CN1102668C - Hafnium alloy and neutron absorbent of nuclear reactor control stick using said alloy - Google Patents
Hafnium alloy and neutron absorbent of nuclear reactor control stick using said alloy Download PDFInfo
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- CN1102668C CN1102668C CN99104147A CN99104147A CN1102668C CN 1102668 C CN1102668 C CN 1102668C CN 99104147 A CN99104147 A CN 99104147A CN 99104147 A CN99104147 A CN 99104147A CN 1102668 C CN1102668 C CN 1102668C
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Abstract
The invention provides a Hafnium alloy with high plastic processability and high corrosion resistance, a neutron absorbent of nuclear reactor control stick using said alloy and a nuclear reactor control stick. The neutron absorbent of nuclear reactor control stick of the invention comprises of a specified component Hf alloy, which contains at least one of 0.03-1.5% Cr, 0.03-1.5% Sn and 0.03-2.0% Fe, Hf and 0.1-4.5% Zr, in which the total amount of Hf and 0.1-4.5% Zr is not less than 97%, or their alloy, and made of rectangle cylindraceous long-member.
Description
The command bundle rods for nuclear reactors that the present invention relates to high corrosion resistance hafnium (Hf) alloy and used this alloy with neutron absorber and reactor with control rod and the nuclear reactor and the Nuclear power plants that use this control rod.
The thermal neutron absorption cross section of hafnium is long-pending not necessarily big, but has a plurality of peak values in the resonance energy zone, therefore, has the character of effective nuclear dimension as the control rod of nuclear reactor.Meanwhile, even if owing to also have good processibility and also have reasonable erosion resistance in high temperature and high pressure steam, old friends attempt it as long lifetime control rod material.Initial being sealed by stainless steel do not contact it with the water of reactor, but now directly contacts with the water (heap water) of reactor.
Use as control rod as if hafnium is installed in the nuclear reactor for a long time, then in its process, can generate the white corrosion resultant from the teeth outwards mottledly, through becoming lamellated loose oxide film after the lumps corrosion.The worry that the oxide film of the oxide film that has these whitenings part in growth will be peeled off.
Now, the control rod of BWR (boiling water formula reactor) usefulness, use as the neutron absorbing material with norbide (B
4C) powder is filled into the control rod that the neutron absorption tube that goes in the thin stainless steel tube is configured to the inboard of criss-cross stainless steel component.This control rod constitutes the unit of 4 groups of fuel units and nuclear reaction pile core (the stove heart).In other words, control the output rating of 4 groups of fuel units with the control rod of one.
From the viewpoint of the utilization ratio that improves Nuclear power plants from now on, be to the long-term development of running period.Therefore, be the task of top priority work-ing life that adds length control rod.For this situation, it is increasing that hafnium (Hf) is applied to the situation of going in the existing BWR control rod.For example, in Japanese Patent Publication 58-44237 number, just proposed to use the scheme of the control rod of Hf in the upper section of control rod and side part.In addition, open in clear 56-74690 number, also show control rod with tabular use Hf or hafnium (Hf) alloy Japanese kokai publication sho 56-978897 number or spy.
It is generally acknowledged that the erosion resistance of Hf material in high-temperature water is very good, still, for using for a long time under the BWR environment, its erosion resistance is not enough.As the alloy that improves the erosion resistance purpose, under the situation of Hf base alloy, at Japanese kokai publication sho 59-208043 number, the spy opens clear 61-66188 number, in the flat 9-500931 of the special table grade, has proposed interpolation Fe, Sn, Ni, Cr, the motion of one or more among Nb and the Zr.But, these alloys since addition many, to adjust multiple alloying element, the price that exists material is expensive, processibility is low, and the problem that will increase the unhomogeneity etc. of characteristic.
If hafnium is installed in the nuclear reactor for a long time as the control rod use, then As time goes on can because of and reactor water between oxidizing reaction form oxide film.This oxide growth gets heterogeneity, will develop into lumps, but also peels off because of producing with white corrosion.Peeling off of oxide compound will make control characteristic reduce, and can constitute a big obstacle to the long lifetime of control rod.
The purpose of this invention is to provide a kind of plastic working height, and the command bundle rods for nuclear reactors that has hafnium (Hf) alloy of high corrosion resistance and used this alloy is with neutron absorber and control rod for nuclear reactor.
The present invention is a kind of calculation by weight, and Cr 0.03～0.8%, and Zr 0.1～4.5%, and remainder is essentially the high corrosion resistance Hf alloy of Hf.
The present invention is a kind of calculation by weight, and Sn 0.03～0.5%, and Fe 0.05～0.5%, and Zr 0.1～4.5% remainder is essentially the high corrosion resistance Hf alloy of Hf.
The present invention is a kind of calculation by weight, contains Sn 0.03～1.5%, and Fe 0.03～2.0%, Zr0.1～4.5%, and the total amount of Hf and Zr is more than 97%, ratio (Sn/Fe) is 0.2～1.6 high corrosion resistance Hf alloy.
The present invention is a kind of calculation by weight, and Sn 0.03～0.5%, and Fe 0.03～0.5%, Cr0.03～0.5%, and Zr 0.1～4.5%, and remainder is essentially the high corrosion resistance Hf alloy of Hf.
The present invention is a kind of calculation by weight, contains Sn 0.03～1.5%, and Fe 0.03～2.0%, Cr0.03～1.5%, and Zr 0.1～4.5%, and the total amount of Hf and Zr is more than 97%, and ratio (Sn/Fe+Cr) is 0.05～0.5 high corrosion resistance Hf alloy.
The present invention is a kind of calculation by weight, and Sn 0.03～0.5%, and Cr 0.03～0.5%, and Zr 0.1～4.5%, and remainder is essentially the high corrosion resistance Hf alloy of Hf.
The present invention is a kind of calculation by weight, contains Sn 0.03～1.5%, and Fe 0.03～2.0%, Cr0.03～1.5%, Nb 0.03～1.5%, and Zr 0.1～4.5%, the total amount of Hf and Zr is more than 97%, and ratio (Sn/Fe+Cr+Nb) is 0.1～0.5 high corrosion resistance Hf alloy.
