CN102400099B - 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
- CN102400099B CN102400099B CN201110344681XA CN201110344681A CN102400099B CN 102400099 B CN102400099 B CN 102400099B CN 201110344681X A CN201110344681X A CN 201110344681XA CN 201110344681 A CN201110344681 A CN 201110344681A CN 102400099 B CN102400099 B CN 102400099B
- 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.)
- Expired - Fee Related
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
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 particularly a kind of in fission-type reactor the new preparation process of chromium aluminium silicon nitrogen (CrAlSiN) gradient cladding of Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface deposition high temperature oxidation corrosion resistance performance and mechanical property excellence.
Background technology
Nuclear energy is as a kind of efficient, economic and lasting energy, and the aspect comprehensive advantages such as the energy dilemma that faces in the solution whole world, protection of the environment quality are remarkable.2002, the 4th generation reactor international symposium filtered out 6 kinds of heap types, and Supercritical-Pressure Light Water Cooled Reactor (SCWR) is one of them.SCWR is the High Temperature High Pressure water-cooled reactor that moves more than its thermodynamic critical point of water, 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 industrialization, 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 is also long-time creep 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 accumulating experience in the design of present pressurized-water reactor and boiling-water reactor.Therefore, existing fuel canning material can not satisfy corrosion resistance and mechanical property requirements in Supercritical-Pressure Light Water Cooled Reactor [optimization design of the effective low activity F/M of Supercritical-Pressure Light Water Cooled Reactor fuel sheath steel. Kang Renmu, Liu Guoquan, Hu Benfu etc. atomic energy science and technology. the 43rd the 6th phase of volume .2009].At present, low swelling austenitic stainless steel such as D9,1.4970,316Ti etc. are the candidate materials of main SCWR fuel sheath, and these materials have the advantages such as intensity is high, void swelling is low, weldability is good, neutron economy is better.Yet, the high temperature oxidation corrosion resistance poor-performing of above-mentioned materials in Supercritical-Pressure Light Water Cooled Reactor, 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 study hotspot of academia and engineering circles in recent years thus.Consider that Cr content in steel is relatively high, the Cr element is on the impact 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 the chemical metallurgy combination, and sticking power is better; On the other hand, the Cr element in coating can form oxide film by the O element in coatingsurface and 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, strong thermal shocking may cause coating ductility distortion, break too early [hardness and the cavitation of hypersonic flame spraying Fe-Cr base coating. Wu Yuping, Lin Pinghua, Wang Zehua. the material heat treatment journal. the 30th the 1st phase of volume .2009].Subsequently, people 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, also have the approximately better hardness of 18GPa [hard and superhard coating-properity, preparation and sign, Song Guihong, Du Hao, He Chunlin; 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 having presented 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 to face a great difficult problem, i.e. the interface binding power problem of coating and steel.Due to the nature difference of coating and base material great disparity, 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 by elemental composition and the weave construction of modulation coating.For example, the coating that has the people also to change in gradient by the forming element composition improves the interface binding power of itself and base material.Because the graded of coated component causes coating without the subgrade interface formation, coating and base material have elemental composition and cause them can realize that chemical metallurgy is combined simultaneously, thereby can increase substantially its interface binding power etc.In addition, 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 research and the application of CrAlSiN gradient cladding are also not yet arranged so far.The novel process of the CrAlSiN gradient cladding of Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface deposition high temperature oxidation corrosion resistance performance and excellent mechanical property in fission-type reactor, this is task of the present invention place just.
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-Pressure Light Water Cooled Reactor fuel sheath in present nuclear fission heap, and in conjunction with the high temperature oxidation corrosion resistance coatings technology, provide a kind of have excellent resistance to high temperature corrosion oxidation susceptibility and mechanical property, be combined good nuclear fission heap fuel sheath top coat chromium aluminium silicon nitrogen (CrAlSiN) gradient cladding novel process with low swelling austenite stainless steel substrate.
