CN101423943A - 用于反应堆金属元件以减少进入核反应堆环境的腐蚀产物的保护涂层 - Google Patents
用于反应堆金属元件以减少进入核反应堆环境的腐蚀产物的保护涂层 Download PDFInfo
- Publication number
- CN101423943A CN101423943A CNA2008102103810A CN200810210381A CN101423943A CN 101423943 A CN101423943 A CN 101423943A CN A2008102103810 A CNA2008102103810 A CN A2008102103810A CN 200810210381 A CN200810210381 A CN 200810210381A CN 101423943 A CN101423943 A CN 101423943A
- Authority
- CN
- China
- Prior art keywords
- coating
- reactor
- reactor water
- corrosion
- metallic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005260 corrosion Methods 0.000 title abstract description 38
- 230000007797 corrosion Effects 0.000 title abstract description 31
- 239000011253 protective coating Substances 0.000 title 1
- 238000000576 coating method Methods 0.000 claims abstract description 59
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 230000004888 barrier function Effects 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 229910052770 Uranium Inorganic materials 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 238000007772 electroless plating Methods 0.000 claims description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000010941 cobalt Substances 0.000 abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 9
- 229910000990 Ni alloy Inorganic materials 0.000 abstract description 8
- 239000010410 layer Substances 0.000 abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000963 austenitic stainless steel Inorganic materials 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 11
- 229910001936 tantalum oxide Inorganic materials 0.000 description 9
- 230000004913 activation Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 208000005189 Embolism Diseases 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- -1 that is Inorganic materials 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/04—Coating on selected surface areas, e.g. using masks
- C23C14/046—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Abstract
本发明涉及用于反应堆金属元件以减少进入核反应堆环境的腐蚀产物的保护涂层，尤其涉及隔离涂层被施加到核反应堆水环境中的金属元件以降低和/或减缓反应堆元件金属表面的一般腐蚀和侵蚀-腐蚀。优选地，涂层为0.1微米至0.3毫米薄层的氧化物涂层，例如氧化钛、氧化锆、氧化钽、Al2O3、CeO2或类似氧化物；或者将在反应堆水环境中发生氧化的金属，例如Ti、Zr、Ta、Hf、Ce、Al。该施加的涂层在元件表面和反应堆水环境之间提供保护层。通过减小和/或清除反应堆金属元件潜在的腐蚀，该涂层消除或最小化活化腐蚀产物污染反应堆水的可能。该涂层对贡献大量钴相关腐蚀产物的镍合金基金属尤其有利，对奥氏体不锈钢元件也有效。
Description
技术领域
[0001]本发明涉及施加至反应堆金属元件以减少元件释放腐蚀产物的保护涂层。
背景技术