The present invention is a kind of calculation by weight, contains Sn 0.03～0.5%, and Fe 0.03～0.5%, Cr0.03～0.5%, and Nb 0.05～0.5%, and Zr 0.1～4.5%, and remainder is essentially the high corrosion resistance Hf alloy of Hf.
The present invention is a kind of high corrosion resistance Hf base alloy, it is characterized in that: constitute by Hf base alloy, this base alloy has the Hf of 97 weight %, Vickers' hardness under the room temperature of this Hf alloy carried out thickness 50% rolling with hot rolling after is 220～250, carried out 8 hours and after 530 ℃ of heating of carrying out in 16 hours the water vapor, its corrosion weight grow is 50mg/cm at 410 ℃
2Below.
The present invention is a kind of command bundle rods for nuclear reactors neutron absorber, this neutron absorber contains Cr 0.03～1.5% by calculating by weight, Sn 0.03～1.5%, at least a in Fe0.03～2.0%, and the total amount of Hf and Zr 0.1～4.5% is that Hf alloy or the above-mentioned various Hf alloys more than 97% constitute, perhaps constitute, and constitute by the long member of rectangle tubular by the alloy that on the surface of these alloys, has the oxide film of alloy itself.
The present invention is a kind of control rod for nuclear reactor, possessing handle, be connected to the shell on this handle, be located at the neutron absorber in this shell, the pull bar that is equipped with making this shell crosswise, the below of being located at this pull bar is controlled at the falling velocity slicer of the falling velocity in the nuclear reactor, and be located in the command bundle rods for nuclear reactors of gang socket of bottom of this falling velocity slicer, it is characterized in that: above-mentioned neutron absorber, contain Cr 0.03～1.5% by calculating by weight, Sn0.03～1.5%, at least a in Fe0.03～2.0%, and the total amount of Hf and Zr 0.1～4.5% is that Hf alloy or the above-mentioned various Hf alloys more than 97% constitute, and perhaps is made of the alloy that has the oxide film of alloy itself on the surface of these alloys, and is made of the long member of rectangle tubular.
The present invention is a kind of neutron source pipeline that possesses in nuclear reactor pressure container, the core supporting plate, neutron is measured pipe, control rod, sheath, top turbogrid plates and have coated tube and the nuclear reactor of the structure member of the fuel assembly of subassembly wrapper (channel box), it is characterized in that: described control rod is made of above-mentioned control rod.
The present invention a kind ofly uses the thermal output that is obtained by the nuclear fuel that is accommodated in the nuclear reactor pressure container that steam turbine is rotated, and by means of the rotating drive generator of this steam turbine, obtain the Nuclear power plants of electric energy output thus, it is characterized in that: the thermal output of above-mentioned nuclear reactor is greater than 3200MW, nuclear reactor pressure is greater than 7.0Mpa, the nuclear reactor water temperature is more than 288 ℃, above-mentioned electric energy output is greater than 1100MW, possess the neutron source pipeline in the above-mentioned nuclear reactor pressure container, the core supporting plate, neutron is measured pipe, control rod, sheath, each member of top turbogrid plates, described control rod is made of above-mentioned control rod.
The present invention adopts with the compound tin that inserts of specific relation, zirconium, chromium, the way of iron and niobium, improved the erosion resistance in high-temperature water significantly, and adopt the novel hafnium alloy make the oxide compound that obtains by oxidizing reaction become fine and close material to constitute the way of control rod, the life-span of having improved control rod for nuclear reactor significantly.
The result that the influence of bringing for the erosion resistance of Hf to element is studied learns: do not damage tin, iron, chromium and the niobium of amount of the mechanical properties of Hf by an amount of interpolation, the effect that can obtain forming compact oxide and improve erosion resistance significantly first.
Zirconium just exists when making hafnium, and its amount is that 0.1～4.5 weight %, particularly this amount are 0.5～2.0%, ideal.
Addition (weight %) Sn as alloying element should be 0.03～1.50%, if less than 0.03% does not then have enough effects for intensity and erosion resistance, conversely, if amount has surpassed 1.5%, the formation of oxide film will become significantly, so be undesirable.Particularly this amount is 0.03～0.5%, ideal.
Even if it also is effectively that Cr adds 0.03～1.5% separately, then oxide film is more stable and can become the structure of densification if carry out compound interpolation with tin.Particularly this amount is 0.05～0.5%, ideal.
Fe improved erosion resistance at 0.03～2.0% o'clock significantly.But, add Fe separately and will become and be attended by the unsettled oxide film of crumby corrosive, so carry out compound interpolation with Sn, the way that forms with the homogeneous corrosion makes the oxide film densification.Surpass 2.0% if Fe adds, then the ductility of material can reduce.Particularly this amount is 0.05～0.5%, ideal.
The trace of Nb interpolation 0.01～1.50% gets final product, if add separately, then the corrosion meeting is quickened slightly, and erosion resistance is reduced, but by means of Sn, the compound interpolation of Fe and Cr but has the effect that suppresses corrosion and make oxide film become strong.Particularly Nb can weaken because of Sn, and the interpolation of Fe and Cr and the increase of the hardness that forms are so can make contributions to improve erosion resistance to increasing Sn, Fe and Cr.Particularly Nb is 0.05～0.5%, ideal.
Equally,, adopt the former is added Cr, the latter is added the way of Sn can similarly weaken the increase of hardness, the raising of erosion resistance, scale resistance is made contributions for the interpolation of Sn+Fe or Cr.
(Sn/Fe) than it is desirable to 0.2～1.6%.In this scope, can obtain high erosion resistance.
(Sn/Fe+Cr+Nb) than being 0.1～0.5% can obtain high erosion resistance equally and can not improve hardness.
It is way more than 97% that employing makes the total amount of Hf and Zr, in the important function that can obtain as the neutron absorbing material, can also obtain becoming for bar-shaped the material that the plastic working of rectangle tubular is high.
More specifically get on very well, the present invention is a kind of control rod, it is characterized in that: the top on each limit of the pull bar of criss-cross shape of cross section is equipped with the shell with U word shape of cross section, and taking in by the cross section in the inside of this shell is the reactivity control member that pole shape, hafnium alloy tabular or the hollow elliptical shape constitute.
