CN105734385A - Iron-based dysprosium iron oxide material and application thereof - Google Patents
Iron-based dysprosium iron oxide material and application thereof Download PDFInfo
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- CN105734385A CN105734385A CN201610217061.2A CN201610217061A CN105734385A CN 105734385 A CN105734385 A CN 105734385A CN 201610217061 A CN201610217061 A CN 201610217061A CN 105734385 A CN105734385 A CN 105734385A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
- C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—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
- 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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0207—Using a mixture of prealloyed powders or a master alloy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21C—NUCLEAR REACTORS
- G21C7/00—Control of nuclear reaction
- G21C7/06—Control of nuclear reaction by application of neutron-absorbing material, i.e. material with absorption cross-section very much in excess of reflection cross-section
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Abstract
The invention discloses an iron-based dysprosium iron oxide material and the application thereof. Dysprosium oxide powder and iron powder are weighted according to the mass percent of Fe-(8-38%)Dy2O3 and then mixed under the inert gas shielding condition. The mixed powder is subjected to ball milling for 2-98 h in the mode that ball milling is conducted for 50-60 min and then stopped for 4-6 min under the conditions that the ball-to-powder weight ratio is 0.8-52:1, the fill factor is 0.15-0.85, and the rotation speed of ball milling is 80-550 rpm; isostatic cool pressing is conducted on the mixed powder subjected to ball milling for 0.15-3.5 h under the condition that the pressure is 80-480 MPa, and billets are obtained through pressing; and finally the billets are sintered for 5-50 h at the temperature of 750-1250 DEG C under the inert gas shielding condition, and iron-based dysprosium iron oxide pellets are obtained. The iron-based dysprosium iron oxide material can serve as excellent neutron absorbers in nuclear reactor control rods; and equipment and a technique are simple, operation is easy, the controllability is excellent, and the preparation cost is low.
Description
Technical field
The present invention relates to belong to nuclear power plant reactor technical field, be specifically related to a kind of iron-based ferrous acid dysprosium material and application thereof.
Background technology
In nuclear power station running, typically realize reactor Steam Generator in Load Follow by regulation control rod and change boric acid concentration and control.Control
Rod processed is neutron absorber, and its translational speed is fast, and operation is reliable, uses flexibly, controls reactive accuracy high.And change
Boric acid concentration can realize reactive is changed control slowly.
The opening of nuclear power plant reactor, stop with power adjustments mainly by control rod control.Nuclear Power Accident once occurs, and control rod can be automatically
Hurtle down, make the chain reaction of nuclear fission in reactor stop, to ensure safety.The conventional neutron absorber material of control rod has carbonization
Boron (B4C), Ag-In-Cd, boron steel and combinations thereof body etc..And with B4C and boron steel material are the neutron absorber material of representative
More serious irradiation damage occur during the most under arms, this is mainly due to B10(n, α) react caused by produced helium and swelling.
Additionally this type of material can under the conditions of reactor disaster with the steam generation of High Temperature High Pressure strongly exothermic property oxidation reaction, produce hydrogen
Gas, occurs hydrogen quick-fried time serious.Ag-In-Cd belongs to strong neutron absorber, and during military service, its small mobile meeting brings reactivity
Change by a relatively large margin, it is generally required to change boric acid concentration to coordinate it to move.But utilize the boric acid concentration changed in cooling water to chase after
With the method for load, can produce a large amount of waste water, thus increase entreprise cost, the time simultaneously using the method to regulate reactivity is long.
Therefore, be designed with in nuclear reactor weak neutron absorber pellet replace regulating in control rod boric acid concentration method realize right
The trace of nuclear reactivity controls and regulation.
Dysprosium has five kinds of relatively large stable isotopes in neutron absorption cross-section, and after carrying out nuclear reaction, thermal neutron absorption cross section will not be sent out
Raw sudden change, beneficially stability contorting nuclear reactivity.The gamma activity of the transmutation product of dysprosium is low, and the half-life is short, and the infringement to heap core equipment is little.
