CN106381433A - Molybdenum-based thulium oxide material for nuclear reactor ash control rod and application of molybdenum-based thulium oxide material - Google Patents
Molybdenum-based thulium oxide material for nuclear reactor ash control rod and application of molybdenum-based thulium oxide material Download PDFInfo
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Abstract
The invention discloses a molybdenum-based thulium oxide material for a nuclear reactor ash control rod and an application of the molybdenum-based thulium oxide material. The molybdenum-based thulium oxide material is prepared by the steps of mixing after weighing dried thulium oxide powder with the purity of higher than 99% and dried molybdenum powder with the purity of higher than 99.5% according to the mass percentage of Mo-(3-55)wt% Tm2O3 under the protection of inert gases; then, adding a process control agent, and enabling the final mass concentration of the process control agent not to exceed 2.5wt% to obtain mixed powder; carrying out ball milling on the mixed powder for 2-160h in a way of stopping for 4-12min after ball milling for 45-60min under the conditions that the ball material ratio is (0.8-35):1, the filling coefficient is 0.05-0.85 and the ball milling rotating speed is 80-650rpm; next, carrying out isostatic cool pressing on the ball-milled mixed powder at the pressure of 80-550MPa for 0.05-4h to form a blank; and then, sintering the blank at 1200-1900 DEG C for 2-110h under the protection of the inert gases to obtain a molybdenum-based thulium oxide pellet which is an excellent neutron absorber pellet material for an ash control rod.
Description
Technical field
The invention belongs to the reactive control technology field of nuclear power plant reactor is and in particular to a kind of nuclear reactor ash controls
Rod molybdenum base thulium oxide neutron absorber material and its application.
Background technology
In conventional pressurized-water reactor nuclear power plant normal course of operation, the general depth passing through regulation control rod intercalation reaction heap reactor core
Degree and change boric acid concentration are tracked to the control of nuclear reactivity with to load.Control used in conventional nuclear reactor
Rod, its internal neutron absorber material is strong neutron absorber material, such as Ag-In-Cd alloy pellet.This containing strong neutron-absorbing
The control rod of body is referred to as black control rod, referred to as black rod.The minute movement of black control rod can bring the strong change of nuclear reactivity,
Typically require and change boric acid concentration to coordinate the movement of black control rod simultaneously.This in conventional pressurized-water reactor nuclear power plant pass through adjust
Black rod simultaneously coordinates change boric acid concentration to realize the method to nuclear reactivity control with to Steam Generator in Load Follow, result in nuclear power station daily
Need to process substantial amounts of main reaction reactor coolant, and need large-sized container to contain waste liquid.Due to needing to adjust boric acid
Solubility and the discarded chemical solution of process are thus complicate control system.Pass through to add water dense with the boric acid in dilute solution simultaneously
Or degree increases the boric acid concentration in solution by adding boric acid, and this process is slow, and the required time is long, thus
The problems such as bring to the insensitive of nuclear reactivity control and feed back slow.
Therefore, US Westinghouse company proposes to be that grey control rod replaces changing boron using the control rod of the weak neutron absorber of a class
Acid concentration coordinates black rod to carry out the control of nuclear reactivity and the tracking of load, and is able in AP600 and AP1000 nuclear reactor
Application.The needs of normal handling main reaction reactor coolant can be preferably minimized using grey control rod, thus enormously simplify
Learn and volume control system and its operation, increased the sensitivity that nuclear reactivity is controlled, and reduce nuclear power cost.Ash controls
Rod is the control rod containing weak neutron absorber pellet, and in nuclear reactor run duration, its most of the time is inserted into heap in-core
Portion.And black control rod is the control rod containing strong neutron absorber pellet, in nuclear reactor run duration, little intercalation reaction heap
In reactor core.In addition, once occur Nuclear Power Accident, grey control rod and black control rod can automatically hurtle down simultaneously, so that nuclear reaction
Heap out of service rapidly it is ensured that nuclear plant safety.