As the manufacture method of boiling-water reactor of the present invention, it is characterized in that: conductive member is used as negative electrode, hafnium alloy is used as anode connects, and, carry out anodic oxidation in the electrolytic solution of bromic acid at ammonium borate with control rod.
Ideal is that platinum or stainless steel etc. is used as negative electrode, hafnium alloy is used as anode connects, and carries out anodic oxidation with direct supply in the scope from constant voltage 10V to 300V in above-mentioned electrolytic solution.
In order on the surface, inside and outside of the hafnium alloy of tube shape, to form oxide film thereon, manufacture method of the present invention it is characterized in that insertion cathod elements in pipe, simultaneously, cathod elements is set on tube outer surface, makes the cathod elements electrically conducting, and carry out anodic oxidation with electrolytic processing apparatus.
Fig. 1 is the curve of the relation of expression oxide thickness and Cr amount.
Fig. 2 is the curve of the relation of expression oxide thickness and Sn amount.
Fig. 3 is the curve of the relation of expression oxide thickness and Sn amount.
Fig. 4 is the curve of the relation between expression corrosion weight grow and the Sn+Fe+Cr+Nb amount.
Fig. 5 be the expression corrosion weight grow with (Sn/Fe) compare between the curve of relation.
Fig. 6 be the expression corrosion weight grow with (Sn/Fe+Cr) compare between the curve of relation.
Fig. 7 be the expression corrosion weight grow with (Sn/Fe+Cr+Nb) compare between the curve of relation.
Fig. 8 is the curve of the relation between expression corrosion weight grow and Fe or the Sn amount.
Fig. 9 be expression after the hot rolling hardness and the curve of the relation between the Sn+Fe+Cr+Nb.
Figure 10 is the curve of the relation between the hardness after expression corrosion weight grow and the hot rolling.
Figure 11 is partly cut-away's oblique drawing of control rod for nuclear reactor.
Figure 12 is the oblique drawing of command bundle rods for nuclear reactors with neutron absorber.
Figure 13 is the oblique drawing of command bundle rods for nuclear reactors with neutron absorber.
Figure 14 is partly cut-away's oblique drawing of Nuclear Reactor Core.
Embodiment
[embodiment 1]
In table 1, (use weight %) and listed for the chemical ingredients of experiment with material.No.2,3,6～8,11,12,14,17 and 18 is the used materials of the present invention, No.20, the 21st, existing material, other then is the material of usefulness relatively.
The chemical ingredients rough segmentation of material gets up to have the alloy of independent interpolation Cr, and the two component system alloy of Sn and Fe and Sn and Cr is arranged, and the ternary alloy of Sn and Cr and Nb and Sn and Fe and Nb is arranged, and the quaternary system alloy of Sn and Fe and Cr and Nb is arranged.Zr maximum 4.5% as the impurity when making hafnium left behind becomes to being 0.02～3.0% to the maximum in material of the present invention.Table 1
| No. | Hua Group becomes (weight %) | |||||||
| Sn | Fe | Cr | Nb | Zr | Sn — Fe | Sn —— Fe+Cr | Sn ———— Fe+Cr+Nb | |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 | - - - - ＜0.01 0.06 0.10 0.47 1.00 ＜0.01 0.05 0.09 0.15 0.12 3.00 - 0.07 0.13 0.30 ＜0.01 ＜0.01 | - - - - 0.15 0.12 0.13 0.13 2.10 0.05 0.06 0.10 2.00 - - - 0.11 0.10 0.15 0.02 0.03 | ＜0.01 0.09 0.50 2.00 - - - - - 0.05 0.10 0.09 0.10 0.15 0.50 - 0.05 0.10 0.40 ＜0.01 ＜0.01 | - - - - - - - - - - - - - - - 0.13 0.12 0.10 2.60 ＜0.01 ＜0.01 | 0.78 0.80 0.75 0.80 1.58 1.78 1.50 1.80 1.85 0.80 0.85 0.85 0.80 0.87 0.75 1.85 1.78 1.85 1.75 1.85 0.80 | - - - - 0 0.50 0.77 3.62 0.48 0 0.83 0.90 0.08 - - 0 0.64 1.30 2.00 0 0 | - - - - - - - - - 0 0.31 0.47 0.07 0.80 6.0 - 0.47 0.65 0.55 0 0 | - - - - - - - - - - - - - - - - 0.25 0.43 0.095 0 0 |
Each sample heated 1 hour at 1100 ℃ after 2 fusings become to desirable ingot in a vacuum carrying out repeatedly with arc-melting, implemented modified thermal treatment, then, carried out hot rolling at 1000 ℃, made it to become desirable thickness of slab.Anneal at 820 ℃, alternatively carry out repeatedly after cold rolling, the annealing under 820 ℃ makes it to become the thin plate that thickness is 1.7mm.
Table 2 has been listed the various characteristics of alloy.Corrosive property is that the 2 step corrosion experiment results that heating is carried out from 410 ℃ of 8 hours and 530 ℃ of water vapors of 16 hours carry out surface observation, obtains corrosion weight grow and oxide thickness postevaluation.Mechanical characteristics is estimated with hot rolling, cold rolling operation and hardness etc.Hot rolling is carried out at 1000 ℃, and making thickness is that the ingot of 10mm carries out 2 times and is 5mm by making it to become.In the present embodiment, measure Vickers' hardness under the constant room temperature of the state after keeping this hot rolling, understand the degree of this work hardening.Then, at 820 ℃ of heating anneals that carry out 1 hour, carry out 3 times cold rolling, carry out the annealing under the same temperature therebetween, make it to become the thickness of 1～2.5mm.Working modulus is calculated as 20～30% by the thickness decrement.In table, the difficulty or ease of processing are represented cold rolling difficulty or ease, are decided to be difficulty, are 10% also can the disruptive sample even if refer to the thickness decrement.
