CN103903664A - Irradiation resistance nano-porous membrane - Google Patents
Irradiation resistance nano-porous membrane Download PDFInfo
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- CN103903664A CN103903664A CN201410154451.0A CN201410154451A CN103903664A CN 103903664 A CN103903664 A CN 103903664A CN 201410154451 A CN201410154451 A CN 201410154451A CN 103903664 A CN103903664 A CN 103903664A
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- 239000012528 membrane Substances 0.000 title claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 34
- 239000002120 nanofilm Substances 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 230000008961 swelling Effects 0.000 abstract description 5
- 238000009377 nuclear transmutation Methods 0.000 abstract description 3
- 230000000149 penetrating effect Effects 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 208000034189 Sclerosis Diseases 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 238000000342 Monte Carlo simulation Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000005262 alpha decay Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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Abstract
The invention discloses an irradiation resistance nano-porous membrane, and belongs to the application field of advanced nuclear energy materials. The irradiation resistance nano-porous membrane comprises longitudinal nano-hole channels penetrating through the surface, the diameter of each longitudinal nano-hole channel is larger than 2 nanometers, the distance between every two adjacent longitudinal nano-hole channels is smaller than the scattering distance of interstitial atoms and the He gas, and branch-shaped nano-hole channels are transversely formed in each longitudinal nano-hole channel. The abundant hole channels of the nano-porous membrane can absorb the interstitial atoms, vacancies, transmutation gas and other flaws produced by irradiation and can also release gas atoms out of a material, the flaw content inside the material can be greatly reduced, the interstitial atoms, the vacancies and the transmutation gas are prevented from being gathered to form an atomic cluster, a cavity, bubbles and the like, and the radiation swelling resisting capability, the hardening resisting capability and the non-crystallizing capability of the material are greatly improved.
Description
?
Technical field
The invention belongs to nuclear energy application, be specifically related to a kind of anti-irradiation nano-porous films.
Background technology
Nuclear energy is to solve one of effective method of the growing energy demand in the world today.And the problem of current most critical is to find resistance to irradiation, corrosion-resistant, resistant to elevated temperatures nuclear reactor material.
In nuclear reactor, can there is neutron transmutation, alpha-decay, can produce a large amount of defects.The gathering of defect can cause the swelling of material, and sclerosis is decrystallized, embrittlement, and creep etc., thus will change the original engineering properties of nuclear power plant components and thermal property, have a strong impact on their performance and life-span.High off normal damage ratio and He generation rate that in fusion reactor equipment, the material of structured material and flux of plasma brings except standing the neutron of 14 MeV, also will withstand some harsh operating conditionss.Therefore the new material that, development can effectively absorb the defect that irradiation produces and administer excessive He atom is a very significant thing.Existing irradiation resistant material can absorb the defect that irradiation produces and can not discharge defect.
Summary of the invention
Technical matters to be solved by this invention is to provide a kind of anti-irradiation nano-porous films.
Anti-irradiation porous nano film of the present invention, there is the longitudinal nano pore that connects surface, the diameter of described longitudinal nano pore is greater than 2 nanometers, the spacing of described longitudinal nano pore is less than the diffusion length of interstitial atom and He gas, and on each longitudinal nano pore also cross growth have branch shape nano pore.
This anti-irradiation nano pore structure feature is:
Longitudinally nano pore and sample surfaces connect, so that gas atom can be diffused into outside material.
The diameter of nano pore is greater than 2 nm, and to guarantee that a certain amount of interstitial atom is diffused into behind surface, duct, duct is not blocked.
Spacing between nano pore is less than the diffusion length of interstitial atom and He gas, makes them can be diffused into nano pore surface.
Anti-irradiation porous nano film of the present invention can be ceramic nano membrane or metal nano film.Such as CrN film or V film.
Anti-irradiation porous nano film of the present invention, thickness can be 450 nanometers.
Can utilize magnetic control sputtering system to generate pottery, the metallic film of this structure.
The nano pore that nanometer film of the present invention penetrates into material surface not only can absorb the defects such as the interstitial atom that produces in irradiation process, room, transmuting gas, gas atom can also be discharged into outside material, thereby significantly reduce defect density in material bodies, the gathering that prevents interstitial atom, room, transmuting gas forms elementide, cavity, bubble etc., has greatly improved the anti-void swelling, sclerosis of material, the ability such as decrystallized.