Dy2TiO5Block is applied at some nuclear power stations as the neutron absorber material of control rod, and its core is to utilize dysprosium element
Superior nucleon characteristic.It is appreciated that Dy from equilbrium phase diagram2TiO5There are three kinds of crystal structures, including orthorhombic 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).Fluorite structure
The anti-radiation performance of block materials best, under identical radiation parameter, its void swelling rate and irradiation growth rate are minimum, and radiation stabilized
Good, irradiation process will not occur the transformation of crystal structure.And under radiation parameter the Dy of orthorhombic crystal structure2TiO5Decrystallized
Crystal conversion can occur before, orthorhombic crystal structural transformation be fluorite structure, the change of crystal structure can cause the body of block materials
Long-pending, thermal conductivity and the change of thermal coefficient of expansion.Therefore researchers are devoted to obtain the Dy of fluorite structure2TiO5Block materials, but
Owing to fluorite structure belongs to high-temperature-phase, and the temperature of control rod long service is less than 1000 DEG C, even if therefore preparing high temperature firefly
The Dy of stone structure2TiO5Block, under arms during will certainly be changed into low temperature orthorhombic crystal structure, this is unfavorable for the steady of nuclear reaction
Qualitative and safety.The another one key property requirement of command bundle rods for nuclear reactors neutron absorber material pellet is the conduction of heat of pellet
Property is superior, in order to the heat generated in pellet due to neutron reaction during under arms can conduct in time, it is ensured that nuclear reaction
Safety, and Dy2TiO5The heat conductivity of ceramic pellet is relatively poor.
Summary of the invention
In place of it is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of iron-based ferrous acid dysprosium material and application thereof, utilize
The iron-based ferrous acid dysprosium pellet that this iron-based ferrous acid dysprosium material prepares can as the excellent neutron absorber in command bundle rods for nuclear reactors,
And equipment, technique are simple, easily operating, controllability is superior, and preparation cost is low.
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, described iron-based ferrous acid dysprosium material is the ferrous acid dysprosium (DyFeO in iron-based by iron-based and disperse3) group
Become, and the mass ratio of ferrous acid dysprosium and iron-based is 1:0.8～1:6.2.Described disperse ferrous acid dysprosium in iron-based can 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 preparing above-mentioned iron-based ferrous acid dysprosium pellet, including:
Under inert gas shielding, by particle mean size 4.5～5.5 μm, the drying dysprosia powder of purity more than 99.5% and average particle
Degree 350～450 mesh, the drying iron powder of purity more than 99.8%, according to mass percent Fe-(8～38%) Dy2O3Weigh
Rear mixing, adds process control agent and makes its whole mass concentration less than 1%, obtaining mixed-powder；Above-mentioned mixed-powder is existed
Under conditions of ratio of grinding media to material 0.8～52:1, packing factor 0.15～0.85, rotational speed of ball-mill 80～550rpm, according to ball milling 50～60min
Stop the mode ball milling 2～98h of 4～6min；Then by the mixed-powder after ball milling under conditions of pressure 80～480MPa
Isostatic cool pressing 0.15～3.5h is to be pressed into base substrate；Again base substrate is placed under inert gas shielding and sinters 5～50 at 750～1250 DEG C
H, obtains described iron-based ferrous acid dysprosium pellet.Wherein, along with the amount of dysprosia increases, correspondingly sintering temperature needs higher, ball
Mill, isostatic cool pressing, the time of sintering need longer.
In one embodiment: described mass percent is Fe-(9～33%) Dy2O3；The parameter of mechanical milling process is ratio of grinding media to material 9～11:1,
Packing factor 0.48～0.52, rotational speed of ball-mill 370～390rpm, Ball-milling Time 2.5～49h；The parameter of isostatic cool pressing process be 250～
Isostatic cool pressing 0.4～0.6h under 270MPa；The parameter of sintering process is to sinter 11～17h at 780～920 DEG C.
In one embodiment: described 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, rotational speed of ball-mill 90～110rpm, Ball-milling Time 95～97h；The parameter of isostatic cool pressing process be 90～
Isostatic cool pressing 2.8～3.2h under 110MPa；The parameter of sintering process is to sinter 47～49h at 1180～1220 DEG C.
In one embodiment: described mass percent is Fe-(9～38%) Dy2O3；The parameter of mechanical milling process is ratio of grinding media to material 9～11:1,
Packing factor 0.48～0.52, rotational speed of ball-mill 370～390rpm, Ball-milling Time 47～49h；The parameter of isostatic cool pressing process be 250～
Isostatic cool pressing 0.4～0.6h under 270MPa；The parameter of sintering process is to sinter 7～49h at 1180～1220 DEG C.
In one embodiment: described 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, rotational speed of ball-mill 490～510rpm, Ball-milling Time 47～49h；The parameter of isostatic cool pressing process be 440～
Isostatic cool pressing 0.18～0.22h under 460MPa；The parameter of sintering process is to sinter 23～25h at 1180～1220 DEG C.