Table 2
| No. | Corrosion weight grow (mg/dm 2) | Oxide thickness (μ m) | Hardness after the hot rolling (Hv) | The difficulty or ease of processing |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 | 150 10 12 15 50 20 25 55 25 30 20 20 20 25 50 250 25 20 40 93 47 | 15.0 1.8 2.0 2.0 10.0 4.8 4.0 4.5 3.0 5.5 2.0 1.5 1.5 1.8 8.0 20.0 1.5 1.5 6.0 9.9 8.4 | 225 243 280 450 220 228 255 446 450 230 225 238 240 230 240 232 239 235 232 | The easy easily difficulty of difficulty difficulty is easy easily easily |
Separately the alloy that adds Cr is when addition is 0.02～1.50wt%, and etching extent is quite few, and oxide thickness is also below 2 microns, and is that a kind of oxide compound of densification generates.Also show good characteristic as for processibility.If put in order as the addition of Cr, then as shown in Figure 1, its amount is considerably less also effective to erosion resistance, even if measure the improvement that big 2.0wt% also shows erosion resistance.But containing Cr in large quantities, can harm the ductility of material, is undesirable.
This 2 yuan is alloy for Sn-Fe, though even if adding Fe separately also is that effectively oxide film is the lumps etch state, might not be desirable.Therefore, adopt Sn compound way to make oxide film become the form of homogeneous, can stop the formation of the oxide film of separability.Its effect is shown in Fig. 2.But a large amount of Sn and the interpolation of Fe can reduce the ductility of member, will become an obstacle in the thin plate manufacturing.
If is alloy for 3 yuan with Sn-Fe-Cr, each element all can be made contributions to erosion resistance, contains multiple element in this wise owing to resembling, so even if addition separately is a spot ofly also can obtain effective characteristic.As for corrosive property, as shown in Figure 3, at Fe, when Cr and Sn contained 0.05wt% respectively, oxide thickness was below 2 microns, and was that fine and close oxide film generates, and had and can't see the superior corrosion resistance of peeling off phenomenon fully.
If this 3 yuan is alloy with Sn-Fe-Cr, containing of Nb will promote the homogeneous corrosion in the formation of oxide film, have the effect that stops oxide compound to be peeled off.
Explanation Sn-Fe-Cr-Nb4 unit of bottom is an alloy.This alloy is self-evident in corrosive improvement, the character of its mechanical aspects, and it is suitable particularly being used as high-intensity member.It is low that but ductility and other invention alloy ratio are estimated, needs careful attention when making plate.
In addition, about the corrosive property in high-temperature water, 288 ℃, 80kg/cm had once been implemented
2Long-time corrosion test has confirmed to have superior corrosion resistance.
Fig. 4 is the graphic representation that shows the relation between corrosion weight grow and the Sn+Fe+Cr+Nb amount.As shown in the figure, as can be seen, because of Cr, Sn+Cr, Sn+Fe+Cr, the trace of Nb and Sn+Fe+Sn+Nb amount adds, and can obtain 50mg/dm
2Following high erosion resistance.Also can not get more than 1% than this bigger effect even if add.
The graphic representation of Fig. 5 show corrosion weight grow and (Sn/Fe) than between relation.As seen from the figure, at (Sn/Fe) than being that 0.2～1.6 o'clock etching extent is 40mg/dm
2, at (Sn/Fe) than being then to show 30mg/dm at 0.3～1.2 o'clock
2Following high corrosion resistance.
Fig. 6 show corrosion weight grow and (Sn+Fe+Cr) than between relation, as can be known 0.05～0.5th, ideal.
Fig. 7 show corrosion weight grow and (Sn+Fe+Cr+Nb) than between relation, as seen from the figure more than 0.1, measure and then can show 40mg/dm more greatly more
2Following etching extent.Particularly 0.1～0.5th, ideal.
The graphic representation of Fig. 8 shows the relation between the amount of corrosion weight grow and Fe or Sn, as seen from the figure, if independent Fe, then has 50mg/dm when above 0.03%
2Following high corrosion resistance, and adopt the way of in the material that contains 0.1～0.3% Fe, mixing 0.03～0.3% Sn, can obtain 30 mg/dm
2Following high corrosion resistance.
The graphic representation of Fig. 9 show after keeping hot rolling Vickers' hardness (Hv) and the Sn of rolling state when constant, Sn+Cr, Sn+Fe+Cr, Nb, the relation between the Sn+Fe+Cr+Nb amount.As seen from the figure,, be below 0.3% particularly so employing makes the former because the interpolation of Sn+Fe and Cr sharply uprises hardness, the latter is the way below 0.5%, can obtain work hardening hardness is the following softish processed goods that is difficult to work hardening of Hv260.Contain Sn+Cr, Sn+Fe+Cr, the increase of the work hardening hardness of the Hf alloy of Nb and NB+Fe-Cr+Nb is not almost found.
Figure 10 shows the relation between corrosion weight grow and the hardness.In the present embodiment, adopt the way that makes it to become appropriate moiety, can obtain corrosion weight grow at 50mg/dm
2Below, the processed goods that work hardening hardness Hv300 is following can obtain processibility height and high corrosion resistance.
[embodiment 2]
Figure 11 has been to use the oblique drawing of the boiling-water reactor of Hf alloy of the present invention with control rod.In the present embodiment, use the weight shown in the No.12 of table 1, found by means of arc-melting and contain 0.09%Sn, 0.10%Fe, 0.09%Cr and 0.85%Zr, remainder come down to the ingot of Hf.After twice fusing, the very aerial modified thermal treatment that is implemented in 1100 ℃, 1 hour is in the hope of adding the homogenization of element.Then, carry out hot rolling (1000 ℃ of heating), then, carry out the annealing of heating in 850 ℃, 1 hour for 2 times.In order to make it to become the thin plate of regulation, carry out cold rolling repeatedly and the thick thin plate of 1.7mm is finally made in annealing (820 ℃ 1 hour heating).The long slab material is processed into the shape of Figure 12, lumps together again and carry out the TIG welding, make the reactivity control member 27 of rectangle tubular shown in Figure 13, install in the control rod shell 23 of SUS316L and go.This shell is provided with communicating pores everywhere, and the reactivity control member 27 of Hf alloy always contacts with reactor water.Therefore, this member requires the erosion resistance in high-temperature water, and the Hf alloy in the present embodiment is the same with embodiment 1, and corrosion weight grow is 20mg/dm
2Below, oxide thickness is below 2.0 microns, the Hv after the hot rolling processing is below 250.Reactivity control member 27 in the present embodiment is wide to be 100mm, and thickness is 10mm, and in each control rod shell, each inserts 2 reactivity control members 27, and crosswise ground has 4 shells.Among the figure, the 22nd, handle, the 23rd, shell, the 24th, pull bar, the 25th, the falling velocity slicer, the 26th, gang socket, the 27th, as the reactivity control member of neutron absorber.
