CN102400099A - Technology for preparing nuclear fission reactor fuel clad surface CrAlSiN gradient coating - Google Patents
Technology for preparing nuclear fission reactor fuel clad surface CrAlSiN gradient coating Download PDFInfo
- Publication number
- CN102400099A CN102400099A CN201110344681XA CN201110344681A CN102400099A CN 102400099 A CN102400099 A CN 102400099A CN 201110344681X A CN201110344681X A CN 201110344681XA CN 201110344681 A CN201110344681 A CN 201110344681A CN 102400099 A CN102400099 A CN 102400099A
- Authority
- CN
- China
- Prior art keywords
- cralsin
- target
- coating
- gradient
- gradient cladding
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a new technology for depositing a CrAlSiN gradient coating with high-temperature oxidation corrosion resistance and excellent mechanical properties on a supercritical water-cooled reactor fuel clad surface in a nuclear fission reactor. The CrAlSiN gradient coating is deposited on the surface of a base material by adopting a multi-target reaction magnetron sputtering method, and the technology comprises the following four continuous stages of: 1, preparing a Cr gradient coating; 2, preparing a CrAl gradient coating; 3, preparing a CrAlN gradient coating; and preparing the CrAlSiN gradient coating, and annealing. By reasonably designing the gradient variable microstructure of each element, the anti-oxidation temperature of the coating reaches 950 DEG C, the hardness of the coating reaches over 37GPa, and the adhesive force of the coating adhered to the base material reaches 34N; the coating also has excellent thermal shock resistance, abrasion resistance and the like; and the service property of the supercritical water-cooled reactor fuel clad part can be greatly improved, and the service life of the clad part can be greatly prolonged.
Description
Technical field
The invention belongs to the modification technology field of fission-type reactor parts surface, relate to a kind of new preparation process of chromium aluminium silicon nitrogen (CrAlSiN) gradient cladding that supercritical water cold dome fuel sheath surface deposition high temperature oxidation corrosion resistance performance and mechanical property are excellent in fission-type reactor particularly.
Background technology
Nuclear energy is as a kind of efficient, economic and persistent energy, and aspect comprehensive advantages such as the energy dilemma that faces in the solution whole world, protection environmental quality are remarkable.2002, the 4th generation the reactor international symposium filter out 6 kinds of heap types, supercritical water cold dome (SCWR) is one of them.SCWR is the HTHP water-cooled reactor that more than its thermodynamic critical point of water, moves, and is the water cooled reactor of following the most worth research and development.SCWR has that system is simple, cycle efficiency is high, the basic advantage such as good of industriallization, is expected to become main force's heap type of low-cost generating from now on.Yet fuel sheath is one of the most key parts of SCWR.The vapor temperature that SCWR is the highest also is long-time strength and the corrosion resistance that maximum thermal efficiency depends on fuel canning material.Under supercritical behavior; The high temperature of fuel sheath up to 650 ℃, its pressure of supercritical steam conditions is up to 25MPa; Temperature surpasses 500 ℃, and the great variety of the interior moderator density of reactor core, all exceeds the scope of being accumulated experience in the design of present pressurized-water reactor and BWR.Therefore; Existing fuel canning material can not satisfy corrosion resistance and mechanical property requirements in the supercritical water cold dome [optimization design of the effective low activity F/M of supercritical water cold dome fuel sheath steel. Kang Renmu; Liu Guoquan, Hu Benfu etc. the atomic energy science technology. the 43rd volume the 6th phase .2009].At present, low swelling austenitic stainless steel such as D9,1.4970,316Ti etc. are the alternative materials of main SCWR fuel sheath, and these materials have advantages such as intensity height, void swelling is low, weldableness good, neutron economy property is better.Yet, the high temperature oxidation corrosion resistance poor-performing of above-mentioned materials in the supercritical water cold dome, in SCWR fuel sheath long service process, excessive erosion rate will cause clad breach.
Functional coating at SCWR fuel sheath surface deposition high temperature oxidation corrosion resistance can address the above problem effectively, and this technology also becomes the research focus of academia and engineering circle in recent years thus.Consider that Cr content in the steel is higher relatively, the Cr element is to the influence of steel passivation, people trend towards the alloy coat at fuel sheath surface deposition Cr at first.On the one hand, the interface of Cr alloy coat and base material can form the Fe-Cr compound, realizes that chemical metallurgy combines, and sticking power is better; On the other hand, the Cr element in the coating can form oxide film at the O element in coatingsurface and the corrosive environment, hinders soaking into of corrosive medium, has high temperature oxidation resistance preferably.But; The intensity of Cr alloy coat, hardness etc. are relatively low; The intensive thermal shocking possibly cause coating ductility distortion, premature rupture [hardness and the cavitation property of HVAF Fe-Cr base coating. Wu Yuping, Lin Pinghua, Wang Zehua. the material heat treatment journal. the 30th rolls up the 1st phase .2009].Subsequently, people then trend towards Cr base nitride coating.With respect to the Cr alloy coat, Cr base nitride coating has more advantage at aspects such as antioxidant anticorrosive performances.For example, the oxidation resistance temperature of CrN coating can reach 600 ℃; In addition, the better hardness [hard and superhard coating-structure, performance, preparation and sign, Song Guihong, Du Hao, the He Chunlin that also have about 18GPa; Beijing: the .2007 of Chemical Industry Press].In recent years, along with developing rapidly of nanotechnology, Cr base nano-composite coating has been owing to demonstrated splendid advantage at aspect of performances such as resistance to high temperature oxidation, hardness, frictional wear, anti-thermal shocks, thereby caused investigator's extensive concern.For example, the resistance to high temperature oxidation temperature of CrAlSiN nano-composite coating can reach more than 1000 ℃, and has excellent mechanical property; The coating hardness value can reach 41GPa [Mechanical properties and oxidation behavior of (Al; Cr) N and (Al, Cr, Si) N coatings for cutting tools deposited by HPPMS.K.Bobzin; N.Bagcivan, P.Immich.Thin Solid Films.517.2008].