[0002]在核反应堆水环境，例如沸水堆(BWR)，压水堆(PWR)或加拿大氘铀反应堆(CANDU)中，金属元件会产生腐蚀产物。如果反应堆元件由镍合金制成，就需要关注含钴腐蚀产物，含钴腐蚀产物用活性物种，尤其是钴—60，对反应堆水产生污染。有些钴是天然存在于镍合金中的杂质元素，此外，镍同位素在中子通量中能够被转变为活化的钴同位素。特定的，含钴腐蚀产物问题成为污染问题的主导。钴在反应堆中子通量中被活化，因此，存在着活化腐蚀产物污染水的可能。反应堆水中的活化腐蚀产物能够转移到反应堆容器外面的元件和系统内，因而提高了工作人员受到的职业性辐射。
[0003]专利号US6630202、名为“CVD Treatment of Hard Friction CoatedSteam Line Plug Grips”的美国专利验证了在温和的环境中化学气相沉积(CVD)涂层在腐蚀方面的保护性。美国专利US6633623支持了在沸水堆(BWR)环境中硬质的、耐侵蚀-腐蚀CVD涂层在结垢方面的作用。
发明内容
[0004]本发明涉及通过向核反应堆中的金属元件表面施加隔离涂层(insulatingcoating)来减少核反应堆水环境中由于金属元件的腐蚀而产生的活化腐蚀产物，例如Co-60，的方法。所述隔离涂层，例如氧化钛(TiO2)、氧化锆(ZrO2)、氧化钽(Ta2O5)、氧化铝(Al2O3)、氧化铪(HFO2)、氧化铈(CeO2)或类似氧化物，是通过化学气相沉积法(CVD)或其他涂覆方法施加到元件表面的。其他的涂覆方法，例如等离子或HVOF热喷涂法、线弧(wire arc)、PVD、RF溅射和电镀法也是可行的。涂层厚度可以在0.1微米至0.3毫米的范围内，这取决于涂覆过程。同样需要指出的是，涂层也可以以金属元素，即，Ti、Zr、Ta、Al、Hf、Ce等施加，这些金属最终在反应堆水中发生氧化得到氧化物，例如TiO2。该涂层在反应堆环境与元件表面之间提供了保护层。反应堆金属元件上的该涂层的主要目的是减少和/或消除腐蚀可能性。通过这样做，因而活化的腐蚀产物污染反应堆水的可能性被消除或最小化。对于贡献出大量含钴腐蚀产物的镍合金基金属而言，该涂层特别有益。该涂层也对奥氏体不锈钢元件有效，因为不锈钢含有大量的镍以及作为杂质元素的钴。例如，CVD处理施加了共形表面涂层(conformal surface coating)，并另外填充了金属元件中的空穴/孔隙。另外，在前述专利中，硬质的、耐侵蚀-腐蚀的CVD涂层已经表明了对反应堆水环境的抵抗力。因此，通过密封表面和空穴，水分侵入基底金属的可能性被减小和/或消除，这样，就减小了腐蚀和随后腐蚀产物向反应堆水中释放的可能性。
[0005]本发明提供了薄的隔离涂层(或在反应堆水环境中发生氧化的金属涂层)，该涂层通过CVD或其它涂覆方法涂覆到将位于反应堆水环境中的反应堆元件的暴露表面上。但是，优选涂层是氧化钛，其它氧化物涂层可以是氧化钽、氧化锆或其他在反应堆水环境中使用不容易退化的类似氧化物。对在反应堆水环境中的金属元件进行CVD表面处理的优点如下：
◆施加最小厚度(例如0.1～5微米)的隔离CVD涂层；
◆能够进行共形表面处理，其覆盖所有表面，包括穿孔、气孔、空间和裂缝的内部；
◆用硬质氧化物材料，例如氧化钽、氧化钛、氧化锆或其它不容易由于反应堆水和中子暴露而老化的类似氧化物，来填充金属元件的孔隙和/或空间。
◆是共形表面处理，允许用CVD材料覆盖金属表面并填充所有孔、空间和裂缝；
◆CVD处理在反应堆水环境中是耐侵蚀性和耐腐蚀性的；
◆CVD处理是金属表面上的硬质的、粘连性的涂层；
◆CVD处理能够消除或减小腐蚀产物从金属元件释放进入反应堆水环境中；并且
◆等离子热喷涂或高速氧燃料热喷涂法(HVOF)、物理气相沉积法(PVD)、射频(RF)溅射处理方法、电镀法和无电镀法是在一些元件上施加5微米到0.3毫米厚的涂层的替换性方法；
◆金属元素，例如Ti、Ta、Al、Zr、Hf、Ce等可以作为保护涂层施加，并在在反应堆水环境中最终氧化。
附图说明
图1示出了化学气相沉积的隔离氧化物涂层的共形性质和强粘结性。
图2是经过CVD处理的不锈钢表面的扫描电镜显微照片，表明了氧化钛(TiO2)涂层在模拟高温和高水流速度下的估计的腐蚀速率。
图3示出了氧化钛(TiO2)涂层的粘连性、耐侵蚀-腐蚀的性能。
图4a和图4b表示经过喷盐测试(salt-spray testing)后，具有和没有氧化钽(Ta2O5)涂层的流线栓塞夹具(stream line plug grip)上的硬质耐磨涂层的表面形态。
图5表示通过CVD生产的氧化钽(Ta2O5)层的横截面图，表明氧化钽层沿着硬质耐摩涂层中的裂缝和孔的表面沉积。
具体实施方式
可以通过化学气相沉积(CVD)施加的各种金属氧化物，例如TiO2、Ta2O5、ZrO2、Al2O3、HfO2和CeO2，由于它们的热稳定性和化学稳定性以及低热膨胀系数，是被广泛地用作腐蚀阻挡层的材料。耐火氧化物的主要特点是在各种各样的腐蚀性和高温环境中都具有优异的耐腐蚀性。因此，给反应堆水环境中的金属元件加上涂层消除和/或减轻了元件腐蚀和因此用活化物种污染反应堆水的可能性。由于钴的贡献大(because of a high level of cobalt contribution)，镍合金元件是其中最受关注的。如图1所示，CVD处理在金属部件的表面形成了共形涂层，该涂层填充了空穴/空间并保护了该部件的基底金属不受腐蚀。由于所述处理，保护了基底金属合金不受反应堆水环境以及最终的腐蚀和进入到水中的腐蚀产物的影响。这些腐蚀抑制性涂层被应用于燃气轮机、航空发动机、推进器、阀门和其他经受腐蚀的元件/表面中的部件上。为该涂层提出的一个这种应用是保持各个燃料棒在BWR燃料束(fuel bundle)中的位置的间隔组件。对一些设计而言，这些间隔物由镍合金X-750制成。在每个燃料束中存在很多间隔物，使得大量表面积的镍合金暴露在反应堆水环境中。由于这些间隔物直接在堆心中，它们被高度辐照，因此有可能释放大量的活化腐蚀产物释放到反应堆水中。氧化物涂层的应用通过把镍合金与反应堆水隔绝开来，从而大大减小或消除所述活化腐蚀产物的释放。