[embodiment 3]
Become the reactivity control member of smooth tubular with the limit of embodiment 2, formed anode oxide film in its surface.The described reactivity control member of present embodiment is identical with the member shown in Figure 11～13.As shown in the figure, end at criss-cross pull bar 24 each sheet is provided with the beveled end shape, the shell 23 that is processed into the U-shaped cross section is welded on the individual sheet of this pull bar 24, each fin is put into 2 reactivity control members 27 with elliptical shape cross section in formed space.In addition, reactivity control member 27 sometimes makes thickness of slab change on the control rod direction of principal axis, sometimes becomes the bar number of further cutting apart on direction of principal axis.
In the present embodiment, be the member that is used in the hafnium alloy plate processing and fabricating shown in the embodiment 2.At first, make the both ends of long slab material have curvature by means of the plate bending machining processing of carrying out with press brake because of bending machining.Secondly, implement the groove mechanical workout that is used to weld.Secondly, the size before welding is confirmed and clean, and the member of コ shape is docked to each other, and forms the oval tube shape by means of welding.Secondly, carry out mechanical workout, on oval tube, form cooling hole and be used for carrying out fixed hole etc., carry out precision work then and handle.In stage after this operation finishes, be dipped into and carry out the oxide film thereon processing in the electrolyzer.
In electrolyzer, be provided with the outside surface that is used for to hafnium alloy and carry out the stainless steel cathode rod of oxide treatment and be used for the hafnium alloy pipe internal surface is carried out the stainless steel cathode rod of oxide treatment, in electrolyzer, fill electrolytic solution.On the reactivity control member in this elliptical shape cross section that becomes the oxide treatment object, for and control rod structure member between fix, be provided with circular hole in the end of long side direction, and utilize under this circular hole and angle.By circular hole, hang with conductor, by elevator be connected to direct supply+electrode on.On the other hand, conductor introduction on the negative electrode in the electrolyzer, be connected to direct supply-electrode on.
In the present embodiment, length is about 1800mm, the above-mentioned reactivity control member that width is about 50mm divides 4 each step to carry out surface treatment.
In step 1,1/4 length of above-mentioned pipe is dipped in the electrolyzer, make it to form oxide film thereon with the direct supply energising.After oxide film thereon is stable, with this lifting device oxidized processing metal hafnium pipe is descended, 2/4 length of this hafnium pipe is dipped into carries out oxide treatment in the electrolyzer again.Below, carry out the formation of stable oxide film thereon successively from step 3 to step 4.
With above operation, carry out dimension inspection after having formed oxide film thereon from the teeth outwards, after cleaning, to get back to usually to control rod mounted inside control rod operation, the control rod of taking in the reactivity control member of having implemented oxide treatment promptly is made into.
Electrolytic solution applying boric acid ammonium [1% (NH
4) 205B
2O
3].As anodised general electrolytic solution, though in addition can also be with KOH or NaOH,,, used above-mentioned electrolytic solution for being difficult to that as impurity borate ion is put into the consideration that the hafnium rod goes.
At room temperature, between above-mentioned 2 utmost points, use 1A/dm respectively
2Current density add constant voltage 100V, 200V and 300V.Energising is decided to be the hold-time makes about about 5 minutes that settle out in the oxide film thereon that forms on the test film.
Test film for carried out anodic oxidation treatment with above method carries out visual inspection, corrosion resistance test and hardness test.The result of visual inspection shows, it is the main oxide film thereon that contains alloying element with Hf that the test film of each electric current has all formed same.In addition because the influence of voltage, from 100V to 300V the tone of formed tunicle from dark blue to dark green variation.This is the variation of formed oxide film thereon thickness, thereby, can come to judge by film thickness to a certain degree with tone.
To resulting reactivity control member, be 410 ℃/8hr+530 ℃/16hr in test temperature, pressure is 105kg/cm2, moltenly deposits oxygen 200～400ppb, under the condition of flow 10L/hr, carries out corrosion test.Formed the hafnium alloy member and the mother metal ratio that does not form oxide film thereon of anodic oxidation coating, corrosion weight grow is less than half, and erosion resistance improves.
In addition, the result who measures the hardness of anodic oxidation coating with little Vickers hardness tester shows, has formed the hafnium alloy member of anodic oxidation coating, and with the mother metal ratio that does not form oxide film thereon, the hardness on surface is increased to more than 1.5 times.That is, demonstrated the raising of wearability.Formed the reactivity control member of surface protection film by means of oxide treatment, can prevent damage and abrasion in following operation, can when keeping the condition of surface of homogeneous more, be assembled in the control rod inside and go.
In addition, during using actual reactor,, further prolong the use aspect, can guarantee the secular erosion resistance under the well-oxygenated environment in reactor than present situation seeking long term maintenance reactivity controllability.
[embodiment 4]
Figure 14 has been to use the local section oblique drawing of core of nuclear reactor of the control rod of embodiment 2 and 3.
This nuclear reactor is 286 ℃ of vapor temperatures, and vapor pressure 70.7atg is operation down, as the generating output rating can carry out 500,800, the generating of 1100MW.Each title is as follows.Core possesses: neutron source pipeline 51, core supporting plate 52, neutron measurement detector tube 53, control rod 54, core guard shield 55, top turbogrid plates 56, fuel assembly 57, nozzle 58 on show, curved nozzle 59, pressure container cover 60, flange 61 is measured with nozzle 62 air water separator 63, guard shield head 64, feed-water intake nozzle 65, jet-pump 66, steam dryer 68, steam outlet nozzle 69, feedwater atomizer 70, core jet nozzle 71, bottom core turbogrid plates 72, recycled water inlet nozzle 73, baffle plate 74 and control rod guide wire 75.