For preparing the candidate material of grey control rod neutron absorber pellet, including the boron carbide (B containing boron element4C)、
Boron steel and combinations thereof body, Ag-In-Cd alloy, material containing rare earth element such as Tb, Dy and Tm etc..But boron carbide
With boron steel neutron absorber material easily under arms during more serious irradiation damage occurs, this mainly due to void swelling and
B10(n, α) reaction produce helium caused by, and B10Neutron absorption cross-section larger.Therefore, boron carbide and boron steel are not suitable for doing ash
Control rod neutron absorber pellet.And it is used for black excellent strong neutron absorber material Ag-In-Cd alloy, due to anti-in core
During answering stack operation, black C＆P systems insert the time of reactor core seldom, and the neutron irradiation dosage suffering from is few, and neutron irradiation is led
The swelling causing and creep compliance are fewer, and therefore Ag-In-Cd alloy is suitable as black control rod neutron absorber material.
But for grey C＆P systems, in nuclear power station run duration, in about half run time, it is to rest on heap core inner, long
Phase suffers from the neutron irradiation of heavy dose.If Ag-In-Cd alloy is as grey control rod neutron absorber pellet, long-term insertion
To in reactor core, substantial amounts of neutron irradiation can be suffered from, its void swelling and creep will be very serious, thus affecting grey control
The service life of rod.Additionally, Ag, the In and Cd element in Ag-In-Cd alloy all has larger neutron absorption cross-section, and Ag,
The neutron absorption cross-section of the transmutation product of In and Cd but significantly reduces.When Ag-In-Cd alloy being used as grey control rod neutron
During absorber pellet, after running 5 years, the reactivity worth of grey C＆P systems will be reduced to its initial reactivity value
80% about, no longer meet the requirement to grey C＆P systems reactivity worth for the mechanical compensation control model.
For manufacturing grey control rod neutron absorber material, mainly consider the nucleon characteristic of its inner element.Thulium is certainly
So the stable isotope in boundary is169Tm.The neutron absorption cross-section of Tm is 108bar, and transmutation product is Yb and Lu etc..After transmuting
Product after filial generation product and filial generation product transmuting all still has the neutron absorption cross-section close with Tm.Long-term through neutron
After irradiation, the pellet containing thulium still has stable neutron absorption capability.Therefore, thulium is excellent control rod neutron absorber
Nucleon element.
According to military service feature, nuclear power reactor core ash control rod neutron absorber pellet needs to have a series of key properties,
Including neutron absorption capability steady in a long-term；Excellent thermophysical property, such as high heat transfer, low thermal coefficient of expansion, with
The heat during housecoat labour generating neutron reaction in pellet conducts in time, to prevent pellet from melting；Good power
Learn performance；Excellent anti-neutron irradiation performance, such as low void swelling and irradiation growth etc..Therefore, the block containing thulium element
Body material, and meet the above-mentioned condition as neutron absorber pellet, all it is expected to inhale as nuclear reactor ash control rod neutron
Acceptor.
Content of the invention
It is an object of the invention in place of overcoming the deficiencies in the prior art, there is provided a kind of nuclear reactor ash control rod molybdenum
Base thulium oxide material and its application.
One of the technical solution adopted for the present invention to solve the technical problems is：
A kind of nuclear reactor ash control rod molybdenum base thulium oxide material, described molybdenum base thulium oxide material by molybdenum as matrix,
Thulium oxide is distributed in Mo substrate as disperse phase, and thulium oxide is 1 with the mass ratio of molybdenum:0.8～1:10.
The two of the technical solution adopted for the present invention to solve the technical problems are：
A kind of molybdenum base thulium oxide 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 molybdenum base thulium oxide pellet, under inert gas shielding, by the baking of purity more than 99%
The baking molybdenum powder end of dry oxidation thulium powder and purity more than 99.5%, according to mass percent Mo- (3～55) wt%Tm2O3Carry out
Mix after weighing, add process control agent and make its whole mass concentration be less than 2.5wt%, obtain mixed-powder；Will be above-mentioned
Mixed-powder is in ratio of grinding media to material 0.8～35:1st, packing factor 0.05～0.85, under conditions of rotational speed of ball-mill 80～650rpm, according to
Ball milling 45～60min stops the mode ball milling 2～160h of 4～12min；Then by the mixed-powder after ball milling pressure 80～
Under conditions of 550MPa, isostatic cool pressing 0.05～4h is to be pressed into base substrate；Again base substrate is placed under inert gas shielding 1200～
1900 DEG C of sintering 2～110h, obtain final product described molybdenum base thulium oxide pellet.
In one embodiment：Described ratio of grinding media to material is 10～30:1.