In one embodiment: described 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, rotational speed of ball-mill 370～390rpm, Ball-milling Time 2.5～3.5h；The parameter of isostatic cool pressing process is
Isostatic cool pressing 0.4～0.6h under 250～270MPa；The parameter of sintering process is to sinter 23～25h at 1180～1220 DEG C.
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 for preparing the purposes of command bundle rods for nuclear reactors.
The five of the technical solution adopted for the present invention to solve the technical problems are:
A kind of command bundle rods for nuclear reactors, including involucrum, is provided with above-mentioned iron-based ferrous acid dysprosium pellet in described involucrum.
Method for expressing Fe-(8～the 38%) Dy of the mass percent of the present invention2O3Refer to dysprosia (Dy2O3) powder and ferrum (Fe)
In the mixture of powder, the mass fraction of dysprosia powder is 8～38%；In like manner, Fe-10%Dy2O3, Fe-19%Dy2O3、
Fe-25.68%Dy2O3, Fe-32%Dy2O3, Fe-37%Dy2O3Refer respectively in the mixture of dysprosia powder and iron powder,
The mass fraction of dysprosia powder is 10%, 19%, 25.68%, 32%, 37%.
It " noble gas " of the present invention can be nitrogen, argon, hydrogen, helium, carbon dioxide etc., or above-mentioned gas
The mixing of one or more, its effect is starvation and keeps certain pressure intensity, and gas itself is not involved in reaction simultaneously.
The technical program is compared with background technology, and it has the advantage that
The invention provides a kind of iron-based ferrous acid dysprosium material and application thereof, use powder metallurgical technique under specific technological parameter, lead to
Cross high-energy ball milling method and make Fe powder and Dy2O3Powder uniformly mixes, then the iron-based ferrous acid obtained after isostatic cool pressing and sintering
Dysprosium material has excellent heat-conductive characteristic, mechanical property and low thermal coefficient of expansion, gives full play to the superior nucleon characteristic of dysprosium element,
Also it is avoided that Dy2TiO5Ceramic material is as the crystal structure multiformity existing for control rod pellet, irradiation unstability and warm
The deficiency of conductive performance difference etc. such that it is able to as the excellent neutron absorber in command bundle rods for nuclear reactors.The equipment of the present invention, work
Skill is simple, easily operates, and controllability is superior, low cost, meanwhile, prepares Dy than using powder metallurgical technique2TiO5Fluorite structure core
The sintering temperature of block is low, is conducive to reducing preparation cost further.
Accompanying drawing explanation
The invention will be further described with embodiment below in conjunction with the accompanying drawings.
Fig. 1 is according to mass percent Fe-32%Dy in the embodiment of the present invention 12O3Mixed-powder after weighing is through different ball millings
Between X ray diffracting spectrum.
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 the percentage elongation of the iron-based ferrous acid dysprosium pellet obtained in the embodiment of the present invention 7 and thermal coefficient of expansion varies with temperature signal
Figure, wherein solid line represents that percentage elongation varies with temperature schematic diagram, and dotted line represents that thermal coefficient of expansion varies with temperature schematic diagram.
Fig. 5 is the iron-based ferrous acid dysprosium pellet obtained in the embodiment of the present invention 7 final pellet schematic diagram after machining.
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.
Detailed description of the invention
Present disclosure is illustrated below by embodiment:
Embodiment 1
It is averaged the drying Dy of granularity 5 μm, purity 99.6%2O3Starting powder and particle mean size 400 mesh, the baking of purity 99.9%
Dry nebulization ferrum starting powder, in glove box under inert gas shielding, respectively according to mass percent Fe-10%Dy2O3、
Fe-25.68%Dy2O3, Fe-32%Dy2O3Mix respectively after weighing, carry out operations described below respectively: load planetary high energy ball
In grinding machine, it is suitably added process control agent such as stearic acid further according to needs and makes its whole mass concentration less than 1%, obtaining mixed powder
End；By above-mentioned mixed-powder under conditions of ratio of grinding media to material 10:1, packing factor 0.5, rotational speed of ball-mill 380rpm, according to ball milling 55min
Stopping the mode ball milling 3～48h of 5min, intermittent duty is possible to prevent ball grinder temperature too high.