Above-mentioned top turbogrid plates 56 have cam body, flange and turbogrid plates, and these can use the rolling member of SUS316 steel polycrystalline.Turbogrid plates 35 only intersect mutually and do not interfix.In addition, core supporting plate 52 can use the rolling member of SUS316 steel polycrystalline too, can be provided with the hole that fuel is supported accessory is installed with a milled sheet manufacturing, is being fixed on the periphery on the reactor capacity.Therefore, no matter be a kind of which parts all do not have welding portion at the centre portions that is subjected to neutron irradiation structure.
Have the rod drive mechanism that can carry out little driving with electro-motor, rotor can be with the chromium carbide (Cr of 20～30 microns of the nickel alloy powder of chromium that contains 25wt% and particle diameters
2O
3) mix 10% by volume and carry out the rotor that sintering is made.Assemble 32 groups of pivots (pin) that constitute by high-strength F e base alloy, be used in the load that round-robin way in the high-temperature water of simulation real reaction heap is equivalent to 40 years and drive test.Test-results fully satisfies standard, and rotor and pivot are all very little because of the dimensional change that abrasion produce.Little destruction of hitting under the loading when in addition, also not finding the scram driving fully.
Rod drive mechanism in the present embodiment is a kind of screw rod of using by the piston driven that makes it to rotate with motor, drives the mechanism of control rod by aerial piston up and down by means of driven plunger, is connected on the reactor pressure vessel with welding process.Control rod drives in the control rod guiding tube.The employing of hydraulic drives piston lifts control rod by means of the way of water tubular stinger insertion water when urgent upward apace, separates with driven plunger.Particularly the part that contacts with high-temperature water will be used SUS316L.In addition, the structure of control rod is made to falling by deadweight.
Figure 15 is the control rod 1 that drives with rod drive mechanism 11, fuel assembly (A), (B), and fuel is supported accessory 14, the assembled configuration figure of core supporting plate 12.Figure 11 (A) is the fuel assembly that does not have handle, is configured in the b part of Figure 11 (C).(B) handle is arranged, be configured in a part of Figure 11 (C).Fuel is supported accessory 14 to be fixed as with the core supporting plate and is contacted the support fuel assembly.
The BWR fuel assembly is made of following part: many fuel sticks and make the multistage liner that they keep with the interval of regulation mutually, take in the subassembly wrapper of their square tube shape in addition, be configured in maintenance and fuel pellet be put into the top backing plate at the two ends of the fuel stick in the fuel coated tube, the follower of the centre portions of bottom backing plate and liner (water rod) is used for carrying the handle of whole assembly.In addition, when making these fuel assemblies, can be via common operation assembling.
Subassembly wrapper is being accommodated in inside by means of the fuel stick and the follower of insert integralization, and top backing plate and bottom backing plate use under the state that has fixed with follower.The length that is shaped as after cutting apart 2 with the plasma body welding process of fuel element case is 4m, and thickness is 80,100,3 kinds of square tube shapes that コ shape plate work material welds of 120mm.This member play when Nuclear power plants moves to the steam that produces on the fuel rod surface and between fuel stick the mobile high-temperature water carry out rectification, forcibly to the effect of top guiding.Because the built-in pressure ratio outside is high slightly, so use under the state of the effect of the stress that in long-time, square tube is being pushed laterally.
Subassembly wrapper in the present embodiment is heat-treated as described below.The thickness of slab direction＜0001〉crystal orientation orientation rate (Fr value) is 0.25～0.6, and the orientation rate (Fl) of length direction is 0.25～0.4, and the orientation rate (Ft) of width is 0.25～0.4.It is desirable to Fr is 0.25～0.5, and Fl is 0.25～0.36, and Ft is 0.25～0.36.By the way that it is orientated in this wise with thermal treatment, 50～300 microns of β Zr grain size average out to (it is desirable to 100～200 microns), can prevent the irradiation elongation significantly, the result does not produce bending, is prevented the interference between subassembly wrapper and the control rod.Therefore, even if degree of combustion is more than the 45GWd/t, can not produce bending even if be configured in the device of periphery, even if higher 50 or 60GWd/t also can use fully out of questionly yet.In addition, for existing degree of combustion 32GWd/t, also can behind exchange fuel, use.
Subassembly wrapper is that the cold rolling bending machining of its alloying constituent zirconium base alloy sheet material as shown in table 3 is become " コ " shape, makes to become 2 コ shape members of long 4m, again the square tube that they are made with laser or plasma body welding.The concavo-convex place of welding portion is trimmed to flat surfaces.To β phase temperature range, and use the water coolant that gushes out from the nozzle of the positive bottom that is located at radio-frequency induction coil to make it chilling to this square tube high-frequency induction heating.From the top down by coil, all thermal treatment finishes square tube with certain speed.Adjust the speed of sending into of square tube and the power of high frequency electric source, make that Heating temperature is 1100 ℃, and the hold-time more than 980 ℃ above 10 seconds.In addition, treatment temp it is desirable to 1000～1200 ℃, particularly can be used in 1050～1100 ℃ of ways that kept 3～10 seconds down and carry out.Thermal treatment is carried out after the axle that austenitic stainless steel is made is fixed on two ends on the tube with screw rod.As seen from table, (0002) bottom surface of 6 corner posts is the face of (1010) with cylinder, is 1/3 no matter be that Fr, Fl and Ft become substantially as the F value, becomes the crystal orientation orientation for completely random.The β Zr average crystal grain size of this object is about 100 microns.After having implemented this thermal treatment, high dimensional accuracy ground carries out moulding sandblasting and pickling, after having removed surface film oxide, implements the steaming of carrying out with water vapor and presses (autoclave) to handle.Table 3
| No. | Alloying element | |||||
| Sn | Fe | Cr | | O | Zr | |
| 1 | 1.50 | 0.21 | 0.10 | - | 0.12 | All the other |
| 2 | 1.50 | 0.15 | 0.10 | 0.10 | 0.12 | All the other |
| 3 | 1.50 | 0.35 | 0.10 | 0.10 | 0.12 | All the other |
Also have, as another example of subassembly wrapper, with respect to the subassembly wrapper of above-mentioned constant wall thickness, the thickness that has made a kind of corner part is thicker than limit portion, this subassembly wrapper with long side direction Thickness Distribution that the wall thickness of limit portion is thinner than the bottom on top.Such forming process is carried out after thermal treatment.The chemical corrosion that forming process is carried out with the mixing acid aqueous fusion liquid that shields earlier then with hydrogen fluoride and nitric acid or the way of mechanical workout are carried out, and in the present embodiment, are that outside one side is processed into concavity.Such Thickness Distribution also can make concavity in inner face one side.