Purpose of the present invention realizes by following technical solution:
The preparation technology of nuclear fission Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface deposition CrAlSiN gradient cladding provided by the invention is characterized in that comprising successively following processing step:
(1) substrate surface polishing and cleaning
Select the Supercritical-Pressure Light Water Cooled Reactor fuel sheath to use austenitic stainless steel as base material, with the different waterproof abrasive paper of roughness, grinding and polishing is carried out on its surface successively; Subsequently, carrying out degreaser in ultrasonic container cleans; Carry out subsequently pickling and rinsed with deionized water, and use N
2Air-blowing is done; At last, dry substrate is put into vacuum chamber, cleaned with bias plasma backwash technique, 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, described 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), within first time period, until vacuum chamber bleed reach the base vacuum degree after, pass into Ar gas in vacuum chamber, its airshed is 200sccm, and operating air pressure is 0.3Pa, opens subsequently the Cr target and carries out sputter, its sputtering power is 200W, depositing time is 4min～6min, and in the pure Cr coating of described substrate surface deposition, deposit thickness is 80～120nm thus;
(b), within second time period, the Ar airshed and the Cr target sputtering power that keep (a) step, open simultaneously the Al target 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, making the thickness of CrAl coating by the adjusting depositing time is 180～220nm;
(c), within the 3rd time period, keep the Ar airshed of (b) step, and the sputtering power of Cr target and Al target, the while passes into N in vacuum chamber
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 mixed atmosphere, thereby obtain the CrAlN coating that N content increases in gradient gradually, to make the thickness of CrAlN coating be 250～300nm by regulating depositing time;
(d), within 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 mixed atmosphere, thereby obtain the CrAlSiN coating that nitrogen, content of silicon and aluminum increase gradually, and form (Cr, Al, Si) N Nanocrystals Embedded at Si at its nearly surf zone
3N
4Microstructure in amorphous phase, making the thickness of CrAlSiN coating by the adjusting depositing time is 2.5～3.0 μ m;
(3) gradient cladding with deposition carries out anneal
With the CrAlSiN gradient cladding of deposition, carry out in-situ annealing in uninterrupted vacuum environment and process, standby until the complete rear taking-up sample of anneal.
In technique scheme, the purpose of described anneal is that interface structure is dissolved each other, strengthened to the unrelieved stress in release coat, the Elements Diffusion of accelerating 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 technique scheme, deposition CrAlSiN gradient cladding Cr target, Al target and Si target used, their purity is 99.99%.
In technique scheme, its roughness of waterproof abrasive paper that roughness used is different is followed successively by 300～1200 orders.
In technique scheme, degreaser used cleans consists of sodium carbonate 160g/L, Trisodium Citrate 45g/L, promoting agent 5g/L, sodium phosphate 50g/L.
In technique scheme, described austenite stainless steel substrate is D9, or 1.4970, or 316Ti.
The CrAlSiN gradient cladding of preparation technology's preparation of nuclear fission Supercritical-Pressure Light Water Cooled Reactor 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 37GPa; More than interface binding power reaches 34N.
The present invention compared with prior art has the following advantages and useful technique effect:
(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 be because Cr, Al all can form fine and close oxide film protection layer with O, thereby can effectively stop O and other impurity element such as Cl to the erosion of matrix; Also can effectively hinder the diffusion of the elements such as O, H due to the N element in the enrichment of crystal boundary; In addition, because the nearly surf zone of coating is Si
3N
4Therefore the nano composite structure of brilliant (Cr, Al, the Si) N of amorphous phase clad nano can significantly strengthen the high temperature oxidation corrosion resistance performance.
(3) the CrAlSiN gradient cladding of the present invention's preparation possesses excellent mechanical property, and its hardness is more than 37GPa.Because the nearly surf zone of CrAlSiN gradient cladding has nano composite structure, so coating has very high surface hardness, also has simultaneously excellent wear resistance; Due to the structure with elemental composition graded, therefore help to alleviate the coating thermal stresses, make simultaneously coating have toughness and thermal shock resistance etc. preferably.
(4) CrAlSiN gradient cladding and the base material of the present invention's preparation have good interface binding power, more than reaching 34N.Therefore coating bottom enrichment Cr element can be combined with base material generation chemical metallurgy; Simultaneously, because the coating elemental composition gradually changes in gradient, the constituent structure at each subgrade interface is without remarkable sudden change, this interface binding power with strengthened coat and base material, interfacial fracture toughness.