Although Cr base nano-composite coating has excellent corrosion resistance and mechanical property, when they are applied to fuel sheath steel matter base material commonly used, need face a great difficult problem, i.e. the interface binding power problem of coating and steel.Because the nature difference of coating and base material is greatly different, often make fuel sheath under arms process floating coat/substrate interface very easily lost efficacy, cause disbonding.Given this, many investigators solve the problems referred to above through the elemental composition and the weave construction of modulation coating.For example, the coating that has the people also to change in gradient through the forming element composition improves the interface binding power of itself and base material.Form because the graded of coated component causes coating not have the subgrade interface, coating causes them can realize that chemical metallurgy combines with the total elemental composition of base material simultaneously, thereby can increase substantially its interface binding power etc.In addition, the gradient-structure coating shows more superior toughness, thermal shock resistance etc. toward contact.The excellent properties that has in view of gradient structure film, but the research and the application of CrAlSiN gradient cladding are not also arranged so far as yet.The novel process of the CrAlSiN gradient cladding of supercritical water cold dome fuel sheath surface deposition high temperature oxidation corrosion resistance performance and excellent mechanical property in fission-type reactor, this task of the present invention just place.
Summary of the invention
The present invention is directed to the low relatively poor technical disadvantages of swelling austenitic stainless steel resistance to high temperature corrosion performance of supercritical water cold dome fuel sheath usefulness in the present nuclear fission heap; And combine the high temperature oxidation corrosion resistance coatings technology, provide a kind of have excellent anti high temperature corrosion oxidation susceptibility and mechanical property, combine good nuclear fission to pile fuel sheath top coat chromium aluminium silicon nitrogen (CrAlSiN) gradient cladding novel process with low swelling austenite stainless steel substrate.
The object of the invention is realized through following technical scheme:
The preparation technology of nuclear fission supercritical water cold dome fuel sheath surface deposition CrAlSiN gradient cladding provided by the invention is characterized in that comprising successively following process step:
(1) substrate surface polishing and cleaning
Selection supercritical water cold dome fuel sheath as base material, carries out grinding and polishing with the different waterproof abrasive paper of roughness to its surface with austenitic stainless steel successively; Subsequently, in the UW container, carrying out degreaser cleans; Carry out pickling and rinsed with deionized water subsequently, and use N
2Air-blowing is done; At last, dry substrate is put into Vakuumkammer, clean with bias plasma backwash technology, its processing parameter is: base vacuum is 5 * 10
-4Pa, backwash bias voltage are Ar gas for-300V, working gas, and backwash air pressure is that 1.0Pa, backwash time are 20min;
(2) deposition chromium aluminium silicon nitrogen (CrAlSiN) gradient cladding
Adopt ultrahigh vacuum(HHV) multi-target magnetic control sputtering coating equipment at substrate surface deposition CrAlSiN gradient cladding, said coating equipment base vacuum degree is 5 * 10
-4200 ℃ of Pa, depositing temperatures, be coated with layer deposition process comprise following 4 continuous time section:
(a), in first time period, treat Vakuumkammer bleed reach the base vacuum degree after, in Vakuumkammer, feed Ar gas; Its airshed is 200sccm, and operating air pressure is 0.3Pa, opens the Cr target subsequently and carries out sputter; Its sputtering power is 200W; Depositing time is 4min～6min, and in the pure Cr coating of said substrate surface deposition, deposit thickness is 80～120nm thus;
(b), in second time period; The Ar airshed and the Cr target sputtering power that keep (a) step; Open the Al target simultaneously and carry out sputter, with Al target sputtering power by 50W gradually linearity increase to 100W, realize Cr target and Al target co-sputtering; Thereby obtain the CrAl coating that Al content increases in gradient gradually, make that through regulating depositing time the thickness of CrAl coating is 180～220nm;
(c), in the 3rd time period, keep the Ar airshed of (b) step, and the sputtering power of Cr target and Al target, in Vakuumkammer, feed N simultaneously
2Gas, N
2Airshed by 0sccm gradually linearity increase to 150sccm, operating air pressure remains on 0.5Pa, realizes that Cr target and Al target are at (Ar+N
2) cosputtering in the mixed atmosphere, thereby obtain the CrAlN coating that N content increases in gradient gradually, make that through regulating depositing time the thickness of CrAlN coating is 250～300nm;
(d), in the 4th time period, open the sputter of Si target, sputtering power increases to 100W by the 50W linearity, the sputtering power with Cr target and Al target is adjusted to 300W and 200W by 200W and 100W linearity respectively simultaneously, with N
2The flow of gas by 150sccm gradually linearity increase to 250sccm, realize that Cr target, Al target and Si target are at (Ar+N
2) cosputtering in the mixed atmosphere, thereby obtain the CrAlSiN coating that nitrogen, silicon and aluminium content increase gradually, and form (Cr, Al, Si) the nanocrystalline Si that is embedded in of N at its nearly surf zone
3N
4Microstructure in the amorphous phase makes that through regulating depositing time the thickness of CrAlSiN coating is 2.5～3.0 μ m;
(3) sedimentary gradient cladding is carried out anneal
With sedimentary CrAlSiN gradient cladding, carry out in-situ annealing in uninterrupted vacuum environment and handle, it is subsequent use to treat to take out sample after anneal finishes.
In the technique scheme, the purpose of said anneal is that interface structure is dissolved each other, strengthened to the unrelieved stress in the release coat, the Elements Diffusion of quickening between coating and base material and each subgrade, and the processing parameter of its in-situ annealing is: vacuum tightness 5 * 10
-4Pa, 400 ℃ of annealing temperatures, 20 ℃/min of temperature rise rate, soaking time 90min, the type of cooling are for cooling to room temperature with the furnace.