图2是经过CVD处理的不锈钢表面的扫描电镜显微图片(“SEM”)。环氧树脂嵌入件不能把TiO2涂层从304SS基底中拉出来，也不能损坏TiO2涂层本身。这表明CVD制备的TiO2涂层具有很好的机械稳定性和与金属基底之间的强粘附力。这种涂层也应用于各种产品中，例如燃气轮机和航空发动机叶片。下表1列出了反应这些结果的数据。
关于图2，需要指出的是，在浸入高通量电极装置(high flow electrode setup)中一个月以后，涂层和不锈钢表面之间的粘附力与其初始值没有变化。此外，发现涂层在该测试过程中没有发生分层，而是在BWR环境中慢慢侵蚀。在测试过程中测量了这种侵蚀-腐蚀速率，从测试结果推出TiO2涂层的可能使用寿命大于20年。下表1列出了反应这些结果的数据。
表1
304 SS 上TiO2涂层的电阻测量
304 SS 上TiO2涂层的粘附强度
(在280℃水中浸没一个月后)
图3是TiO2涂层的粘附性的耐侵蚀-腐蚀性能示意图。耐腐蚀涂层，例如氧化钽(Ta2O5)、氧化钛(TiO2)、氧化铝(Al2O3)等，涂覆在流线栓塞夹具的硬质摩擦表面。涂层的目的是使用各种涂覆方法，例如PVD或CVD，填充该摩擦表面中的孔隙和裂纹。
图5示出了沿着流线栓塞夹具的硬质摩擦层中的裂缝和孔隙的表面沉积的CVD氧化钽层的SEM横截面图。这表明了涂层进入孔隙/裂纹/空间的深度。通过喷盐法(ASTM标准G112)评估了氧化钽耐腐蚀层的效果。
图4a和图4b表示经过喷盐测试后，具有和没有氧化钽涂层的硬质摩擦表面的腐蚀后的表面形态。可以看出通过氧化钽涂层显著地减小或减缓了摩擦表面的腐蚀。
[0006]虽然通过目前认为是最实用和优选的实施方案描述了本发明，但是应理解本发明不限于所公开的实施方案，相反，旨在覆盖包括在本发明所附权利要求的精神和范围内的各种变化和等同设置。
Claims (10)
1、减少和/或减缓核反应堆水环境中金属元件腐蚀的方法，包括在金属元件的表面上施加隔离涂层的步骤。
2、根据权利要求1所述的方法，其中所述核反应堆水环境是选自沸水堆(BWR)、压水堆(PWR)和加拿大氘铀反应堆(CANDU)中的环境。
3、根据权利要求1所述的方法，其中所述隔离涂层为氧化物隔离涂层。
4、根据权利要求3所述的方法，其中所述氧化物隔离涂层从TiO2、ZrO2、Ta2O5、Al2O3、CeO2和HfO2中选择。
5、根据权利要求1所述的方法，其中所述隔离涂层是在反应堆水环境中氧化的金属涂层。
6、根据权利要求5所述的方法，其中所述金属涂层从Ti、Zr、Ta、Al、Ce和Hf中选择。
7、根据权利要求1所述的方法，其中所述在金属元件的表面施加隔离涂层的步骤还包括使用化学气相沉积法(CVD)的施加方法，施加厚度基本为0.1～5微米。
8、根据权利要求1所述的方法，其中所述在金属元件的表面施加隔离涂层的步骤还包括使用选自等离子热喷涂或高速氧燃料热喷涂法(HVOF)、物理气相沉积法(PVD)、射频(RF)喷溅处理、电镀法和无电镀法的施加方法。
9、根据权利要求8所述的方法，其中所述在金属元件表面施加隔离涂层的步骤还包括施加厚度基本为0.1微米至0.3毫米的涂层。
10、根据权利要求1所述的方法，其中所述涂层为0.1微米至0.3毫米的氧化物或者最终在反应堆水中氧化形成氧化物例如TiO2的金属元素，即，Ti、Zr、Ta、Al、Hf、Ce等的薄层。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/889,757 US20090046825A1 (en) | 2007-08-16 | 2007-08-16 | Protective coating applied to metallic reactor components to reduce corrosion products into the nuclear reactor environment |
| US11/889757 | 2007-08-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101423943A true CN101423943A (zh) | 2009-05-06 |
Family
ID=40010740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008102103810A Pending CN101423943A (zh) | 2007-08-16 | 2008-08-15 | 用于反应堆金属元件以减少进入核反应堆环境的腐蚀产物的保护涂层 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20090046825A1 (zh) |
| EP (1) | EP2031091A1 (zh) |
| JP (1) | JP2009047692A (zh) |
| CN (1) | CN101423943A (zh) |
| MX (1) | MX2008010475A (zh) |
| TW (1) | TW200925316A (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104294205A (zh) * | 2014-09-11 | 2015-01-21 | 芜湖鼎瀚再制造技术有限公司 | 一种ZrO2-HfO2涂层及其制备方法 |