In one embodiment：Described packing factor is 0.3～0.8.
In one embodiment：Described rotational speed of ball-mill is 300～600rpm.
In one embodiment：The pressure of described isostatic cool pressing is 200～500MPa.
The four of the technical solution adopted for the present invention to solve the technical problems are：
A kind of above-mentioned molybdenum base thulium oxide pellet is used for preparing the purposes of nuclear reactor ash control rod.
The five of the technical solution adopted for the present invention to solve the technical problems are：
A kind of nuclear reactor ash control rod, including involucrum, is provided with above-mentioned molybdenum base thulium oxide pellet in described involucrum.
Method for expressing Mo- (3～55) wt%Tm of the mass percent of the present invention2O3Refer to thulium oxide (Tm2O3) powder
In the mixture of molybdenum (Mo) powder, the mass fraction of thulium oxide powder is 3～55wt%.In the same manner, Mo-15wt%Tm2O3、Mo-
18wt%Tm2O3, Mo-21wt%Tm2O3, Mo-25wt%Tm2O3And Mo-50wt%Tm2O3Refer respectively in thulium oxide powder
In the mixture of molybdenum powder, the mass fraction of thulium oxide powder is respectively 15%, 18%, 21%, 25% and 50%.
Its " inert gas " of the present invention can be argon gas and helium etc., or one or more of above-mentioned gas is mixed
Close, its effect is starvation and keeps certain pressure intensity, gas is not involved in reacting in itself simultaneously.
Compared with background technology, it has the advantage that the technical program：
The present invention adopts powder metallurgical technique, under specific technological parameter, is protected by ball milling isostatic cool pressing gas
The processes such as shield sintering, that is,：Ball-milling method is made molybdenum powder fully be refined with thulium oxide powder, uniformly mixes, then through isostatic cool pressing
Preformed compact, obtains molybdenum base thulium oxide block materials, equipment needed thereby and process is simple, easily after finally sintering under inert gas shielding
Operation, preparation cost is low；Prepared molybdenum base thulium oxide material has a stable neutron absorption capability, excellent heat-conductive characteristic,
Low thermal coefficient of expansion, excellent mechanical behavior under high temperature, anti-neutron irradiation performance, good high-temperature machinery stability etc., material
Material Stability Analysis of Structures；Tm simultaneously2O3Even dispersion is distributed in Mo substrate, can give full play to the excellent nucleon characteristic of thulium element.
According to nucleon property calculation, heap heat analysis, correlated performance calculate and practical application in pellet dimensioned
Requirement of energy etc. understands, the molybdenum base thulium oxide block materials of the present invention are excellent grey control rod neutron absorber pellet materials
Material, meets reactor being required to neutron absorber performance.The core of molybdenum base thulium oxide pellet is excellent using thulium element
Nucleon performance.2425 DEG C of the fusing point of thulium oxide, at high temperature, the Tm of cubic crystal structure2O3There is good stability；?
During military service, its crystal structure will not variation with temperature and change.Metal molybdenum has high-melting-point, good creep resistant
The advantages of performance, high thermal conductivity, low thermal coefficient of expansion, excellent elevated temperature strength and good high-temperature machinery stability.
Meanwhile, there is not chemical reaction, at high temperature still with Tm in thulium oxide and molybdenum2O3The form Dispersed precipitate of particle in Mo substrate, molybdenum
Base thulium oxide block materials under arms during dimensionally stable.Therefore, molybdenum base thulium oxide has the institute that molybdenum and thulium oxide have
There is excellent specific property.Can very easily pass through to change Tm simultaneously2O3The line density to change Tm in block for the addition, with full
Sufficient reactor core is to the strong and weak requirement of the neutron absorption capability of neutron absorber pellet of grey control rod.Therefore, the molybdenum base oxygen of the present invention
Change thulium block materials to can be used to replace in nuclear reactor as the excellent neutron absorber of nuclear reactor ash control rod
In by changing the control to nuclear reactivity for the boric acid concentration and the effect to Steam Generator in Load Follow, improve the nuclear reactivity to reactor
Control accuracy, significantly reduces regulating time needed for control；Reduce the corrosion to reaction pile element for the boric acid, reduce and need daily
The waste liquid to process in a large number, simplifies chemical treatment and regulation and control system.