The main specification in the BWR power station that obtains with above formation is: the reactor temperature is 288 ℃, and operation factor is more than 85%, and even more ideal is more than 90%, it is desirable to 92% especially, and thermo-efficiency is 35%.
[embodiment 5]
The same with embodiment 4, present embodiment shows fuel assembly of the present invention and rod drive mechanism is applied to the example that goes in the novel boiling water formula used in nuclear power station reactor (ABWR).
Nuclear reactor pressure container is the center machine of Nuclear power plants, in ABWR, the nozzle segment of internal pump particularly is installed, be a kind of optimum shape of socket type: even if produced the temperature and pressure variation in nuclear reactor pressure container inside, also can not influence the spinfunction of internal pump, also can reduce to the thermal conduction of motor portion.
In addition, the structure in the reactor has also reduced the influence to the vibration of flowing because of adopting internal pump to produce.The state of the part running of internal pump is considered in the measurement of reactor thermal core flow, comprises with testing the checking of carrying out guaranteeing precision.Flow to the measurement of the steam flow of steam turbine, carry out with the structure of Venturi (Venturi) formula on the main steam nozzle segment that is arranged on nuclear reactor pressure container, in order to ensure measuring accuracy.RPV (nuclear reactor pressure container) also has function built-in and the internal tank structure that keep-ups pressure in the pressure boundary that constitutes cooling component.
In existing RPV, though become about 6.4m because of taking in 764 fuel assemblies, jet-pump and its internal diameter of internal structure thing,, in ABWR, because of fuel assembly is increased to 872, and in order to ensure the processing space of internal pump in reactor, internal diameter has become about 7.1m.The internal height of existing RPV is 22m, but in ABWR, because of the former of following (a)～(d) thereby become 21m.
(a) owing to having adopted the high-level efficiency air water separator to shorten the length of support pipeline.
(b) owing to having adopted FMCRD to remove the excellent speed of fall slicer of restriction.
(c) because of changing the height that loam cake and main flange configuration have reduced loam cake.
(d) reduced the height of the dish-like shape of time mirror.
Following mirror shape is along with the employing of internal pump, consider and should guarantee that internal pump installs needed space to the bottom of pressurized vessel, and the circulation of considering water coolant made the shape of mirror down into dish from existing semisphere.In addition, internal pump forged be integral, become and be the few design of welding line number.
Supporting plate should be guaranteed the needed spatial whiles such as the processing of internal pump, the heat exchanger that internal pump is used also will be set, so partly made taper shape at body in pedestal.
Along with the employing of internal pump,,, there is no need to suppose big coolant loss accident so become to there not being the zone of heavy caliber nozzle below the body partial reaction pile core zone owing to cancelled the recirculation exit and entry nozzle of the refrigerant of existing Nuclear power plants.
In existing Nuclear power plants, though flow restrictor is arranged on the sloping portion of the segregaion valve that arrives the main team pipe top, but adopt it is arranged on way on the main steam nozzle, can improves safe clearance, can make accepting container space optimizing main team pipe pipeline breaking accident.
Structure is positioned at RPV in the reactor, formation except the runner of support in the reactor and refrigerant, and outside the significant feature to the hot water that in core, takes place, the function that steam carries out gas-water separation etc., also to guarantee the core water filling road of water coolant under hypothetical accident etc., because of its characteristic requires sufficient viability and reliability.
, compare with the BWR Nuclear power plants if take 50Hz to come comparison with equipment with the basic specification of steam turbine gen-set in the ABWR power station, in the ABWR Nuclear power plants, the nuclear reactor thermal output has increased by 19.2%, and electric power output has increased by 23.3%, is a kind of Nuclear power plants of high-level efficiency form.
In the present embodiment, also can obtain similarly to Example 4 life-span, make regular check on, operational efficiency and thermo-efficiency.
If adopt the present invention as mentioned above, then owing to the erosion resistance of having improved the neutron absorber in high-temperature water significantly, so the time limit of service of command bundle rods for nuclear reactors in nuclear reactor can prolong by leaps and bounds.In addition, the oxide film that generates on this control rod is fine and close, is difficult to peel off and stable, so the number of the control rod of finishing using can reduce, simultaneously, all right long term maintenance reactivity controllability is so can reduce the amount of radioactive waste significantly.
Claims (11)
1. a high corrosion resistance Hf alloy is characterized in that: calculate by weight, comprise Zr0.1～4.5%; That selects from Cr0.03～0.8%, Sn0.03～1.5%, Fe0.03～2.0% is individual at least one by one; And when the Zr, the Cr that contain above content simultaneously, Sn, Fe, can select Nb0.03～1.5% that adds; Remainder is Hf and unavoidable impurities.
2. high corrosion resistance Hf alloy as claimed in claim 1 is characterized in that: calculate by weight, comprise Sn 0.03～0.5%, Fe 0.05～0.5%, and Zr 0.1～4.5%, and remainder is essentially Hf.
3. high corrosion resistance Hf alloy as claimed in claim 1 is characterized in that: calculate by weight, comprise and contain Sn0.03～1.5%, Fe 0.03～2.0%, and Zr 0.1～4.5%, and the total amount of Hf and Zr is more than 97%, and ratio (Sn/Fe) is 0.2～1.6.