| CN104409118A (zh) * | 2014-10-23 | 2015-03-11 | 华北电力大学 | 研究聚变堆腐蚀产物沉积的热工水力实验系统及方法 |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX343479B (es) * | 2009-03-30 | 2016-11-07 | Toshiba Kk | Miembro resistente a la corrosion y metodo para producirlo. |
| WO2010121143A2 (en) * | 2009-04-16 | 2010-10-21 | Chevron U.S.A. Inc. | Structural components for oil, gas, exploration, refining and petrochemical applications |
| US8871306B2 (en) * | 2009-04-16 | 2014-10-28 | Chevron U.S.A. Inc. | Structural components for oil, gas, exploration, refining and petrochemical applications |
| US20100266790A1 (en) * | 2009-04-16 | 2010-10-21 | Grzegorz Jan Kusinski | Structural Components for Oil, Gas, Exploration, Refining and Petrochemical Applications |
| US8320427B2 (en) * | 2009-12-16 | 2012-11-27 | General Electric Company | Cold walled induction guide tube |
| JP6088173B2 (ja) * | 2011-11-24 | 2017-03-01 | 日立Ｇｅニュークリア・エナジー株式会社 | 原子力プラントの構成部材への放射性核種付着抑制方法 |
| US8971476B2 (en) * | 2012-11-07 | 2015-03-03 | Westinghouse Electric Company Llc | Deposition of integrated protective material into zirconium cladding for nuclear reactors by high-velocity thermal application |
| US20140349013A1 (en) * | 2013-05-23 | 2014-11-27 | Uni-Pixel Displays, Inc. | Method of manufacturing a low volume transfer anilox roll for high-resolution flexographic printing |
| JP2016186430A (ja) * | 2015-03-27 | 2016-10-27 | 日立Ｇｅニュークリア・エナジー株式会社 | 原子炉構造部材の防食方法と製造方法、及び原子炉構造部材 |
| JP6588356B2 (ja) * | 2016-02-09 | 2019-10-09 | 日立Ｇｅニュークリア・エナジー株式会社 | 原子炉構造部材の製造方法および防食方法 |
| US20180016678A1 (en) * | 2016-07-15 | 2018-01-18 | Applied Materials, Inc. | Multi-layer coating with diffusion barrier layer and erosion resistant layer |
| WO2018017145A1 (en) * | 2016-07-22 | 2018-01-25 | Westinghouse Electric Company Llc | Spray methods for coating nuclear fuel rods to add corrosion resistant barrier |
| EP3519604B1 (fr) * | 2016-09-28 | 2020-07-29 | Commissariat à l'Énergie Atomique et aux Énergies Alternatives | Composant nucléaire a substrat metallique, procédé de fabrication par dli-mocvd et utilisations contre l'oxydation/hydruration |
| CN114902374A (zh) | 2019-11-08 | 2022-08-12 | 艾伯林基督大学 | 高熔点液体中成分的识别与量化 |
| CN114085098B (zh) * | 2021-11-26 | 2023-02-28 | 云南警官学院 | 一种耐腐蚀抗烧结抗高温蠕变的氧化铝复合陶瓷及其制备方法 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3389055A (en) * | 1965-04-05 | 1968-06-18 | Gen Electric | Jet pump assembly in a nuclear reactor |
| EP0209048B1 (en) * | 1985-07-10 | 1990-06-13 | Hitachi, Ltd. | Process and apparatus for cleaning nuclear reactor cooling water |