Brief description
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is Mo-21wt%Tm in embodiment 12O3Mixed-powder is through the X ray diffracting spectrum of different Ball-milling Times.
Fig. 2 is the Mo-Tm of different Ball-milling Times in embodiment 12O3The base substrate through cold isostatic compaction for the mixed-powder is 1600
X ray diffracting spectrum after DEG C sintering 24h, wherein three curves represent Ball-milling Time 48h, 24h, 3h from top to bottom respectively.
Fig. 3 is the Mo-21wt%Tm of ball milling 24h in embodiment 32O3The base substrate through cold isostatic compaction for the mixed-powder is not
X ray diffracting spectrum after synthermal lower sintering 12h, wherein four curves represent respectively from top to bottom 1600 DEG C of sintering temperature,
1550℃、1500℃、1400℃.
Fig. 4 is the Mo-21wt%Tm of ball milling 48h in embodiment 62O3The base substrate through cold isostatic compaction for the mixed-powder exists
Percentage elongation after 1600 DEG C of sintering 24h and thermal coefficient of expansion variation with temperature curve.
Fig. 5 is the Mo-21wt%Tm of ball milling 48h in embodiment 62O3The base substrate through cold isostatic compaction for the mixed-powder exists
Scanning electron microscope diagram after 1600 DEG C of sintering 24h and element power spectrum line scanning result.
Fig. 6 is the Mo-21wt.%Tm of ball milling 48h in embodiment 62O3Block after cold isostatic compaction for the powder is 1600
DEG C sintering 24h after transmission electron microscope pattern and EDAX results.
Specific embodiment
Illustrate present disclosure below by embodiment：
Embodiment 1
Take the baking molybdenum powder end drying thulium oxide starting powder and purity 99.9% of purity 99.5%, protect in inert gas
In the glove box of shield, respectively according to mass percent Mo-15wt%Tm2O3, Mo-18wt%Tm2O3, Mo-21wt%Tm2O3With
Mo-25wt%Tm2O3Mix respectively after being weighed, add stearic acid process control agent and so that its whole quality accounting is less than
1wt%, obtains mixed-powder；Load in ball grinder and tighten ball grinder lid, by above-mentioned mixed-powder in ratio of grinding media to material 10:1st, fill
Fill out coefficient 0.4, under conditions of rotational speed of ball-mill 500rpm, stop the mode ball milling 3～144h of 5min according to ball milling 55min,
Operation of having a rest can prevent ball grinder temperature too high.
Fig. 1 is mass percent Mo 21wt.%Tm2O3Mixed-powder is through the X ray diffracting spectrum of different Ball-milling Times.
It can be seen that with the prolongation of Ball-milling Time, Mo and Tm2O3Diffraction maximum gradually wideization, diffraction peak intensity gradually drops
Low.The main cause of diffraction peaks broadening is the powder distortion of lattice that the crystal grain refinement of powder and ball milling cause.As shown in figure 1, with
The prolongation of Ball-milling Time, oxide Tm2O3The diffraction peak intensity of phase is gradually lowered, and is wholly absent, shows oxygen after 96h ball milling
Compound perfection of crystal is destroyed by ball milling, the crystal particle scale of powder is greatly reduced and constituent element gradually Mo crystal is entered in solid solution
In structure so that participate in diffraction crystal grain quantity reduce thus cause diffraction peak intensity be gradually lowered until disappear.And Mo
Main diffraction maximum develops into the peak shape of amorphous bulge after ball milling to 144h, illustrate now powder grain yardstick have been reduced to extremely low,
Change for substantial amounts of amorphous phase.High-energy ball milling makes Mo particle and Tm2O3New surface and crystalline substance in a large number is created while particle refinement
Lattice defect, crystallite dimension reduces diffusion length while reduction, is conducive to diffusion and the rearrangement of atom, simultaneously ball-milled powder
Activity is very high, is conducive to the carrying out of sintering reaction.