(5) the present invention at Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface deposition the CrAlSiN gradient cladding, can increase substantially 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
The below is described in further detail the present invention with specific embodiment, but and does not mean that any restriction to protection domain of the present invention.
Embodiment of the present invention instrument:
Ultrahigh vacuum(HHV) multi-target magnetic control sputtering coating equipment, model QX-500 type;
The Supercritical-Pressure Light Water Cooled Reactor 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 successively according to foregoing processing step and processing condition.
316Ti stainless steel substrate surface deposition CrAlSiN gradient cladding the Supercritical-Pressure Light Water Cooled Reactor fuel sheath is used comprises following processing step:
(1) polishing of base material specimen surface and cleaning
At first, successively with 300～1200 purpose waterproof abrasive papers, the base material sample is carried out the surface grinding polishing; Subsequently, carry out degreaser and clean in ultrasonic container, its degreaser moiety is sodium carbonate 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 completed
2Gas dries up the base material sample; At last, the base material sample is placed in vacuum chamber carries out the cleaning of bias plasma backwash, 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 base vacuum degree used is 5 * 10
-4200 ℃ of Pa, depositing temperatures are coated with layer deposition process and comprise following 4 continuous time phases:
(a), within first time period, until vacuum chamber bleed reach base vacuum degree used after, at first pass into Ar gas in vacuum chamber, its airshed is 200sccm, and operating air pressure is 0.3Pa, opens subsequently the Cr target 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 described base material specimen surface deposition;
(b), within second time period, the Ar airshed and the Cr target sputtering power that keep (a) step, open simultaneously the Al target 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 at the base material specimen surface CrAl coating that Al content increases in gradient gradually, making the thickness of deposition CrAl coating by the adjusting depositing time is 180nm;
(c), within the 3rd time period, keep the Ar airshed of (b) step, and the sputtering power of Cr target and Al target, begin simultaneously to pass into N in vacuum chamber
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 mixed atmosphere, thereby obtain at the base material specimen surface CrAlN coating that N content increases in gradient gradually, to make the thickness of deposition CrAlN coating be 250nm by regulating depositing time;
(d), within 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, realizes carrying out Cr target, Al target and Si target at (Ar+N at the base material specimen surface
2) cosputtering in 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 completed the CrAlSiN gradient cladding, in uninterrupted vacuum environment, it is carried out in-situ annealing and process, 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; Standby until the complete rear taking-up sample of anneal.
The purpose of described anneal is that interface structure is dissolved each other, strengthened to the unrelieved stress in release coat, the Elements Diffusion of accelerating between coating and base material and each subgrade coating.
Performance to 316Ti austenitic stainless steel substrate surface CrAlSiN gradient cladding in above-described embodiment 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 cone diamond penetrator.To 8 points of coating sample different surfaces domain test, with its mean value as coating tested for hardness value.The result demonstration, 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 in conjunction with situation
Test parameter is: cut speed 1.5mm/min, loading rate 5N/min to 150N/min etc.The result demonstration, the interface sticking power of CrAlSiN gradient cladding and 316Ti steel substrate is 34N.
(3) adopt the high temperature oxidation resistance of self-control chamber type electric resistance furnace testing coating
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 anneal, the weightening finish of finding to contain the coating sample is not obvious, and remarkable without the weightening finish of coating sample.Result shows: the oxidation resistance temperature of CrAlSiN gradient cladding is at 950 ℃.
Embodiment 2
Adopt processing step, processing condition and the processing parameter identical with embodiment 1 to prepare the CrAlSiN gradient cladding; Be subject to the impact of base material character, subgrade thickness, component gradient etc. due to coating performance, embodiment 2 is base materials employed as different from Example 1 is 1.4970 austenite stainless steel substrates, and the 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 above-mentioned, other processing parameter is all identical with embodiment 1.Adopt coating performance testing method in the same manner as in Example 1.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 ℃.