| JPS63274751A (ja) * | 1987-05-01 | 1988-11-11 | Toyota Motor Corp | セラミック溶射部材 |
| JPH07228963A (ja) * | 1994-02-17 | 1995-08-29 | Nuclear Fuel Ind Ltd | 原子燃料用折出硬化型ニッケル基合金材 |
| JP3605969B2 (ja) * | 1996-10-31 | 2004-12-22 | 石川島播磨重工業株式会社 | 防食用チタン酸化膜の作製方法および防食用チタン酸化膜 |
| US6633623B2 (en) * | 2000-11-29 | 2003-10-14 | General Electric Company | Apparatus and methods for protecting a jet pump nozzle assembly and inlet-mixer |
| JP2003232886A (ja) * | 2002-02-06 | 2003-08-22 | Toshiba Corp | 金属材料の腐食低減方法 |
| US6630202B1 (en) * | 2002-09-30 | 2003-10-07 | General Electric Company | CVD treatment of hard friction coated steam line plug grips |
| JP4430372B2 (ja) * | 2003-04-15 | 2010-03-10 | 株式会社神戸製鋼所 | 耐食性に優れた金属構造体、前記金属構造体を製造するための材料および前記金属構造体の製法 |
| US8023609B2 (en) * | 2004-12-30 | 2011-09-20 | General Electric Company | Dielectric coating for surfaces exposed to high temperature water |
| US20070003001A1 (en) * | 2005-06-30 | 2007-01-04 | General Electric Company | Method for mitigation oxide fouling in structural components in light water reactors |
| JP3828139B2 (ja) * | 2005-07-05 | 2006-10-04 | 株式会社東芝 | 構造物の補修装置 |
-
2007
- 2007-08-16 US US11/889,757 patent/US20090046825A1/en not_active Abandoned
-
2008
- 2008-08-04 TW TW097129547A patent/TW200925316A/zh unknown
- 2008-08-06 EP EP08161949A patent/EP2031091A1/en not_active Withdrawn
- 2008-08-08 JP JP2008204936A patent/JP2009047692A/ja active Pending
- 2008-08-14 MX MX2008010475A patent/MX2008010475A/es unknown
- 2008-08-15 CN CNA2008102103810A patent/CN101423943A/zh active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104294205A (zh) * | 2014-09-11 | 2015-01-21 | 芜湖鼎瀚再制造技术有限公司 | 一种ZrO2-HfO2涂层及其制备方法 |
| CN104294205B (zh) * | 2014-09-11 | 2017-01-25 | 芜湖鼎瀚再制造技术有限公司 | 一种ZrO2‑HfO2涂层及其制备方法 |
| CN104409118A (zh) * | 2014-10-23 | 2015-03-11 | 华北电力大学 | 研究聚变堆腐蚀产物沉积的热工水力实验系统及方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009047692A (ja) | 2009-03-05 |
| TW200925316A (en) | 2009-06-16 |
| US20090046825A1 (en) | 2009-02-19 |
| MX2008010475A (es) | 2009-03-05 |
| EP2031091A1 (en) | 2009-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101423943A (zh) | 用于反应堆金属元件以减少进入核反应堆环境的腐蚀产物的保护涂层 | |
| Ševeček et al. | Development of Cr cold spray–coated fuel cladding with enhanced accident tolerance | |
| Tang et al. | Protective coatings on zirconium-based alloys as accident-tolerant fuel (ATF) claddings | |
| Hollenberg et al. | Tritium/hydrogen barrier development | |