Take above-mentioned according to mass percent Mo-21%Tm2O3Weigh, mix, and mixed after difference ball milling 3h, 24h and 48h
Close powder and carry out operations described below respectively：In glove box, mixed-powder is loaded rubber package set tightening, then by the rubber tightening
Jacket is placed in the hydraulic cylinder in isostatic cool pressing instrument, and under conditions of pressure 280MPa, isostatic cool pressing 0.5h is to be pressed into column
Base substrate；Again base substrate is placed in Ar-sintering stove, sinters 24h at 1600 DEG C, obtain final product the molybdenum base of three kinds of different Ball-milling Times
Thulium oxide pellet, thulium oxide is 1 with the mass ratio of molybdenum base:3.67 and 1:3.
Fig. 2 is the X-ray diffractogram of the molybdenum base thulium oxide pellet of mixed-powder sintering of above-mentioned three kinds different Ball-milling Times
Spectrum.As can be seen that after 1600 DEG C of sintering 24h, only existing Mo and Tm2O3, there is not cenotype diffraction maximum in the diffraction maximum of two phases,
Mo and Tm in sintering process is described2O3Chemical reaction is not occurred to generate novel substance.Because ball milling leads to Tm2O3Decompose and solid solution
Enter in the crystal structure of Mo, therefore in sintering process oxygen and thulium atom slowly separate out from Mo crystal structure, agglomeration more
Dissipate and be distributed in matrix molybdenum, define the molybdenum base thulium oxide block of thulium oxide even dispersion.
Above-mentioned molybdenum base thulium oxide pellet, after over mechanical processing, can obtain the final pellet of regular shape, and this is final
Pellet is placed in nuclear reactor ash control rod involucrum, constitutes a kind of nuclear reactor ash control rod, can use together with other parts
In the operation controlling nuclear power plant reactor.
Embodiment 2
Take the baking molybdenum powder end drying thulium oxide starting powder and purity 99.9% of purity 99.5%, protect in inert gas
In the glove box of shield, according to mass percent Mo-10wt%Tm2O3Mix after being weighed, add stearic acid process control agent simultaneously
Make its whole quality accounting be less than 1wt%, obtain mixed-powder；Load in ball grinder and tighten ball grinder lid, will be above-mentioned mixed
Close powder in ratio of grinding media to material 1:1st, packing factor 0.1, under conditions of rotational speed of ball-mill 100rpm, stop 5min according to ball milling 55min
Mode ball milling 24h, intermittent duty can prevent ball grinder temperature too high.Then by the mixed-powder after ball milling in glove box
Load rubber package set and tighten, then the rubber package set tightening is placed in the hydraulic cylinder in isostatic cool pressing instrument, in pressure
Under conditions of 100MPa, isostatic cool pressing 3h is to be pressed into column base substrate；Again base substrate is placed in Ar-sintering stove, 1800
DEG C sintering 100h, obtains final product molybdenum base thulium oxide pellet, thulium oxide is 1 with the mass ratio of molybdenum base:9.
Above-mentioned molybdenum base thulium oxide pellet, after over mechanical processing, can obtain the final pellet of regular shape, and this is final
Pellet is placed in nuclear reactor ash control rod involucrum, constitutes a kind of nuclear reactor ash control rod, can use together with other parts
In the operation controlling nuclear power plant reactor.
Embodiment 3
Take the baking molybdenum powder end drying thulium oxide starting powder and purity 99.9% of purity 99.5%, protect in inert gas
In the glove box of shield, according to mass percent Mo-21wt%Tm2O3Mix after being weighed, add stearic acid process control agent simultaneously
Make its whole quality accounting be less than 1wt%, obtain mixed-powder；Load in ball grinder and tighten ball grinder lid, will be above-mentioned mixed
Close powder in ratio of grinding media to material 10:1st, packing factor 0.4, under conditions of rotational speed of ball-mill 500rpm, stop 5min according to ball milling 55min
Mode ball milling 24h, intermittent duty can prevent ball grinder temperature too high.Then by the mixed-powder after ball milling in glove box
Load rubber package set and tighten, then the rubber package set tightening is placed in the hydraulic cylinder in isostatic cool pressing instrument, in pressure
Under conditions of 280MPa, isostatic cool pressing 0.5h is to be pressed into column base substrate；Again base substrate is placed in Ar-sintering stove, respectively
In 1400 DEG C, 1500 DEG C, 1550 DEG C, 1600 DEG C of sintering 12h, obtain final product four kinds of molybdenum base thulium oxide pellets, the matter of thulium oxide and molybdenum base
Amount is than for being 1:3.76.