In the technique scheme, used Cr target, Al target and the Si target of deposition CrAlSiN gradient cladding, their purity is 99.99%.
In the technique scheme, its roughness of waterproof abrasive paper that used roughness is different is followed successively by 300～1200 orders.
In the technique scheme, used degreaser cleans consists of yellow soda ash 160g/L, Trisodium Citrate 45g/L, promoting agent 5g/L, sodium phosphate 50g/L.
In the technique scheme, said austenite stainless steel substrate is D9, or 1.4970, or 316Ti.
The CrAlSiN gradient cladding of preparation technology's preparation of nuclear fission supercritical water cold dome fuel sheath surface deposition CrAlSiN gradient cladding provided by the invention, its coat-thickness is changed to 2.5～3.0 μ m; Temperature can be up to 950 ℃; Hardness is more than the 37GPa; Interface binding power reaches more than the 34N.
The present invention compared with prior art has the following advantages and beneficial technical effects:
(1) the CrAlSiN gradient cladding of the present invention's preparation possesses excellent high temperature oxidation corrosion resistance performance, and its temperature can be up to 950 ℃.
(2) the CrAlSiN gradient cladding of the present invention preparation since Cr, Al all can form fine and close oxide film protection layer, thereby can effectively stop O and other impurity element such as Cl erosion matrix with O; Because the N element also can effectively hinder elemental diffusion such as O, H in the enrichment of crystal boundary; In addition, because the nearly surf zone of coating is Si
3N
4The amorphous phase clad nano is brilliant, and (therefore Si) the nano composite structure of N can significantly strengthen the high temperature oxidation corrosion resistance performance for Cr, Al.
(3) the CrAlSiN gradient cladding of the present invention's preparation possesses excellent mechanical property, and its hardness is more than the 37GPa.Because the nearly surf zone of CrAlSiN gradient cladding has nano composite structure, so coating has very high surface hardness, also has excellent abrasive simultaneously; Owing to have the structure of elemental composition graded, therefore help to alleviate the coating thermal stresses, make coating have toughness and thermal shock resistance etc. preferably simultaneously.
(4) the CrAlSiN gradient cladding and the base material of the present invention's preparation have the good interface bonding force, reach more than the 34N.Therefore coating bottom enrichment Cr element can combine with base material generation chemical metallurgy; Simultaneously, because the coating elemental composition gradually changes in gradient, the constituent structure at each subgrade interface does not have remarkable sudden change, this interface binding power with strengthened coat and base material, interfacial fracture toughness.
(5) the present invention at supercritical water cold dome fuel sheath surface deposition the CrAlSiN gradient cladding, can increase substantially the military service performance and the work-ing life of fuel sheath.
Description of drawings
Fig. 1 is the structural representation of CrAlSiN gradient cladding.
Embodiment
With specific embodiment the present invention is done further explain below, but and do not mean that any qualification protection domain of the present invention.
The used instrument of the embodiment of the invention:
Ultrahigh vacuum(HHV) multi-target magnetic control sputtering coating equipment, model QX-500 type;
Supercritical water cold dome fuel sheath is the 316Ti stainless steel substrate; Its geometrical dimension is: long 5cm * wide 5cm * high 2cm.
Embodiment 1
CrAlSiN gradient cladding preparation technology of the present invention carries out according to foregoing process step and processing condition successively.
316Ti stainless steel substrate surface deposition CrAlSiN gradient cladding in that supercritical water cold dome fuel sheath is used comprises following process step:
(1) polishing of base material specimen surface and cleaning
With 300～1200 purpose waterproof abrasive papers the base material sample is carried out the surface grinding polishing at first, successively; Subsequently, in the UW container, carry out degreaser and clean, its degreaser moity is yellow soda ash 160g/L, Trisodium Citrate 45g/L, promoting agent 5g/L, sodium phosphate 50g/L; Next carry out pickling and rinsed with deionized water, use N after pickling and rinsing are accomplished
2Gas dries up the base material sample; At last, place Vakuumkammer to carry out the bias plasma backwash on the base material sample and clean, its processing parameter is: base vacuum 5 * 10
-4Pa, backwash bias voltage are that 200V, sputter Ar air pressure 0.3Pa, backwash time are 20min;
(2) CrAlSiN gradient cladding deposition
Adopt QX-500 type ultrahigh vacuum(HHV) multi-target magnetic control sputtering coating equipment at 316Ti austenite stainless steel substrate specimen surface deposition CrAlSiN gradient cladding, depositing used base vacuum degree is 5 * 10
-4200 ℃ of Pa, depositing temperatures are coated with layer deposition process and comprise following 4 successive time phases:
(a), in first time period, treat Vakuumkammer bleed reach used base vacuum degree after, at first in Vakuumkammer, feed Ar gas; Its airshed is 200sccm, and operating air pressure is 0.3Pa, opens the Cr target subsequently and carries out sputter; Its sputtering power is 200W; Depositing time is 4min, and this moment, the thickness of deposition Cr coating was 80nm in the pure Cr coating of said base material specimen surface deposition;
(b), in second time period; The Ar airshed and the Cr target sputtering power that keep (a) step; Open the Al target simultaneously and carry out sputter, with Al target sputtering power by 50W gradually linearity increase to 100W, realize the cosputtering of Cr target and Al target; Thereby obtain the CrAl coating that Al content increases in gradient gradually at the base material specimen surface, make that through regulating depositing time the thickness of deposition CrAl coating is 180nm;
(c), in the 3rd time period, keep the Ar airshed of (b) step, and the sputtering power of Cr target and Al target, begin in Vakuumkammer, to feed N simultaneously
2Gas, N
2Airshed by 0sccm gradually linearity increase to 150sccm, operating air pressure remains on 0.5Pa, realizes that Cr target and Al target are at (Ar+N
2) cosputtering in the mixed atmosphere, thereby obtain the CrAlN coating that N content increases in gradient gradually at the base material specimen surface, make that through regulating depositing time the thickness of deposition CrAlN coating is 250nm;
(d), in the 4th time period, keep the Ar airshed of (c) step, open the sputter of Si target, sputtering power increases to 100W by the 50W linearity, with the sputtering power of Cr target and Al target respectively linearity increase to 300W and 200W, and with N
2The flow of gas increases to 250sccm by the 150sccm linearity, is implemented in the base material specimen surface and carries out Cr target, Al target and Si target at (Ar+N
2) cosputtering in the mixed atmosphere, thereby obtaining the CrAlSiN coating that each constituent content increases in gradient, the thickness of deposition CrAlSiN coating is 2.5 μ m;
(3) coating anneal
After base material specimen surface deposition is accomplished the CrAlSiN gradient cladding, in uninterrupted vacuum environment it is carried out in-situ annealing and handle, its processing parameter is: vacuum tightness 5 * 10
-4Pa, 400 ℃ of annealing temperatures, 20 ℃/min of temperature rise rate, soaking time 90min, the type of cooling are for cooling to room temperature with the furnace; It is subsequent use to treat to take out sample after anneal finishes.