Nanometer film of the present invention, applies to resist as coating in the environment of irradiation, can suppress the defects such as interstitial atom, room, transmuting gas and reunite.This invention is applicable to fusion reactor ion irradiation environment and is also applicable to fission-type reactor radiation environment, is a kind of anti-void swelling, sclerosis of excellence, the nano pore structure of the irradiation effect such as decrystallized.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope cross section picture that utilizes closely knit CrN film (b) prepared by nano pore CrN film (a) prepared by reaction magnetocontrol sputtering and multi-Arc Ion Plating, (a) illustration in is corresponding plane and the scanning electron microscope (SEM) photograph in cross section, and the illustration in (b) is corresponding electron diffraction pattern.When irradiation dose is 3 × 10
17he
+ions/cm
2time, the transmission electron microscope cross section picture of the nano pore CrN film (c) after irradiation and closely knit CrN film (d).(c) illustration in is the amplification transmission electron microscope picture of the corresponding ion path near zone of dotted line collimation mark note.(d) illustration in is corresponding scanning electron microscope image plane.
Fig. 2 is the schematic diagram of the absorption of defect and the release of bubble in the CrN film of nano pore structure.
Fig. 3 is the transmission electron microscope cross section picture of nano pore V film after predose, and illustration is corresponding electron diffraction pattern and local regional enlarged drawing.
Embodiment
Below in conjunction with accompanying drawing and two experiment embodiments, the anti-irradiation nano pore structure of one provided by the invention is further described and be experimental results show that.
Embodiment 1
To use the single crystalline Si (100) of RCA method cleaning as substrate, wash the SiO on Si surface
2oxide layer and some impurity.By the method deposition radioresistance nanometer film of magnetron sputtering.Before deposition, substrate temperature is room temperature.In deposition process, pass into pure Ar, N
2, flow is fixed as respectively 5 sccm, 20 sccm.When depositing nano duct CrN film, the power of target is 150 W.Sedimentation time reaches after 8000 s, forms thickness and is approximately the uniform nano pore CrN of 450 nm film.Wherein in the whole process of reaction magnetocontrol sputtering, sample stage transfers the homogeneity that keeps long film at grade certainly.
Sample prepared by the present embodiment is analyzed, and Fig. 1 (a) is cross section transmission electron microscope picture and corresponding plane and the scanning electron microscope (SEM) photograph in cross section of the nano pore CrN film prepared with this example.From Fig. 1 (a), can observe nano pore CrN film that we prepare and be the nano pore structure of lateral direction penetrating in a kind of nano pore of longitudinal perforation and single crystal column.Fig. 1 (b) is in order to contrast, the very closely knit CrN film of preparing with multi-Arc Ion Plating.According to SRIM Monte Carlo simulation, the He ion irradiation CrN dosage of 30 keV reaches 3 × 10
17ions/cm
2time, damage peak value and He ion concentration peak value are respectively 17.8 dpa and 24.1 at.%.From Fig. 1 (c) with can observe (d) in the closely knit CrN film of irradiation and occurred that width is approximately the crack of 10 nm, and only there is being of a size of the bubble of 0.8 nm in nanoporous CrN film after irradiation.Meanwhile, the nano pore in the nanoporous CrN film after irradiation does not have obvious broadening, and the good physical stability of the nano pore CrN structure of brilliant veiny has been described.In nano pore CrN film, can absorb the defect that irradiation produces by the nano pore of lateral direction penetrating in the nano pore of longitudinally perforation and single crystal column, and the He bubble of formation is discharged into material bodies outer (Fig. 2).And in closely knit CrN film, He is combined with room and is become the nucleating centre that He steeps, grow up by absorbing He atom and room around, finally can change into the macroscopic-void of harm and cause the swelling of material and final cracking.Therefore, the CrN film of this special nano pore structure that we prepare is compared closely knit CrN film, has good absorption and the control ability that discharges bubble, has shown the anti-radiation performance that it is good.
Embodiment 2
On silicon substrate, deposit V film, sputtering power is 150 W, and film thickness is 450 nm.With 40 keV He
+ion carries out irradiation, and irradiation dose is 1 × 10
17ions/cm
2.The peak concentration of He is 5 at.%, and peak displacement damage is 9 dpa.From figure (3), can find out, after high dosage irradiation, in sample, only occurred that size is less than the helium bubble of 1 nm, the existence of nano pore has suppressed the growth of helium bubble greatly, has increased substantially the Radiation hardness of material.