Fig. 3 is that above-mentioned four kinds identical Ball-milling Time mixed-powders burn at different temperatures through the base substrate of cold isostatic compaction
The X ray diffracting spectrum of the molybdenum base thulium oxide pellet of knot 12h.As can be seen that after 1400～1600 DEG C of sintering 12h, only Mo
And Tm2O3, there is not cenotype diffraction maximum in the diffraction maximum of two phases, sintering, Mo and Tm at a temperature of 1400～1600 DEG C are described2O3
Chemical reaction is not occurred to generate novel substance.Because ball milling leads to Tm2O3Decompose and solid solution is entered in the crystal structure of Mo, therefore sinter
During oxygen and thulium atom slowly separate out from Mo crystal structure, agglomeration Dispersed precipitate in matrix molybdenum, define oxygen
Change the molybdenum base thulium oxide block of thulium even dispersion.
Above-mentioned molybdenum base thulium oxide pellet, after over mechanical processing, can obtain the final pellet of regular shape, and this is final
Pellet is placed in nuclear reactor ash control rod involucrum, constitutes a kind of nuclear reactor ash control rod, can use together with other parts
In the operation controlling nuclear power plant reactor.
Embodiment 4
Take the baking molybdenum powder end drying thulium oxide starting powder and purity 99.9% of purity 99.5%, protect in inert gas
In the glove box of shield, according to mass percent Mo-25wt%Tm2O3Mix after being weighed, add stearic acid process control agent simultaneously
Make its whole quality accounting be less than 1wt%, obtain mixed-powder；Load in ball grinder and tighten ball grinder lid, will be above-mentioned mixed
Close powder in ratio of grinding media to material 30:1st, packing factor 0.8, under conditions of rotational speed of ball-mill 600rpm, stop 5min according to ball milling 55min
Mode ball milling 48h, intermittent duty can prevent ball grinder temperature too high.Then by the mixed-powder after ball milling in glove box
Load rubber package set and tighten, then the rubber package set tightening is placed in the hydraulic cylinder in isostatic cool pressing instrument, in pressure
Under conditions of 500MPa, isostatic cool pressing 0.1h is to be pressed into column base substrate；Again base substrate is placed in Ar-sintering stove,
1500 DEG C of sintering 24h, obtain final product molybdenum base thulium oxide pellet, and thulium oxide is 1 with the mass ratio of molybdenum base:3.
Above-mentioned molybdenum base thulium oxide pellet, after over mechanical processing, can obtain the final pellet of regular shape, and this is final
Pellet is placed in nuclear reactor ash control rod involucrum, constitutes a kind of nuclear reactor ash control rod, can use together with other parts
In the operation controlling nuclear power plant reactor.
Embodiment 5
Take the baking molybdenum powder end drying thulium oxide starting powder and purity 99.9% of purity 99.5%, protect in inert gas
In the glove box of shield, according to mass percent Mo-50wt%Tm2O3Mix after being weighed, add stearic acid process control agent simultaneously
Make its whole quality accounting be less than 2wt%, obtain mixed-powder；Load in ball grinder and tighten ball grinder lid, will be above-mentioned mixed
Close powder in ratio of grinding media to material 10:1st, packing factor 0.5, under conditions of rotational speed of ball-mill 100rpm, stop 5min according to ball milling 55min
Mode respectively ball milling 150h, intermittent duty can prevent ball grinder temperature too high.Then by the mixed-powder after ball milling in hand
Load rubber package set in casing and tighten, then the rubber package set tightening is placed in the hydraulic cylinder in isostatic cool pressing instrument, in pressure
Under conditions of power 500MPa, isostatic cool pressing 3h is to be pressed into column base substrate；Again base substrate is placed in Ar-sintering stove,
1800 DEG C of sintering 3h, obtain final product molybdenum base thulium oxide pellet, and thulium oxide is 1 with the mass ratio of molybdenum base:1.