Fig. 1 is according to mass percent Fe-32%Dy2O3Mixed-powder after weighing is through the X-ray diffraction of different Ball-milling Times
Collection of illustrative plates.It can be seen that along with the increase of Ball-milling Time, Dy2O3Phase and diffraction maximum gradually wideization of Fe phase, intensity is gradually
Reduce.Wideization of diffraction maximum is mainly by caused by two aspect factors, including refinement and the generation of distortion of lattice of crystal particle scale.From figure
In 1, it can be observed that along with the increase Dy of Ball-milling Time2O3The diffraction peak intensity of phase is to reduce, and disappears completely after 48h ball milling
Lose, show that perfection of crystal be there occurs continuous solid solution by destruction and the constituent element of ball milling, this number of die making to participate in diffraction
Reduce thus cause peak to be gradually lowered until disappearing.High-energy ball milling makes Dy2O3Create a large amount of while granule and Fe grain refine
New surface and lattice defect, crystallite dimension reduces diffusion length while reducing, beneficially the diffusion of atom and rearrangement, and activity is very
Height, beneficially the carrying out of sintering reaction.
Take above-mentioned according to mass percent Fe-10%Dy2O3, Fe-25.68%Dy2O3, Fe-32%Dy2O3Weighing, mixing, ball milling
Mixed-powder after 3h carries out operations described below respectively: loads rubber package set in glove box, then is placed in cold by the rubber package set tightened
In hydraulic cylinder in isostatic pressed instrument, under conditions of pressure 260MPa, isostatic cool pressing 0.5h is to be pressed into column base substrate；Again will
Base substrate is placed in Ar-sintering stove and sinters 16h at 900 DEG C, obtains the iron-based ferrous acid dysprosium pellet of three kinds of different ferrous acid dysprosium content,
Ferrous acid dysprosium is respectively 1:6.10,1:1.82,1:1.28 with the mass ratio of iron-based.
Fig. 2 is the X ray diffracting spectrum of above-mentioned three kinds of iron-based ferrous acid dysprosium pellets.It can be seen that after 900 DEG C of sintering 16h, do not have
Dy detected2O3Diffraction maximum, be also not detected by the diffraction maximum of the oxide of Fe, only detected Fe and DyFeO3's
Diffraction maximum, illustrates Dy2O3It has been completely reformed into DyFeO with Fe reaction3, define iron-based ferrous acid dysprosium block.
Above-mentioned iron-based ferrous acid dysprosium pellet, after machining, can obtain the final pellet of regular shape, is placed in by this final pellet
In command bundle rods for nuclear reactors involucrum, constitute a kind of command bundle rods for nuclear reactors together with other parts, can be used for controlling nuclear power station reaction
The operation of heap.
Embodiment 2
It is averaged the drying Dy of granularity 5 μm, purity 99.6%2O3Starting powder and particle mean size 400 mesh, the baking of purity 99.9%
Dry nebulization ferrum starting powder, in glove box under inert gas shielding, according to mass percent Fe-10%Dy2O3Mix after weighing
Close, load in planetary high-energy ball mill, be suitably added process control agent such as stearic acid further according to needs and make its whole mass concentration not
More than 1%, obtain mixed-powder；By above-mentioned mixed-powder at ratio of grinding media to material 10:1, packing factor 0.5, rotational speed of ball-mill 380rpm
Under the conditions of, the mode ball milling 3h of 5min is stopped according to ball milling 55min, intermittent duty is possible to prevent ball grinder temperature too high；So
After the mixed-powder after ball milling loaded in glove box rubber package set, then the rubber package set tightened is placed in isostatic cool pressing instrument
In hydraulic cylinder, under conditions of pressure 260MPa, isostatic cool pressing 0.5h is to be pressed into column base substrate；Base substrate is placed in argon again protect
Protecting in sintering furnace and sinter 12h at 800 DEG C, obtain iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium is 1:6.10 with the mass ratio of iron-based.
Above-mentioned iron-based ferrous acid dysprosium pellet, after machining, can obtain the final pellet of regular shape, is placed in by this final pellet
In command bundle rods for nuclear reactors involucrum, constitute a kind of command bundle rods for nuclear reactors together with other parts, and it is anti-to can be used for controlling nuclear power station
Answer the operation of heap.
Embodiment 3
It is averaged the drying Dy of granularity 5 μm, purity 99.6%2O3Starting powder and particle mean size 400 mesh, the baking of purity 99.9%
Dry nebulization ferrum starting powder, in glove box under inert gas shielding, according to mass percent Fe-10%Dy2O3Mix after weighing
Close, load in planetary high-energy ball mill, be suitably added process control agent such as stearic acid further according to needs and make its whole mass concentration not
More than 1%, obtain mixed-powder；By above-mentioned mixed-powder at ratio of grinding media to material 1:1, packing factor 0.2, rotational speed of ball-mill 100rpm
Under the conditions of, the mode ball milling 96h of 5min is stopped according to ball milling 55min, intermittent duty is possible to prevent ball grinder temperature too high；
Then the mixed-powder after ball milling is loaded in glove box rubber package set, then the rubber package set tightened is placed in isostatic cool pressing instrument
Hydraulic cylinder in, under conditions of pressure 100MPa, isostatic cool pressing 3h is to be pressed into column base substrate；Base substrate is placed in argon again protect
Protecting in sintering furnace and sinter 48h at 1200 DEG C, obtain iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium is 1:6.10 with the mass ratio of iron-based.