The purpose of said anneal is that interface structure is dissolved each other, strengthened to the unrelieved stress in the release coat, the Elements Diffusion of quickening between coating and base material and each the subgrade coating.
Performance to 316Ti austenitic stainless steel substrate surface CrAlSiN gradient cladding in the foregoing description 1 detects, and comprises following performance index and test technology thereof:
(1) adopt MH-5 type microhardness tester to measure coating hardness
Test parameter is: loaded load 70mN, hold time 10min, positive four-wheel awl brale.To 8 points of coating sample different surfaces domain test, with its MV as coating tested for hardness value.The result shows that the hardness value of CrAlSiN gradient cladding is 38GPa.
(2) adopt the interface of the automatic scratching instrument testing coating/base material of WS-2005 type coating adhesion to combine situation
Test parameter is: cut speed 1.5mm/min, loading rate 5N/min to 150N/min etc.The result shows that the interface sticking power of CrAlSiN gradient cladding and 316Ti steel substrate is 34N.
(3) adopt the high temperature oxidation resistance of making the chamber type electric resistance furnace testing coating by oneself
Thermal treatment process is: atmosphere heating atmosphere, 950 ℃ of holding temperatures, soaking time 90min, 50 ℃/min of temperature rise rate, type of cooling stove are cold.As a comparison, the 316Ti steel substrate sample of deposited coatings is not put into stove in the lump.The test of weighing after the anneal, the weightening finish of finding to contain the coating sample is not obvious, and it is remarkable not have the weightening finish of coating sample.The result shows: the oxidation resistance temperature of CrAlSiN gradient cladding is at 950 ℃.
Embodiment 2
Adopt and prepare the CrAlSiN gradient cladding with embodiment 1 identical process step, processing condition and processing parameter; Because coating performance receives the influence of base material character, subgrade thickness, component gradient etc., different with embodiment 1 is embodiment 2 is base materials employed to be 1.4970 austenite stainless steel substrates, and present embodiment is at 1.4970 steel substrate surface deposition CrAlSiN gradient claddings.
The experimental result of embodiment 2 is: the thickness of Cr, CrAl and CrAlN subgrade coating is respectively 120nm, 220nm and 300nm; CrAlSiN gradient cladding thickness is 3.0 μ m.
Except that above-mentioned, other processing parameter is all identical with embodiment 1.Adopt with embodiment 1 in identical coating performance testing method.The result shows: the hardness value of CrAlSiN gradient cladding be 39GPa, with the interface sticking power of base material be that 36N, oxidation resistance temperature still can reach 950 ℃.
Experimental result by embodiment 1, embodiment 2 is visible, and the CrAlSiN gradient cladding can significantly strengthen the surface property of supercritical water cold dome fuel sheath.Than stainless steel substrate, have more excellent high temperature oxidation resistance and mechanics of surface performance, and have higher interface binding power, thereby can significantly promote the military service performance and the work-ing life of fuel sheath part with base material.