Above-mentioned molybdenum base thulium oxide pellet, after over mechanical processing, can obtain the final pellet of regular shape, and this is final
Pellet is placed in nuclear reactor ash control rod involucrum, constitutes a kind of nuclear reactor ash control rod, can use together with other parts
In the operation controlling nuclear power plant reactor.
Embodiment 6
Take the baking molybdenum powder end drying thulium oxide starting powder and purity 99.9% of purity 99.5%, protect in inert gas
In the glove box of shield, according to mass percent Mo-21wt%Tm2O3Mix after being weighed, add stearic acid process control agent simultaneously
Make its whole quality accounting be less than 1wt%, obtain mixed-powder；Load in ball grinder and tighten ball grinder lid, will be above-mentioned mixed
Close powder in ratio of grinding media to material 10:1st, packing factor 0.4, under conditions of rotational speed of ball-mill 500rpm, stop 5min according to ball milling 55min
Mode ball milling 48h, intermittent duty can prevent ball grinder temperature too high.Then by the mixed-powder after ball milling in glove box
Load rubber package set and tighten, then the rubber package set tightening is placed in the hydraulic cylinder in isostatic cool pressing instrument, in pressure
Under conditions of 280MPa, isostatic cool pressing 0.5h is to be pressed into column base substrate；Again base substrate is placed in Ar-sintering stove,
1600 DEG C of sintering 24h, obtain final product molybdenum base thulium oxide pellet, and thulium oxide is 1 with the mass ratio of molybdenum base:3.76.
According to standard GB/T/T-5163-2006《The mensure of density of sintered material, oil content and percent opening》Tested
The density of above-mentioned molybdenum base thulium oxide pellet is 9.2351g cm-3.
The above-mentioned molybdenum base thulium oxide block tested using heat transfer analysis instrument is in the thermal diffusion system of room temperature, 500 DEG C and 800 DEG C
Number, thermal capacitance, the value of thermal conductivity are listed in Table 1 below.
Table 1 molybdenum base thulium oxide sinters the physical property test result of block
Fig. 4 is the Mo-21wt%Tm of above-mentioned condition2O3The percentage elongation of pellet and thermal coefficient of expansion variation with temperature curve.
As shown in figure 4, the percentage elongation of sample is in line rising with the increase of temperature, reach the 0.51% of maximum at 800 DEG C；In temperature relatively
When low, thermal coefficient of expansion quickly raises with the rising of temperature, rises high thermal expansion coefficient with temperature and be slowly increased after 250 DEG C
In stable.
Fig. 5 is scanning electron microscope diagram and the elemental line scan EDAX results of molybdenum base thulium oxide pellet.From scanning
Electron microscope in figure is not it is observed that after sintered, thulium oxide Dispersed precipitate in molybdenum base, advise by the shape of thulium oxide
Then；Can learn that oxygen element is consistent with the variation tendency of thulium element from EDAX results, and become with the change of molybdenum element
Gesture is contrary, shows that the material of white is thulium oxide, the material of black is Mo substrate.
Fig. 6 is transmission electron microscope pattern and the EDAX results of molybdenum base thulium oxide pellet, can learn brilliant in molybdenum
In grain, Dispersed precipitate the thulium oxide precipitated phase of nano-scale simultaneously.
Above-mentioned molybdenum base thulium oxide pellet, after over mechanical processing, can obtain the final pellet of regular shape, and this is final
Pellet is placed in nuclear reactor ash control rod involucrum, constitutes a kind of nuclear reactor ash control rod, can use together with other parts
In the operation controlling 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 obtaining
Same as the previously described embodiments or close technique effect：
Under inert gas shielding, by the baking drying thulium oxide powder and purity more than 99.9% of purity more than 99.5%
Dry molybdenum powder, according to mass percent Mo- (5～50) wt%Tm2O3Mix after being weighed, add process control agent and make
Its whole mass concentration is less than 2wt%, obtains mixed-powder；By above-mentioned mixed-powder in ratio of grinding media to material 1～30:1st, packing factor
0.1～0.8, under conditions of rotational speed of ball-mill 100～600rpm, stop the mode ball of 5～10min according to ball milling 50～55min
Mill 3～150h；Then by the mixed-powder after ball milling under conditions of pressure 100～500MPa isostatic cool pressing 0.1～3h to press
Make base substrate；Again base substrate is placed under inert gas shielding and sinters 3～100h at 1300～1800 DEG C, obtain final product described molybdenum base oxygen
Change thulium pellet, by molybdenum as matrix, thulium oxide is distributed in Mo substrate as disperse phase, and thulium oxide is 1 with the mass ratio of molybdenum:
1～1:9.