Above-mentioned iron-based ferrous acid dysprosium pellet, after machining, can obtain the final pellet of regular shape, is placed in by this final pellet
In command bundle rods for nuclear reactors involucrum, constitute a kind of command bundle rods for nuclear reactors together with other parts, and it is anti-to can be used for controlling nuclear power station
Answer the operation of heap.
Embodiment 4
It is averaged the drying Dy of granularity 5 μm, purity 99.6%2O3Starting powder and particle mean size 400 mesh, the baking of purity 99.9%
Dry nebulization ferrum 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%Dy2O3Mix respectively after weighing, carry out operations described below respectively: dress
Enter in planetary high-energy ball mill, be suitably added process control agent such as stearic acid further according to needs and make its whole mass concentration be less than
1%, obtain mixed-powder；By above-mentioned mixed-powder in ratio of grinding media to material 10:1, packing factor 0.5, the condition of rotational speed of ball-mill 380rpm
Under, the mode ball milling 48h of 5min is stopped according to ball milling 55min, intermittent duty is possible to prevent ball grinder temperature too high；Then
Mixed-powder after ball milling is loaded in glove box rubber package set, then the rubber package set tightened is placed in the liquid in isostatic cool pressing instrument
In cylinder pressure, under conditions of pressure 260MPa, isostatic cool pressing 0.5h is to be pressed into column base substrate；Again base substrate is placed in argon shield
Sintering furnace sinters 8h at 1200 DEG C, obtains the matter of the iron-based ferrous acid dysprosium pellet of three kinds of different ferrous acid dysprosium content, ferrous acid dysprosium and iron-based
Amount ratio 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-based ferrous acid dysprosium pellets.It can be seen that after 1200 DEG C of sintering 8h, do not have
Dy detected2O3Diffraction maximum, be also not detected by the diffraction maximum of the oxide of Fe, only detected Fe and DyFeO3's
Diffraction maximum, illustrates Dy2O3It has been completely reformed into DyFeO with Fe reaction3, define iron-based ferrous acid dysprosium block.
Above-mentioned iron-based ferrous acid dysprosium pellet, after machining, can obtain the final pellet of regular shape, is placed in by this final pellet
In command bundle rods for nuclear reactors involucrum, constitute a kind of command bundle rods for nuclear reactors together with other parts, and it is anti-to can be used for controlling nuclear power station
Answer the operation of heap.
Embodiment 5
It is averaged the drying Dy of granularity 5 μm, purity 99.6%2O3Starting powder and particle mean size 400 mesh, the baking of purity 99.9%
Dry nebulization ferrum starting powder, in glove box under inert gas shielding, according to mass percent Fe-37%Dy2O3Mix after weighing
Close, load in planetary high-energy ball mill, be suitably added process control agent such as stearic acid further according to needs and make its whole mass concentration not
More than 1%, obtain mixed-powder；By above-mentioned mixed-powder at ratio of grinding media to material 10:1, packing factor 0.5, rotational speed of ball-mill 380rpm
Under the conditions of, the mode ball milling 48h of 5min is stopped according to ball milling 55min, intermittent duty is possible to prevent ball grinder temperature too high；
Then the mixed-powder after ball milling is loaded in glove box rubber package set, then the rubber package set tightened is placed in isostatic cool pressing instrument
Hydraulic cylinder in, under conditions of pressure 260MPa, isostatic cool pressing 0.5h is to be pressed into column base substrate；Again base substrate is placed in argon
Sintering 48h at 1200 DEG C in protection sintering furnace, obtain iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium is 1:1 with the mass ratio of iron-based.
Above-mentioned iron-based ferrous acid dysprosium pellet, after machining, can obtain the final pellet of regular shape, is placed in by this final pellet
In command bundle rods for nuclear reactors involucrum, constitute a kind of command bundle rods for nuclear reactors together with other parts, and it is anti-to can be used for controlling nuclear power station
Answer the operation of heap.