Claims (7)
1. the preparation technology of a nuclear fission supercritical water cold dome fuel sheath surface deposition CrAlSiN gradient cladding is characterized in that comprising successively following process step:
(1) substrate surface polishing and cleaning
Select supercritical water cold dome fuel sheath to adopt austenitic stainless steel, with the different waterproof abrasive paper of roughness grinding and polishing is carried out on its surface successively as base material; Subsequently, in the UW container, carrying out degreaser cleans; Carry out pickling and rinsed with deionized water subsequently, and use N
2Air-blowing is done; At last, dry substrate is put into Vakuumkammer, clean with bias plasma backwash technology, its processing parameter is: base vacuum is 5 * 10
-4Pa, backwash bias voltage are Ar gas for-300V, working gas, and backwash air pressure is that 1.0Pa, backwash time are 20min;
(2) deposition chromium aluminium silicon nitrogen (CrAlSiN) gradient cladding
Adopt ultrahigh vacuum(HHV) multi-target magnetic control sputtering coating equipment at substrate surface deposition CrAlSiN gradient cladding, said coating equipment base vacuum degree is 5 * 10
-4200 ℃ of Pa, depositing temperatures, be coated with layer deposition process comprise following 4 continuous time section:
(a), in first time period, treat Vakuumkammer bleed reach the base vacuum degree after, in Vakuumkammer, feed Ar gas; Its airshed is 200sccm, and operating air pressure is 0.3Pa, opens the Cr target subsequently and carries out sputter; Its sputtering power is 200W; Depositing time is 4min～6min, obtains sedimentary pure Cr coating at said substrate surface thus, and deposit thickness is 80～120nm;
(b), in second time period; The Ar airshed and the Cr target sputtering power that keep (a) step; Open the Al target simultaneously and carry out sputter, with Al target sputtering power by 50W gradually linearity increase to 100W, realize Cr target and Al target co-sputtering; Thereby obtain the CrAl coating that Al content increases in gradient gradually, make that through regulating depositing time the thickness of CrAl coating is 180～220nm;
(c), in the 3rd time period, keep the Ar airshed of (b) step, and the sputtering power of Cr target and Al target, in Vakuumkammer, feed N simultaneously
2Gas, N
2Airshed by 0sccm gradually linearity increase to 150sccm, operating air pressure remains on 0.5Pa, realizes that Cr target and Al target are at (Ar+N
2) cosputtering in the mixed atmosphere, thereby obtain the CrAlN coating that N content increases in gradient gradually, make that through regulating depositing time the thickness of CrAlN coating is 250～300nm;
(d), in the 4th time period, open the sputter of Si target, its sputtering power increases to 100W by the 50W linearity, the sputtering power with Cr target and Al target is adjusted to 300W and 200W by 200W and 100W linearity respectively simultaneously, with N
2The flow of gas by 150sccm gradually linearity increase to 250sccm, realize that Cr target, Al target and Si target are at (Ar+N
2) cosputtering in the mixed atmosphere, thereby obtain the CrAlSiN gradient cladding that nitrogen, silicon and aluminium content increase gradually, and surf zone forms (Cr, Al, Si) the nanocrystalline Si that is embedded in of N near gradient cladding
3N
4Microstructure in the amorphous phase makes that through regulating depositing time the thickness of CrAlSiN gradient cladding is 2.5～3.0 μ m;
(3) sedimentary gradient cladding is carried out anneal
With sedimentary CrAlSiN gradient cladding, carry out in-situ annealing in uninterrupted vacuum environment and handle, it is subsequent use to treat to take out sample after anneal finishes.
2. the preparation technology of nuclear fission supercritical water cold dome fuel sheath surface deposition CrAlSiN gradient cladding according to claim 1 is characterized in that the processing parameter that carries out in-situ annealing is: vacuum tightness 5 * 10
-4Pa, 400 ℃ of annealing temperatures, 20 ℃/min of temperature rise rate, soaking time 90min, the type of cooling are for cooling to room temperature with the furnace.
3. the preparation technology of nuclear fission supercritical water cold dome fuel sheath surface deposition CrAlSiN gradient cladding according to claim 1 is characterized in that depositing the used Cr target of CrAlSiN gradient cladding, Al target and Si target, and their purity is 99.99%.
4. according to the preparation technology of claim 1 or 3 described nuclear fission supercritical water cold dome fuel sheath surface deposition CrAlSiN gradient claddings, it is characterized in that its roughness of the different waterproof abrasive paper of said roughness is followed successively by 300～1200 orders.
5. the preparation technology of nuclear fission supercritical water cold dome fuel sheath surface deposition CrAlSiN gradient cladding according to claim 1 and 2, what it is characterized in that said degreaser consists of yellow soda ash 160g/L, Trisodium Citrate 45g/L, promoting agent 5g/L, sodium phosphate 50g/L.
6. the preparation technology of nuclear fission supercritical water cold dome fuel sheath surface deposition CrAlSiN gradient cladding according to claim 1 is characterized in that said austenite stainless steel substrate is D9, or 1.4970, or 316Ti.