By the experimental result of embodiment 1, embodiment 2 as seen, the CrAlSiN gradient cladding can significantly strengthen the surface property of Supercritical-Pressure Light Water Cooled Reactor fuel sheath.Than stainless steel substrate, have more excellent high temperature oxidation resistance and surface mechanical properties, and have higher interface binding power with base material, thereby can significantly promote military service performance and the work-ing life of fuel sheath part.
Claims (7)
1. the preparation technology of a nuclear fission Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface deposition CrAlSiN gradient cladding is characterized in that comprising successively following processing step:
(1) substrate surface polishing and cleaning
Select the Supercritical-Pressure Light Water Cooled Reactor fuel sheath to adopt austenitic stainless steel as base material, with the different waterproof abrasive paper of roughness, grinding and polishing is carried out on its surface successively; Subsequently, carrying out degreaser in ultrasonic container cleans; Carry out subsequently pickling and rinsed with deionized water, and use N
2Air-blowing is done; At last, dry substrate is put into vacuum chamber, cleaned with bias plasma backwash technique, its processing parameter is: the base vacuum degree is 5 * 10
-4Pa, backwash bias voltage are that-300 V, working gas are Ar gas, and backwash air pressure is that 1.0 Pa, backwash time are 20 min;
(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, described 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), within first time period, until vacuum chamber bleed reach the base vacuum degree after, pass into Ar gas in vacuum chamber, its airshed is 200 sccm, and operating air pressure is 0.3 Pa, opens subsequently the Cr target and carries out sputter, its sputtering power is 200 W, depositing time is 4min ~ 6min, and in the pure Cr coating of described substrate surface deposition, deposit thickness is 80 ~ 120 nm thus;
(b), within second time period, the Ar airshed and the Cr target sputtering power that keep (a) step, open simultaneously the Al target and carry out sputter, with Al target sputtering power by 50 W gradually linearity increase to 100 W, realize Cr target and Al target co-sputtering, thereby obtain the CrAl coating that Al content increases in gradient gradually, making the thickness of CrAl coating by the adjusting depositing time is 180 ~ 220 nm;
(c), within the 3rd time period, keep the Ar airshed of (b) step, and the sputtering power of Cr target and Al target, the while passes into N in vacuum chamber
2Gas, N
2Airshed by 0 sccm gradually linearity increase to 150 sccm, operating air pressure remains on 0.5 Pa, realizes that Cr target and Al target are at (Ar+N
2) cosputtering in mixed atmosphere, thereby obtain the CrAlN coating that N content increases in gradient gradually, to make the thickness of CrAlN coating be 250 ~ 300 nm by regulating depositing time;
(d), within the 4th time period, open the sputter of Si target, its sputtering power increases to 100 W by 50 W linearities, the sputtering power with Cr target and Al target is adjusted to 300 W and 200 W by 200 W and 100 W linearities respectively simultaneously, with N
2The flow of gas by 150 sccm gradually linearity increase to 250 sccm, realize that Cr target, Al target and Si target are at (Ar+N
2) cosputtering in mixed atmosphere, thereby obtain the CrAlSiN gradient cladding that nitrogen, content of silicon and aluminum increase gradually, and surf zone forms (Cr, Al, Si) N Nanocrystals Embedded at Si near gradient cladding
3N
4Microstructure in amorphous phase, making the thickness of CrAlSiN gradient cladding by the adjusting depositing time is 2.5 ~ 3.0 μ m;
(3) gradient cladding with deposition carries out anneal
With the CrAlSiN gradient cladding of deposition, carry out in-situ annealing in uninterrupted vacuum environment and process, standby until the complete rear taking-up sample of anneal.
2. the preparation technology of nuclear fission Supercritical-Pressure Light Water Cooled Reactor 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 90 min, the type of cooling are for cooling to room temperature with the furnace.
3. the preparation technology of nuclear fission Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface deposition CrAlSiN gradient cladding according to claim 1, is characterized in that depositing CrAlSiN gradient cladding Cr target used, Al target and Si target, and their purity is 99.99%.
4. the preparation technology of according to claim 1 or 3 described nuclear fission Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface deposition CrAlSiN gradient claddings, is characterized in that its roughness of the different waterproof abrasive paper of described roughness is followed successively by 300 ~ 1200 orders.