Claims (4)
1. an anti-irradiation nano-porous films, it is characterized in that: there is the longitudinal nano pore that connects surface, the diameter of described longitudinal nano pore is greater than 2 nanometers, the spacing of described longitudinal nano pore is less than the diffusion length of interstitial atom and He gas, and on each longitudinal nano pore also cross growth have branch shape nano pore.
2. anti-irradiation nanometer film according to claim 1, is characterized in that, described anti-irradiation porous nano film is ceramic nano membrane or metal nano film.
3. anti-irradiation nanometer film according to claim 2, is characterized in that, described anti-irradiation porous nano film is CrN film or V film.
4. anti-irradiation nanometer film according to claim 1 and 2, is characterized in that, described nanometer film thickness is 450 nanometers.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410154451.0A CN103903664B (en) | 2014-04-17 | 2014-04-17 | A kind of Flouride-resistani acid phesphatase nano-porous films |
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| CN201410154451.0A CN103903664B (en) | 2014-04-17 | 2014-04-17 | A kind of Flouride-resistani acid phesphatase nano-porous films |
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| CN103903664A true CN103903664A (en) | 2014-07-02 |
| CN103903664B CN103903664B (en) | 2016-06-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109910396A (en) * | 2019-01-21 | 2019-06-21 | 西安交通大学 | A kind of metallic composite spontaneously forming gas passage |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382519A (en) * | 2002-05-30 | 2002-12-04 | 复旦大学 | Process for preparing zeolite film with self-supporting multi-stage artery structure |
| CN1807224A (en) * | 2005-12-27 | 2006-07-26 | 北京大学 | Si base membrane nanometer pore canal and its preparation method |
| CN1974884A (en) * | 2006-11-16 | 2007-06-06 | 武汉大学 | Prepn process of nanometer monocrystalline zinc oxide film material |
| US20110176997A1 (en) * | 2010-01-21 | 2011-07-21 | Zhuo Joe Zhang | Method to make porous materials and their applications |
| CN103630572A (en) * | 2013-10-21 | 2014-03-12 | 天津大学 | Preparation method of porous silicon/tungsten oxide nanowire composite structure for gas-sensitive material |
| JP2014052348A (en) * | 2012-09-10 | 2014-03-20 | Kuraray Living Kk | Radiation shield material and method for manufacturing the same |
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2014
- 2014-04-17 CN CN201410154451.0A patent/CN103903664B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382519A (en) * | 2002-05-30 | 2002-12-04 | 复旦大学 | Process for preparing zeolite film with self-supporting multi-stage artery structure |
| CN1807224A (en) * | 2005-12-27 | 2006-07-26 | 北京大学 | Si base membrane nanometer pore canal and its preparation method |
| CN1974884A (en) * | 2006-11-16 | 2007-06-06 | 武汉大学 | Prepn process of nanometer monocrystalline zinc oxide film material |
| US20110176997A1 (en) * | 2010-01-21 | 2011-07-21 | Zhuo Joe Zhang | Method to make porous materials and their applications |
| JP2014052348A (en) * | 2012-09-10 | 2014-03-20 | Kuraray Living Kk | Radiation shield material and method for manufacturing the same |
| CN103630572A (en) * | 2013-10-21 | 2014-03-12 | 天津大学 | Preparation method of porous silicon/tungsten oxide nanowire composite structure for gas-sensitive material |
Non-Patent Citations (4)
| Title |
|---|
| L.X.FAN,ET.AL.: "Substrate grain boundary effects on the ordering of nanopores in anodic aluminum oxide", 《SOLID STATE COMMUNICATIONS》 * |
| TENGFEI YANG,ET.AL.: "Enhanced structural stability of nanoporous zirconia under irradiation of He", 《JOURNAL OF NUCLEAR MATERIALS》 * |
| 任峰 等: "纳米结构核材料抗辐照性能研究", 《中国核科学技术进展报告》 * |
| 张红秀 等: "抗辐照纳米多层膜研究进展", 《原子核物理评论》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109910396A (en) * | 2019-01-21 | 2019-06-21 | 西安交通大学 | A kind of metallic composite spontaneously forming gas passage |
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