after ball milling in pressure 80
Under conditions of~480MPa after 0.15~3.5h of isostatic cool pressing；Be placed in again under inert gas shielding 750~1250 DEG C sinter 5~
50h, is produced.
2. the iron-based ferrous acid dysprosium pellet that a kind of material as described in claim 1 is made.
3. a kind of method of the iron-based ferrous acid dysprosium pellet prepared described in claim 2, it is characterised in that：Including：
Under inert gas shielding, by 4.5~5.5 μm of particle mean size, the drying dysprosia powder peace of purity more than 99.5%
The equal mesh of granularity 350~450, the drying iron powder of purity more than 99.8%, according to mass percent Fe- (8~38%) Dy2O3Enter
Row is mixed after weighing, and is added process control agent and its whole mass concentration is no more than 1%, obtains mixed-powder；Will be above-mentioned mixed
Powder is closed in ratio of grinding media to material 0.8~52:1st, under conditions of packing factor 0.15~0.85,80~550rpm of rotational speed of ball-mill, according to ball
Grind 50~60min -4~6min of stopping 2~98h of mode ball milling；Then by the mixed-powder after ball milling pressure 80~
0.15~3.5h of isostatic cool pressing is to be pressed into base substrate under conditions of 480MPa；Base substrate is placed under inert gas shielding 750 again
~1250 DEG C of 5~50h of sintering, produce described iron-based ferrous acid dysprosium pellet.
4. method according to claim 3, it is characterised in that：The mass percent is Fe- (9~33%) Dy2O3；Ball
The parameter of honed journey is ratio of grinding media to material 9~11:1, packing factor 0.48~0.52,370~390rpm of rotational speed of ball-mill, Ball-milling Time
2.5~49h；The parameter of isostatic cool pressing process is 0.4~0.6h of isostatic cool pressing under 250~270MPa；The parameter of sintering process is
11~17h is sintered at 780~920 DEG C.
5. method according to claim 3, it is characterised in that：The mass percent is Fe- (9~11%) %Dy2O3；
The parameter of mechanical milling process is ratio of grinding media to material 0.9~1.1:1, packing factor 0.18~0.22,90~110rpm of rotational speed of ball-mill, during ball milling
Between 95~97h；The parameter of isostatic cool pressing process is 2.8~3.2h of isostatic cool pressing under 90~110MPa；The parameter of sintering process is
47~49h is sintered at 1180~1220 DEG C.
6. method according to claim 3, it is characterised in that：The mass percent is Fe- (9~38%) Dy2O3；Ball
The parameter of honed journey is ratio of grinding media to material 9~11:1, packing factor 0.48~0.52,370~390rpm of rotational speed of ball-mill, Ball-milling Time 47
~49h；The parameter of isostatic cool pressing process is 0.4~0.6h of isostatic cool pressing under 250~270MPa；The parameter of sintering process is 1180
7~49h is sintered at~1220 DEG C.
7. method according to claim 3, it is characterised in that：The mass percent is Fe- (36~38%) Dy2O3；Ball
The parameter of honed journey is ratio of grinding media to material 49~51:1, packing factor 0.78~0.82,490~510rpm of rotational speed of ball-mill, Ball-milling Time
47~49h；The parameter of isostatic cool pressing process is 0.18~0.22h of isostatic cool pressing under 440~460MPa；The parameter of sintering process is
23~25h is sintered at 1180~1220 DEG C.
8. method according to claim 3, it is characterised in that：The mass percent is Fe- (18~26%) Dy2O3；Ball
The parameter of honed journey is ratio of grinding media to material 9~11:1, packing factor 0.48~0.52,370~390rpm of rotational speed of ball-mill, Ball-milling Time
2.5~3.5h；The parameter of isostatic cool pressing process is 0.4~0.6h of isostatic cool pressing under 250~270MPa；The parameter of sintering process is
23~25h is sintered at 1180~1220 DEG C.
9. a kind of iron-based ferrous acid dysprosium pellet is used for the purposes for preparing command bundle rods for nuclear reactors, it is characterised in that：The iron-based ferrous acid
Dysprosium pellet is the iron-based ferrous acid dysprosium pellet according to claim 2, or for according to any one of claim 3 to 8
Iron-based ferrous acid dysprosium pellet prepared by method.
10. a kind of command bundle rods for nuclear reactors, including involucrum, it is characterised in that：Provided with according to claim 2 in the involucrum
Iron-based ferrous acid dysprosium pellet, or provided with the iron-based ferrous acid dysprosium core prepared by the method according to any one of claim 3 to 8
Block.
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