Embodiment 6
It is averaged the drying Dy of granularity 5 μm, purity 99.6%2O3Starting powder and particle mean size 400 mesh, the baking of purity 99.9%
Dry nebulization ferrum starting powder, in glove box under inert gas shielding, according to mass percent Fe-37%Dy2O3Mix after weighing
Close, load in planetary high-energy ball mill, be suitably added process control agent such as stearic acid further according to needs and make its whole mass concentration not
More than 1%, obtain mixed-powder；By above-mentioned mixed-powder at ratio of grinding media to material 50:1, packing factor 0.8, rotational speed of ball-mill 500rpm
Under the conditions of, the mode ball milling 48h of 5min is stopped according to ball milling 55min, intermittent duty is possible to prevent ball grinder temperature too high；
Then the mixed-powder after ball milling is loaded in glove box rubber package set, then the rubber package set tightened is placed in isostatic cool pressing instrument
Hydraulic cylinder in, under conditions of pressure 450MPa, isostatic cool pressing 0.2h is to be pressed into column base substrate；Again base substrate is placed in argon
Sintering 24h at 1200 DEG C in protection sintering furnace, obtain iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium is 1:1 with the mass ratio of iron-based.
Above-mentioned iron-based ferrous acid dysprosium pellet, after machining, can obtain the final pellet of regular shape, is placed in by this final pellet
In command bundle rods for nuclear reactors involucrum, constitute a kind of command bundle rods for nuclear reactors together with other parts, and it is anti-to can be used for controlling nuclear power station
Answer the operation of heap.
Embodiment 7
It is averaged the drying Dy of granularity 5 μm, purity 99.6%2O3Starting powder and particle mean size 400 mesh, the baking of purity 99.9%
Dry nebulization ferrum starting powder, in glove box under inert gas shielding, according to mass percent Fe-25.68%Dy2O3Weigh
Rear mixing, loads in planetary high-energy ball mill, is suitably added process control agent such as stearic acid further according to needs and makes its whole quality dense
Degree, less than 1%, obtains mixed-powder；By above-mentioned mixed-powder at ratio of grinding media to material 10:1, packing factor 0.5, rotational speed of ball-mill 380rpm
Under conditions of, the mode ball milling 3h of 5min is stopped according to ball milling 55min, intermittent duty is possible to prevent ball grinder temperature too high；
Then the mixed-powder after ball milling is loaded in glove box rubber package set, then the rubber package set tightened is placed in isostatic cool pressing instrument
Hydraulic cylinder in, under conditions of pressure 260MPa, isostatic cool pressing 0.5h is to be pressed into column base substrate；Again base substrate is placed in argon
Sintering 24h at 1200 DEG C in protection sintering furnace, obtain iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium is 1:1.82 with the mass ratio of iron-based.
The above-mentioned ferrum tested according to standard GB/T/T-5163-2006 " mensuration of density of sintered material, oil content and percent opening "
The density of base ferrous acid dysprosium pellet is 6.54g/cm3。
Use heat transfer analysis instrument test above-mentioned iron-based ferrous acid dysprosium block room temperature, 500 DEG C and the thermal diffusion coefficient of 800 DEG C, thermal capacitance,
The value of thermal conductivity is shown in Table 1.
The physical property test result of table 1 iron-based ferrous acid dysprosium sintering block
The percentage elongation and the thermal coefficient of expansion that use the above-mentioned sintering block of thermal dilatometer test vary with temperature as shown in Figure 4.
Above-mentioned iron-based ferrous acid dysprosium pellet, after machining, can obtain the final pellet of regular shape, as shown in Figure 5.Should
Final pellet is placed in command bundle rods for nuclear reactors involucrum, constitutes a kind of command bundle rods for nuclear reactors, and can be used for together with other parts
Control the operation of nuclear power plant reactor.
Embodiment 8
It is averaged the drying Dy of granularity 5 μm, purity 99.6%2O3Starting powder and particle mean size 400 mesh, the baking of purity 99.9%
Dry nebulization ferrum starting powder, in glove box under inert gas shielding, according to mass percent Fe-19%Dy2O3Mix after weighing
Close, load in planetary high-energy ball mill, be suitably added process control agent such as stearic acid further according to needs and make its whole mass concentration not
More than 1%, obtain mixed-powder；By above-mentioned mixed-powder at ratio of grinding media to material 10:1, packing factor 0.5, rotational speed of ball-mill 380rpm
Under the conditions of, the mode ball milling 3h of 5min is stopped according to ball milling 55min, intermittent duty is possible to prevent ball grinder temperature too high；So
After the mixed-powder after ball milling loaded in glove box rubber package set, then the rubber package set tightened is placed in isostatic cool pressing instrument
In hydraulic cylinder, under conditions of pressure 260MPa, isostatic cool pressing 0.5h is to be pressed into column base substrate；Base substrate is placed in argon again protect
Protecting in sintering furnace and sinter 24h at 1200 DEG C, obtain iron-based ferrous acid dysprosium pellet, ferrous acid dysprosium is 1:2.78 with the mass ratio of iron-based.