| Ma et al. | Evaluation of corrosion and oxidation behaviors of TiAlCrN coatings for nuclear fuel cladding | |
| JP2007192219A (ja) | タービンエンジンコンポーネント、その保護方法およびコーティング系 | |
| US20060188056A1 (en) | Method for forming coatings on structural components with corrosion-mitigating materials | |
| US20180366234A1 (en) | Cladding for a fuel rod for a light water reactor | |
| Yamaki et al. | Corrosion resistance of Fe-Al-alloy-coated ferritic/martensitic steel under bending stress in high-temperature lead-bismuth eutectic | |
| Suhr | Microstructure and durability of zirconia thermal barrier coatings | |
| Hong et al. | Cracking and spalling of the oxide layer developed in high-burnup Zircaloy-4 cladding under normal operating conditions in a PWR | |
| Tang et al. | Metallic and ceramic coatings for enhanced accident tolerant fuel cladding | |
| Pazderová et al. | Improvement of steels' corrosion resistance in liquid lead and lead-bismuth by coatings | |
| Wei et al. | Effect of 3.5% NaCl solution with different Na2S concentrations on ultrasonic cavitation erosion behaviors of HVOF sprayed WC-Ni coatings | |
| Sagiroun et al. | Zirconium-based cladding coating technique for oxidation, corrosion and embrittlement reduction at high-temperature: an overview | |
| Lee et al. | The effect of bond coat oxidation on the failure of thermal barrier coatings | |
| Shirvani et al. | The effect of aluminide coating on the steam oxidation behavior of SS321 steel at 700° C | |
| Kashkarov et al. | Formation of titanium interlayer by vacuum arc deposition to increase the durability of titanium nitride coatings under thermal cycling conditions | |
| Angiolini et al. | Towards a new approach for structural materials of Lead Fast Reactors | |
| Sahoo et al. | On the suitability and application of MCrAlY coatings under various operating conditions | |
| Greving et al. | Effects of coating thickness and residual stresses on bond strength of C633-79 Thermal spray coating test specimens | |
| Van Nieuwenhove et al. | Investigation of the Impact of Coatings on Corrosion and Hydrogen Uptake of Nuclear Components | |
| RU2228969C2 (ru) | Способ локальной защиты изделия от газового алитирования | |
| Belous et al. | Structure and properties of coatings based on FeCrAl and Cr18Ni10T | |
| Brachet et al. | Out-of-pile RandD on chromium coated nuclear fuel zirconium based claddings for enhanced accident tolerance in LWRs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090506 |