7. the CrAlSiN gradient cladding of the said prepared of claim 1-5, the variation in thickness that it is characterized in that said CrAlSiN gradient cladding is 2.5～3.0 μ m, temperature can be up to 950 ℃; Hardness is more than the 37GPa; Interface binding power reaches more than the 34N.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110344681XA CN102400099B (en) | 2011-11-04 | 2011-11-04 | Technology for preparing nuclear fission reactor fuel clad surface CrAlSiN gradient coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110344681XA CN102400099B (en) | 2011-11-04 | 2011-11-04 | Technology for preparing nuclear fission reactor fuel clad surface CrAlSiN gradient coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102400099A true CN102400099A (en) | 2012-04-04 |
| CN102400099B CN102400099B (en) | 2013-06-12 |
Family
ID=45882731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110344681XA Expired - Fee Related CN102400099B (en) | 2011-11-04 | 2011-11-04 | Technology for preparing nuclear fission reactor fuel clad surface CrAlSiN gradient coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102400099B (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776474A (en) * | 2012-07-12 | 2012-11-14 | 济南大学 | Nano composite coating layer for surface treatment of substrate, and preparation method and device of nano composite coating layer |
| CN103757597A (en) * | 2014-02-07 | 2014-04-30 | 上海理工大学 | TiN/CrAlSiN nano composite multilayer coating and preparation method thereof |
| CN104441828A (en) * | 2014-12-04 | 2015-03-25 | 马鞍山多晶金属材料科技有限公司 | AlCrSiN film with resistance to seawater corrosion and multilayer compound structure and preparation method of AlCrSiN film |
| CN104674164A (en) * | 2015-03-24 | 2015-06-03 | 四川大学 | Method for preparing component oscillatory metal nitride coating |
| CN104766980A (en) * | 2015-04-28 | 2015-07-08 | 安徽工业大学 | Acid medium flue cell bipolar plate protection coating and preparing method thereof |
| CN104928637A (en) * | 2015-05-19 | 2015-09-23 | 上海新弧源涂层技术有限公司 | Nanometer composite structure protective coating made from high hardness CrAlSiN and preparation method of nanometer composite structure protective coating |
| CN105671499A (en) * | 2016-04-01 | 2016-06-15 | 中国科学院宁波材料技术与工程研究所 | Wear-resisting corrosion-resistant CrAlSiN composite coating and preparation method thereof |
| CN106521413A (en) * | 2016-11-15 | 2017-03-22 | 山东大学 | Cutter surface CrN-CrAlSiN stepped multi-element composite coating and production method thereof |
| CN107513694A (en) * | 2017-08-22 | 2017-12-26 | 四川大学 | A kind of zirconium cladding surface resistance to high temperature oxidation ZrCrFe/AlCrFeTiZr complex gradient coating preparation technologies |
| CN107858647A (en) * | 2017-11-09 | 2018-03-30 | 天津职业技术师范大学 | CrAlSiN nano-composite coatings that a kind of Al content changes in gradient and preparation method thereof |
| CN108118301A (en) * | 2017-12-29 | 2018-06-05 | 安徽多晶涂层科技有限公司 | A kind of AlCrSiN coatings in the interlayer with the variation of Si concentration gradients, preparation method |
| CN108486537A (en) * | 2018-03-09 | 2018-09-04 | 中国科学院宁波材料技术与工程研究所 | A kind of amorphous protective coating and its preparation method and application for zircaloy |
| CN109207953A (en) * | 2018-10-29 | 2019-01-15 | 四川大学 | Resistance to high temperature oxidation ZrNx/ (ZrAlFe) N/ (ZrAlFeM) N complex gradient coating preparation process |
| CN109234694A (en) * | 2018-10-29 | 2019-01-18 | 中国科学院宁波材料技术与工程研究所 | A kind of nanometer gradient composite laminated coating of vapor corrosion resistant to high temperatures and its preparation method and application |
| CN110004409A (en) * | 2019-04-23 | 2019-07-12 | 天津职业技术师范大学(中国职业培训指导教师进修中心) | CrAlN nanometer gradient coating and its preparation process with high rigidity and high-bond |
| WO2020143101A1 (en) * | 2019-01-10 | 2020-07-16 | 广东省测试分析研究所（中国广州分析测试中心） | Magnetron sputtering preparation method for gradient self-doped pure-phase multi-element metal oxide thin film |
| CN111441023A (en) * | 2020-04-29 | 2020-07-24 | 金堆城钼业股份有限公司 | Molybdenum surface oxygen barrier film and preparation method thereof |
| JP2020537048A (en) * | 2017-12-29 | 2020-12-17 | 安徽工業大学Ａｎｈｕｉ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｔｅｃｈｎｏｌｏｇｙ | AlCrSiN coating that changes the gradient of Si content and crystal size of ion source reinforcement |
| CN112853287A (en) * | 2020-12-31 | 2021-05-28 | 中国科学院宁波材料技术与工程研究所 | Protective coating with long-time high-temperature-resistant steam oxidation and preparation method thereof |
| CN112906274A (en) * | 2021-02-22 | 2021-06-04 | 中国核动力研究设计院 | Visual interface and method for annealing simulation of cladding material |
| CN114231901A (en) * | 2021-12-22 | 2022-03-25 | 昆山欧思克精密工具有限公司 | CrAlSiN gradient composite coating and preparation method thereof |
| CN114351087A (en) * | 2021-12-15 | 2022-04-15 | 核工业西南物理研究院 | Preparation method of CrAlVSiN coating |
| CN114807834A (en) * | 2021-01-18 | 2022-07-29 | 重庆理工大学 | CrAlN/CrAlSiN/TaC composite coating with low friction coefficient and high wear resistance and preparation method thereof |
| CN115029677A (en) * | 2022-06-27 | 2022-09-09 | 商丘市鸿大光电有限公司 | Preparation process of high-hydrogen-permeability isotope and high-temperature-resistant TaVNbZr/(TaVNbZrM) Nx gradient barrier layer |
| CN115679263A (en) * | 2022-10-11 | 2023-02-03 | 中国核动力研究设计院 | Corrosion-resistant coating and cladding material for nuclear reactor and preparation method of corrosion-resistant coating and cladding material |
| CN116180005A (en) * | 2022-12-19 | 2023-05-30 | 中国科学院高能物理研究所 | Gradient multilayer film, preparation method and characterization method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004016399A1 (en) * | 2002-07-30 | 2004-02-26 | Robert Bosch Gmbh | Housing unit |
| CN101033539A (en) * | 2006-03-08 | 2007-09-12 | 中国科学院金属研究所 | CrN/CrAlN protective coating capable of resisting high temperature corrosion in wide temperature range and preparing method |