The above, only present pre-ferred embodiments, therefore can not limit according to this present invention enforcement scope, that is, 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 (9)
1. a kind of nuclear reactor ash control rod with molybdenum base thulium oxide material it is characterised in that：Described molybdenum base thulium oxide material is by molybdenum
As matrix, thulium oxide is distributed in Mo substrate as disperse phase, and thulium oxide is 1 with the mass ratio of molybdenum:0.8～1:10.
2. a kind of molybdenum base thulium oxide pellet being made up of the material described in claim 1.
3. a kind of method of the molybdenum base thulium oxide pellet prepared described in claim 2 it is characterised in that：In inert gas shielding
Under, by the baking molybdenum powder end drying thulium oxide powder and purity more than 99.5% of purity more than 99%, according to mass percent
Mo- (3～55) wt%Tm2O3Mix after being weighed, add process control agent and so that its whole mass concentration is less than
2.5wt%, obtains mixed-powder；By above-mentioned mixed-powder in ratio of grinding media to material 0.8～35:1st, packing factor 0.05～0.85, ball milling
Under conditions of rotating speed 80～650rpm, stop the mode ball milling 2～160h of 4～12min according to ball milling 45～60min；Then
By the mixed-powder after ball milling under conditions of pressure 80～550MPa isostatic cool pressing 0.05～4h to be pressed into base substrate；Again by base
Body is placed in and sinters 2～110h at 1200～1900 DEG C under inert gas shielding, obtains final product described molybdenum base thulium oxide pellet.
4. method according to claim 3 it is characterised in that：Described ratio of grinding media to material is 10～30:1.
5. method according to claim 3 it is characterised in that：Described packing factor is 0.3～0.8.
6. method according to claim 3 it is characterised in that：Described rotational speed of ball-mill is 300～600rpm.
7. method according to claim 3 it is characterised in that：The pressure of described isostatic cool pressing is 200～500MPa.
8. a kind of molybdenum base thulium oxide pellet be used for prepare nuclear reactor ash control rod purposes it is characterised in that：Described molybdenum base oxygen
Change the molybdenum base thulium oxide pellet that thulium pellet is described in claim 2, or be the side according to any one of claim 3 to 7
Molybdenum base thulium oxide pellet prepared by method.
9. a kind of nuclear reactor ash control rod, including involucrum it is characterised in that：It is provided with described in claim 2 in described involucrum
Molybdenum base thulium oxide pellet, or be the molybdenum base thulium oxide pellet prepared by the method according to any one of claim 3 to 7.
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|---|---|---|---|---|
| JPH0777594A (en) * | 1993-09-08 | 1995-03-20 | Nippon Nuclear Fuel Dev Co Ltd | Control rod for fast breeder reactor |
| EP0364650B1 (en) * | 1988-10-19 | 1996-10-09 | General Electric Company | Sintered polycrystalline neutron-absorbent bodies comprising lanthanide rare-earth oxides and same water stabilized with a 4A-group metal oxide. |
| 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 |
| CN105734385A (en) * | 2016-04-08 | 2016-07-06 | 厦门大学 | Iron-based dysprosium iron oxide material and application thereof |
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2016
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0364650B1 (en) * | 1988-10-19 | 1996-10-09 | General Electric Company | Sintered polycrystalline neutron-absorbent bodies comprising lanthanide rare-earth oxides and same water stabilized with a 4A-group metal oxide. |
| JPH0777594A (en) * | 1993-09-08 | 1995-03-20 | Nippon Nuclear Fuel Dev Co Ltd | Control rod for fast breeder reactor |
| 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 |
| CN105734385A (en) * | 2016-04-08 | 2016-07-06 | 厦门大学 | Iron-based dysprosium iron oxide material and application thereof |
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