4. high corrosion resistance Hf alloy as claimed in claim 1 is characterized in that: calculates by weight, comprises Sn 0.03～0.5%, and Fe0.03～0.5%, Cr 0.03～0.5%, and Zr 0.1～4.5%, and remainder is essentially Hf.
5. high corrosion resistance Hf alloy as claimed in claim 1 is characterized in that: calculate by weight, comprise Sn0.03～1.5%, Fe 0.03～2.0%, and Cr 0.03～1.5%, and Zr 0.1～4.5%, the total amount of Hf and Zr is more than 97%, and ratio (Sn/Fe+Cr) is 0.05～0.5.
6. high corrosion resistance Hf alloy as claimed in claim 1 is characterized in that: calculate by weight, comprise Sn 0.03～0.5%, Cr 0.03～0.5%, and Zr 0.1～4.5%, and remainder is essentially Hf.
7. high corrosion resistance Hf alloy as claimed in claim 1, it is characterized in that: calculate by weight, comprise Sn 0.03～1.5%, Fe 0.03～2.0%, Cr 0.03～1.5%, and Nb 0.03～1.5%, and Zr 0.1～4.5%, the total amount of Hf and Zr is more than 97%, and ratio (Sn/Fe+Cr+Nb) is 0.1～0.5.
8. high corrosion resistance Hf alloy as claimed in claim 1 is characterized in that: calculate by weight, comprise Sn0.03～0.5%, Fe 0.03～0.5%, and Cr 0.03～0.5%, and Nb 0.05～0.5%, and Zr 0.1～4.5%, and remainder is essentially Hf.
9. high corrosion resistance Hf alloy as claimed in claim 1, it is characterized in that: comprise the above Hf of 97 weight %, Vickers' hardness under the room temperature of this Hf alloy carried out thickness 50% rolling with hot rolling after is 220～250,410 ℃ carried out 8 hours and 530 ℃ carry out 16 hours the heating in water vapor after, its corrosion weight grow is 50mg/cm
2Below.
10. command bundle rods for nuclear reactors neutron absorber is characterized in that: this neutron absorber is by constituting as the described Hf alloy of claim 1～9, and comprises the long member of rectangle tubular.
11. the described command bundle rods for nuclear reactors neutron absorber of claim 10 is characterized in that: the oxide film that is formed with this member on above-mentioned long component surface.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06976498A JP3489428B2 (en) | 1998-03-19 | 1998-03-19 | High corrosion resistance Hf alloy, neutron absorber for reactor control rod using the same, and control rod for reactor |
| JP069764/1998 | 1998-03-19 | ||
| JP069764/98 | 1998-03-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1236018A CN1236018A (en) | 1999-11-24 |
| CN1102668C true CN1102668C (en) | 2003-03-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99104147A Expired - Fee Related CN1102668C (en) | 1998-03-19 | 1999-03-19 | Hafnium alloy and neutron absorbent of nuclear reactor control stick using said alloy |
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| Country | Link |
|---|---|
| JP (1) | JP3489428B2 (en) |
| CN (1) | CN1102668C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2735842C1 (en) * | 2020-06-09 | 2020-11-09 | Акционерное общество "Чепецкий механический завод" | Method of producing thin sheets of hafnium with isotropic mechanical properties |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000266882A (en) * | 1999-03-16 | 2000-09-29 | Hitachi Ltd | Neutron absorber for reactor control rod, control rod for reactor, reactor and unclear power plant |
| FR2841368B1 (en) * | 2002-06-25 | 2004-09-24 | Framatome Anp | ARRANGEMENT FOR ADJUSTING THE REACTIVITY OF THE HEART OF A NUCLEAR REACTOR, ARRAY ABSORBING THE ARRANGEMENT AND METHOD FOR PROTECTING AGAINST THE WEAR OF THE ABSORBENT ARRAY |
| KR100698744B1 (en) * | 2003-03-07 | 2007-03-23 | 닛코킨조쿠 가부시키가이샤 | Hafnium alloy target and process for producing the same |
| JP5305716B2 (en) * | 2008-04-09 | 2013-10-02 | 株式会社東芝 | Reactor control rod |
| US9336910B2 (en) * | 2010-10-07 | 2016-05-10 | Bwxt Nuclear Energy, Inc. | Control rod/control rod drive mechanism couplings |
| RU2445399C1 (en) * | 2010-10-20 | 2012-03-20 | Открытое акционерное общество "Чепецкий механический завод" | Manufacturing method of flat hafnium profile |
| CN102915773B (en) * | 2012-04-27 | 2015-08-26 | 上海核工程研究设计院 | A kind of grey control rod and absorber |
| CN102915772B (en) * | 2012-04-27 | 2015-08-26 | 上海核工程研究设计院 | A kind of long service life gray control rod and absorber |
| JP2013054037A (en) * | 2012-11-20 | 2013-03-21 | Toshiba Corp | Reactor control rod |
| RU2742176C1 (en) * | 2020-05-12 | 2021-02-02 | Акционерное общество "Чепецкий механический завод" | Method of making rods and wires from hafnium |
| CN115838913B (en) * | 2022-12-06 | 2023-11-17 | 西安交通大学 | Method for improving high-temperature lead/lead bismuth corrosion resistance of material by coupling temperature control and irradiation effect |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59208043A (en) * | 1983-05-13 | 1984-11-26 | Toshiba Corp | Corrosion-resistant hafnium alloy and its production |
-
1998
- 1998-03-19 JP JP06976498A patent/JP3489428B2/en not_active Expired - Fee Related
-
1999
- 1999-03-19 CN CN99104147A patent/CN1102668C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59208043A (en) * | 1983-05-13 | 1984-11-26 | Toshiba Corp | Corrosion-resistant hafnium alloy and its production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2735842C1 (en) * | 2020-06-09 | 2020-11-09 | Акционерное общество "Чепецкий механический завод" | Method of producing thin sheets of hafnium with isotropic mechanical properties |
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| Publication number | Publication date |
|---|---|
| CN1236018A (en) | 1999-11-24 |
| JP3489428B2 (en) | 2004-01-19 |
| JPH11264885A (en) | 1999-09-28 |
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