Fig. 6 is the scanning electron microscope (SEM) photograph on iron-based ferrous acid dysprosium pellet surface, is formed from scanning electron microscope (SEM) photograph it will be seen that in sintering process
DyFeO3It is distributed in iron-based, DyFeO3In irregular shape.
Above-mentioned iron-based ferrous acid dysprosium pellet, after machining, can obtain the final pellet of regular shape, is placed in by this final pellet
In command bundle rods for nuclear reactors involucrum, constitute a kind of command bundle rods for nuclear reactors together with other parts, and it is anti-to can be used for controlling nuclear power station
Answer the operation of heap.
Skilled person will appreciate that, when technical parameter change in the range of following of the present invention, it is contemplated that obtain and above-mentioned reality
Execute the technique effect that example is same or like:
Under inert gas shielding, by particle mean size 5 μm, the drying dysprosia powder of purity more than 99.5% and particle mean size 400
Mesh, the drying iron powder of purity more than 99.8%, according to mass percent Fe-(10～37%) Dy2O3Mix after weighing, then
Adition process controlling agent also makes its whole mass concentration less than 1%, obtains mixed-powder；By above-mentioned mixed-powder in ratio of grinding media to material 1～
Under conditions of 50:1, packing factor 0.2～0.8, rotational speed of ball-mill 100～500rpm, stop 5min's according to ball milling 55min
Mode ball milling 3～96h；Then by the isostatic cool pressing 0.2～3h under conditions of pressure 100～450MPa of the mixed-powder after ball milling
To be pressed into base substrate；Again base substrate is placed under inert gas shielding and sinters 8～48h at 800～1200 DEG C, obtain iron-based ferrous acid dysprosium
Pellet, by iron-based and disperse, the ferrous acid dysprosium in iron-based forms for it, and the mass ratio of ferrous acid dysprosium and iron-based is 1:1～1:6.1；Described more
Dissipating the ferrous acid dysprosium in iron-based can be p-type ferrous acid dysprosium.
The above, only present pre-ferred embodiments, therefore the scope that the present invention implements can not be limited according to this, i.e. according to the present invention
The equivalence change that the scope of the claims and description are made with modify, all should still belong in the range of the present invention contains.
Claims (10)
1. an iron-based ferrous acid dysprosium material, it is characterised in that: described iron-based ferrous acid dysprosium material is the ferrum in iron-based by iron-based and disperse
Acid dysprosium forms, and the mass ratio of ferrous acid dysprosium and iron-based is 1:0.8～1:6.2.
2. the iron-based ferrous acid dysprosium pellet that a kind is made up of the material described in claim 1.
3. the method for the iron-based ferrous acid dysprosium pellet that a kind is prepared described in claim 2, it is characterised in that: including:
Under inert gas shielding, by particle mean size 4.5～5.5 μm, the drying dysprosia powder of purity more than 99.5% and average
Granularity 350～450 mesh, the drying iron powder of purity more than 99.8%, according to mass percent Fe-(8～38%) Dy2O3Carry out
Mix after weighing, add process control agent and make its whole mass concentration less than 1%, obtaining mixed-powder；By above-mentioned mixing
Powder is under conditions of ratio of grinding media to material 0.8～52:1, packing factor 0.15～0.85, rotational speed of ball-mill 80～550rpm, according to ball milling
50～60min stop the mode ball milling 2～98h of 4～6min；Then by the mixed-powder after ball milling at pressure 80～480
Under conditions of MPa, isostatic cool pressing 0.15～3.5h is to be pressed into base substrate；Again base substrate is placed under inert gas shielding 750～
1250 DEG C of sintering 5～50h, obtain described iron-based ferrous acid dysprosium pellet.
Method the most according to claim 3, it is characterised in that: described 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, rotational speed of ball-mill 370～390rpm, Ball-milling Time
2.5～49h；The parameter of isostatic cool pressing process is isostatic cool pressing 0.4～0.6h under 250～270MPa；The parameter of sintering process is
11～17h are sintered at 780～920 DEG C.