| CN101310972A (en) * | 2007-05-25 | 2008-11-26 | 中国科学院金属研究所 | Codeposition gradient Ni-base superalloy coating and preparation technique thereof |
| CN101724301A (en) * | 2008-10-15 | 2010-06-09 | 中国科学院金属研究所 | MCrAlY+AlSiY composite coating and preparation technique thereof |
-
2011
- 2011-11-04 CN CN201110344681XA patent/CN102400099B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004016399A1 (en) * | 2002-07-30 | 2004-02-26 | Robert Bosch Gmbh | Housing unit |
| CN101033539A (en) * | 2006-03-08 | 2007-09-12 | 中国科学院金属研究所 | CrN/CrAlN protective coating capable of resisting high temperature corrosion in wide temperature range and preparing method |
| CN101310972A (en) * | 2007-05-25 | 2008-11-26 | 中国科学院金属研究所 | Codeposition gradient Ni-base superalloy coating and preparation technique thereof |
| CN101724301A (en) * | 2008-10-15 | 2010-06-09 | 中国科学院金属研究所 | MCrAlY+AlSiY composite coating and preparation technique thereof |
Cited By (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776474A (en) * | 2012-07-12 | 2012-11-14 | 济南大学 | Nano composite coating layer for surface treatment of substrate, and preparation method and device of nano composite coating layer |
| CN103757597B (en) * | 2014-02-07 | 2016-03-23 | 上海理工大学 | A kind of TiN/CrAlSiN nanocomposite laminated coating and preparation method thereof |
| CN103757597A (en) * | 2014-02-07 | 2014-04-30 | 上海理工大学 | TiN/CrAlSiN nano composite multilayer coating and preparation method thereof |
| CN104441828A (en) * | 2014-12-04 | 2015-03-25 | 马鞍山多晶金属材料科技有限公司 | AlCrSiN film with resistance to seawater corrosion and multilayer compound structure and preparation method of AlCrSiN film |
| CN104441828B (en) * | 2014-12-04 | 2016-08-17 | 安徽多晶涂层科技有限公司 | A kind of AlCrSiN thin film of anti-seawater corrosion multi-layer compound structure and preparation method thereof |
| CN104674164A (en) * | 2015-03-24 | 2015-06-03 | 四川大学 | Method for preparing component oscillatory metal nitride coating |
| CN104766980A (en) * | 2015-04-28 | 2015-07-08 | 安徽工业大学 | Acid medium flue cell bipolar plate protection coating and preparing method thereof |
| CN104766980B (en) * | 2015-04-28 | 2017-01-18 | 安徽工业大学 | Acid medium flue cell bipolar plate protection coating and preparing method thereof |
| CN104928637A (en) * | 2015-05-19 | 2015-09-23 | 上海新弧源涂层技术有限公司 | Nanometer composite structure protective coating made from high hardness CrAlSiN and preparation method of nanometer composite structure protective coating |
| CN104928637B (en) * | 2015-05-19 | 2017-12-22 | 上海新弧源涂层技术有限公司 | High rigidity CrAlSiN nano composite structure protective coatings and preparation method thereof |
| CN105671499A (en) * | 2016-04-01 | 2016-06-15 | 中国科学院宁波材料技术与工程研究所 | Wear-resisting corrosion-resistant CrAlSiN composite coating and preparation method thereof |
| CN105671499B (en) * | 2016-04-01 | 2018-08-10 | 中国科学院宁波材料技术与工程研究所 | A kind of wear-and corrosion-resistant CrAlSiN composite coatings and preparation method thereof |
| CN106521413A (en) * | 2016-11-15 | 2017-03-22 | 山东大学 | Cutter surface CrN-CrAlSiN stepped multi-element composite coating and production method thereof |
| CN107513694A (en) * | 2017-08-22 | 2017-12-26 | 四川大学 | A kind of zirconium cladding surface resistance to high temperature oxidation ZrCrFe/AlCrFeTiZr complex gradient coating preparation technologies |
| CN107513694B (en) * | 2017-08-22 | 2019-05-14 | 四川大学 | One kind being used for Zr alloy surface resistance to high temperature oxidation ZrCrFe/AlCrFeTiZr complex gradient alloy coat preparation process |
| CN107858647A (en) * | 2017-11-09 | 2018-03-30 | 天津职业技术师范大学 | CrAlSiN nano-composite coatings that a kind of Al content changes in gradient and preparation method thereof |
| CN107858647B (en) * | 2017-11-09 | 2019-10-25 | 天津职业技术师范大学 | A kind of CrAlSiN nano-composite coating and preparation method thereof that Al content changes in gradient |
| CN108118301A (en) * | 2017-12-29 | 2018-06-05 | 安徽多晶涂层科技有限公司 | A kind of AlCrSiN coatings in the interlayer with the variation of Si concentration gradients, preparation method |
| JP2020537048A (en) * | 2017-12-29 | 2020-12-17 | 安徽工業大学Ａｎｈｕｉ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｔｅｃｈｎｏｌｏｇｙ | AlCrSiN coating that changes the gradient of Si content and crystal size of ion source reinforcement |
| CN108118301B (en) * | 2017-12-29 | 2020-01-21 | 安徽多晶涂层科技有限公司 | AlCrSiN coating with intermediate layer with gradient change of Si content and preparation method |
| US10941479B2 (en) | 2017-12-29 | 2021-03-09 | Anhui DuojinTuceng Technology Co. Ltd. | Ion source enhanced AlCrSiN coating with gradient Si content and gradient grain size |
| CN108486537A (en) * | 2018-03-09 | 2018-09-04 | 中国科学院宁波材料技术与工程研究所 | A kind of amorphous protective coating and its preparation method and application for zircaloy |
| CN108486537B (en) * | 2018-03-09 | 2020-05-12 | 中国科学院宁波材料技术与工程研究所 | Amorphous protective coating for zirconium alloy and preparation method and application thereof |
| CN109207953A (en) * | 2018-10-29 | 2019-01-15 | 四川大学 | Resistance to high temperature oxidation ZrNx/ (ZrAlFe) N/ (ZrAlFeM) N complex gradient coating preparation process |
| CN109234694A (en) * | 2018-10-29 | 2019-01-18 | 中国科学院宁波材料技术与工程研究所 | A kind of nanometer gradient composite laminated coating of vapor corrosion resistant to high temperatures and its preparation method and application |
| WO2020143101A1 (en) * | 2019-01-10 | 2020-07-16 | 广东省测试分析研究所（中国广州分析测试中心） | Magnetron sputtering preparation method for gradient self-doped pure-phase multi-element metal oxide thin film |
| CN110004409A (en) * | 2019-04-23 | 2019-07-12 | 天津职业技术师范大学(中国职业培训指导教师进修中心) | CrAlN nanometer gradient coating and its preparation process with high rigidity and high-bond |
| CN111441023A (en) * | 2020-04-29 | 2020-07-24 | 金堆城钼业股份有限公司 | Molybdenum surface oxygen barrier film and preparation method thereof |
| CN112853287B (en) * | 2020-12-31 | 2022-12-06 | 中国科学院宁波材料技术与工程研究所 | Protective coating with long-time high-temperature-resistant steam oxidation and preparation method thereof |
| CN112853287A (en) * | 2020-12-31 | 2021-05-28 | 中国科学院宁波材料技术与工程研究所 | Protective coating with long-time high-temperature-resistant steam oxidation and preparation method thereof |
| CN114807834A (en) * | 2021-01-18 | 2022-07-29 | 重庆理工大学 | CrAlN/CrAlSiN/TaC composite coating with low friction coefficient and high wear resistance and preparation method thereof |
| CN112906274A (en) * | 2021-02-22 | 2021-06-04 | 中国核动力研究设计院 | Visual interface and method for annealing simulation of cladding material |
| CN114351087A (en) * | 2021-12-15 | 2022-04-15 | 核工业西南物理研究院 | Preparation method of CrAlVSiN coating |
| CN114231901A (en) * | 2021-12-22 | 2022-03-25 | 昆山欧思克精密工具有限公司 | CrAlSiN gradient composite coating and preparation method thereof |
| CN115029677A (en) * | 2022-06-27 | 2022-09-09 | 商丘市鸿大光电有限公司 | Preparation process of high-hydrogen-permeability isotope and high-temperature-resistant TaVNbZr/(TaVNbZrM) Nx gradient barrier layer |
| CN115029677B (en) * | 2022-06-27 | 2023-10-31 | 商丘市鸿大光电有限公司 | Preparation process of high-hydrogen-permeability isotope and high-temperature-resistant TaVNbZr/(TaVNbZrM) Nx composite gradient barrier layer |
| CN115679263A (en) * | 2022-10-11 | 2023-02-03 | 中国核动力研究设计院 | Corrosion-resistant coating and cladding material for nuclear reactor and preparation method of corrosion-resistant coating and cladding material |
| CN115679263B (en) * | 2022-10-11 | 2023-12-01 | 中国核动力研究设计院 | Corrosion-resistant coating and cladding material for nuclear reactor and preparation method thereof |
| CN116180005A (en) * | 2022-12-19 | 2023-05-30 | 中国科学院高能物理研究所 | Gradient multilayer film, preparation method and characterization method thereof |
| CN116180005B (en) * | 2022-12-19 | 2024-05-14 | 中国科学院高能物理研究所 | Gradient multilayer film, preparation method and characterization method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102400099B (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102400099B (en) | Technology for preparing nuclear fission reactor fuel clad surface CrAlSiN gradient coating | |
| Zhang et al. | Preparation, structure, and properties of an AlCrMoNbZr high-entropy alloy coating for accident-tolerant fuel cladding | |
| Li et al. | Microstructure, high-temperature corrosion and steam oxidation properties of Cr/CrN multilayer coatings prepared by magnetron sputtering | |
| CN109666911B (en) | High-entropy alloy coating resistant to high-temperature corrosion on surface of nuclear zirconium alloy cladding and preparation method thereof | |
| Sidelev et al. | Nickel-chromium (Ni–Cr) coatings deposited by magnetron sputtering for accident tolerant nuclear fuel claddings | |
| Xiao et al. | Effect of roughness of substrate and sputtering power on the properties of TiN coatings deposited by magnetron sputtering for ATF | |
| CN107513694A (en) | A kind of zirconium cladding surface resistance to high temperature oxidation ZrCrFe/AlCrFeTiZr complex gradient coating preparation technologies | |
| Jiang et al. | Comparative study on the tensile cracking behavior of CrN and Cr coatings for accident-tolerant fuel claddings | |
| Wang et al. | Study on nanocrystalline Cr2O3 films deposited by arc ion plating: II. Mechanical and tribological properties | |
| Chen et al. | Microstructure evolution and adhesion properties of thick Cr coatings under different thermal shock temperatures | |
| CN109972098A (en) | A kind of preparation method of cladding materials surface C rN thick coating | |
| CN106884149A (en) | Water environment wear-resistant coating, its preparation method and application | |
| CN109852943A (en) | The preparation method and product of nuclear-used zirconium alloy surface C rN coating | |
| CN102787300A (en) | Cr/CrAlN gradient coating technology of supercritical water-cooled reactor fuel can surface | |
| CN104561891B (en) | Double component gradient hydrogen permeation preventing coatings and preparation method thereof | |
| Chen et al. | Effect of the Ar/N2 flow ratio on the microstructure, mechanical properties, and high-temperature steam oxidation behavior of Cr/CrxN coatings for accident-tolerant fuel coatings | |
| CN109207953A (en) | Resistance to high temperature oxidation ZrNx/ (ZrAlFe) N/ (ZrAlFeM) N complex gradient coating preparation process | |
| Chen et al. | Microstructure and corrosion characteristics of CrCuFeMoNi HEA coatings with different compositions in high-temperature and high-pressure water | |
| CN109913771A (en) | A kind of VAlTiCrSi high-entropy alloy film and its application under briny environment | |
| Li et al. | Effect of buffer layer on oxidation and corrosion resistance of CrN coatings on Zr alloy prepared by FCVAD technology | |
| CN110983257B (en) | Surface treatment method for improving corrosion resistance and anti-icing performance of titanium alloy surface | |
| CN103014621B (en) | Preparation method of Cr-Si-C-N nanoscale composite coating | |
| CN106929799A (en) | High temperature resistant protective coating and preparation method and application | |
| CN115142018A (en) | High-entropy alloy coating resistant to high-temperature liquid lead/lead bismuth alloy corrosion and preparation method thereof | |
| Meng et al. | Improving the high-temperature oxidation resistance of CrN coating by gradient deposition considering internal stress effects |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130612 Termination date: 20131104 |