Method the most according to claim 3, it is characterised in that: described 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, and rotational speed of ball-mill 90～110rpm, during ball milling
Between 95～97h；The parameter of isostatic cool pressing process is isostatic cool pressing 2.8～3.2h under 90～110MPa；The parameter of sintering process
It is at 1180～1220 DEG C, to sinter 47～49h.
Method the most according to claim 3, it is characterised in that: described 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, rotational speed of ball-mill 370～390rpm, Ball-milling Time
47～49h；The parameter of isostatic cool pressing process is isostatic cool pressing 0.4～0.6h under 250～270MPa；The parameter of sintering process is
7～49h are sintered at 1180～1220 DEG C.
Method the most according to claim 3, it is characterised in that: described 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, and rotational speed of ball-mill 490～510rpm, during ball milling
Between 47～49h；The parameter of isostatic cool pressing process is isostatic cool pressing 0.18～0.22h under 440～460MPa；The ginseng of sintering process
Number is to sinter 23～25h at 1180～1220 DEG C.
Method the most according to claim 3, it is characterised in that: described 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, and rotational speed of ball-mill 370～390rpm, during ball milling
Between 2.5～3.5h；The parameter of isostatic cool pressing process is isostatic cool pressing 0.4～0.6h under 250～270MPa；The ginseng of sintering process
Number is to sinter 23～25h at 1180～1220 DEG C.
9. an iron-based ferrous acid dysprosium pellet is for preparing the purposes of command bundle rods for nuclear reactors, it is characterised in that: described iron-based ferrous acid dysprosium
Pellet is according to the iron-based ferrous acid dysprosium pellet described in claim 2, or for according to the side according to any one of claim 3 to 8
Iron-based ferrous acid dysprosium pellet prepared by method.
10. a command bundle rods for nuclear reactors, including involucrum, it is characterised in that: it is provided with in described involucrum according to claim 2 institute
The iron-based ferrous acid dysprosium pellet stated, or be provided with according to the iron-based ferrous acid dysprosium prepared by the method according to any one of claim 3 to 8
Pellet.
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| CN106282713A (en) * | 2016-09-14 | 2017-01-04 | 厦门大学 | A kind of nuclear reactor ash control rod molybdenio dysprosia material and application thereof |
| CN106381433A (en) * | 2016-09-14 | 2017-02-08 | 厦门大学 | Molybdenum-based thulium oxide material for nuclear reactor ash control rod and application of molybdenum-based thulium oxide material |
| CN113201677A (en) * | 2021-05-07 | 2021-08-03 | 四川坤天硬质合金有限责任公司 | Production process for producing ultrafine grain hard alloy by using sub-fine tungsten carbide |
| CN114835492A (en) * | 2022-05-18 | 2022-08-02 | 厦门稀土材料研究所 | Rare earth-based zirconium-hafnium composite ceramic material and preparation method and application thereof |
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| CN105161144A (en) * | 2015-08-07 | 2015-12-16 | 厦门大学 | Preparation method of dysprosium titanium oxide pellet serving as neutron absorbing material of nuclear reactor core |
| CN105185424A (en) * | 2015-08-07 | 2015-12-23 | 厦门大学 | Nuclear reactor core neutron absorbing material terbium titanate pellet and preparation method thereof |
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| CN105161144A (en) * | 2015-08-07 | 2015-12-16 | 厦门大学 | Preparation method of dysprosium titanium oxide pellet serving as neutron absorbing material of nuclear reactor core |
| CN105185424A (en) * | 2015-08-07 | 2015-12-23 | 厦门大学 | Nuclear reactor core neutron absorbing material terbium titanate pellet and preparation method thereof |
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| CN106282713A (en) * | 2016-09-14 | 2017-01-04 | 厦门大学 | A kind of nuclear reactor ash control rod molybdenio dysprosia material and application thereof |
| CN106381433A (en) * | 2016-09-14 | 2017-02-08 | 厦门大学 | Molybdenum-based thulium oxide material for nuclear reactor ash control rod and application of molybdenum-based thulium oxide material |
| CN106381433B (en) * | 2016-09-14 | 2018-07-10 | 厦门大学 | A kind of nuclear reactor ash control rod molybdenum base thulium oxide material and its application |
| CN113201677A (en) * | 2021-05-07 | 2021-08-03 | 四川坤天硬质合金有限责任公司 | Production process for producing ultrafine grain hard alloy by using sub-fine tungsten carbide |
| CN114835492A (en) * | 2022-05-18 | 2022-08-02 | 厦门稀土材料研究所 | Rare earth-based zirconium-hafnium composite ceramic material and preparation method and application thereof |
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