5. the preparation technology of nuclear fission Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface deposition CrAlSiN gradient cladding according to claim 1 and 2, what it is characterized in that described degreaser consists of sodium carbonate 160 g/L, Trisodium Citrate 45 g/L, promoting agent 5 g/L, sodium phosphate 50 g/L.
6. the preparation technology of nuclear fission Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface deposition CrAlSiN gradient cladding according to claim 1 is characterized in that described austenite stainless steel substrate is D9,1.4970 or 316Ti.
7. the CrAlSiN gradient cladding of according to claim 1-5 described techniques of any one preparations, the variation in thickness that it is characterized in that described CrAlSiN gradient cladding is 2.5 ~ 3.0 μ m, its resistance to high temperature oxidation temperature is up to 950 ℃; Hardness is more than 37 GPa; More than interface binding power reaches 34 N.
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 CN102400099A (en) | 2012-04-04 |
| CN102400099B true 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) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776474B (en) * | 2012-07-12 | 2014-03-05 | 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN106521413B (en) * | 2016-11-15 | 2019-04-02 | 山东大学 | A kind of ladder-like multicomponent composite coating of tool surface CrN-CrAlSiN and preparation method thereof |
| 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 |
| 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 |
| 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 |
| JP6884495B2 (en) * | 2017-12-29 | 2021-06-09 | 安徽工業大学Ａｎｈｕｉ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｔｅｃｈｎｏｌｏｇｙ | AlCrSiN coating with varying gradients in ion source-enhanced Si content and crystal dimensions |
| 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 |
| CN109234694B (en) * | 2018-10-29 | 2020-12-11 | 中国科学院宁波材料技术与工程研究所 | High-temperature steam corrosion resistant nano gradient composite multilayer coating and preparation method and application thereof |
| CN109207953B (en) * | 2018-10-29 | 2020-07-03 | 四川大学 | Preparation process of high-temperature oxidation resistant ZrNx/(ZrAlFe) N/(ZrAlFeM) N composite gradient coating |
| CN109576659A (en) * | 2019-01-10 | 2019-04-05 | 广东省测试分析研究所（中国广州分析测试中心） | The magnetron sputtering preparation method of gradient auto-dope pure phase multi-element metal oxide film |
| CN110004409B (en) * | 2019-04-23 | 2021-08-27 | 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 nano gradient coating with high hardness and high binding force and preparation process thereof |
| 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 |
| 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 |
| CN112906274B (en) * | 2021-02-22 | 2023-02-28 | 中国核动力研究设计院 | Visual interface and method for annealing simulation of cladding material |
| CN114351087B (en) * | 2021-12-15 | 2023-03-17 | 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 |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10259518A1 (en) * | 2002-12-19 | 2004-07-01 | Robert Bosch Gmbh | housing unit |
-
2011
- 2011-11-04 CN CN201110344681XA patent/CN102400099B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102400099A (en) | 2012-04-04 |
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 | |
| CN109666911B (en) | High-entropy alloy coating resistant to high-temperature corrosion on surface of nuclear zirconium alloy cladding and preparation method thereof | |
| Li et al. | Microstructure, high-temperature corrosion and steam oxidation properties of Cr/CrN multilayer coatings prepared by magnetron sputtering | |
| Wang et al. | Study on nanocrystalline Cr2O3 films deposited by arc ion plating: II. Mechanical and tribological properties | |
| 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 | |
| CN104561891B (en) | Double component gradient hydrogen permeation preventing coatings and preparation method thereof | |
| Soboyejo et al. | High temperature oxidation interfacial growth kinetics in YSZ thermal barrier coatings with bond coatings of NiCoCrAlY with 0.25% Hf | |
| Chen et al. | Microstructure evolution and adhesion properties of thick Cr coatings under different thermal shock temperatures | |
| CN106884149A (en) | Water environment wear-resistant coating, its preparation method and application | |
| CN102787300A (en) | Cr/CrAlN gradient coating technology of supercritical water-cooled reactor fuel can surface | |
| CN109852943A (en) | The preparation method and product of nuclear-used zirconium alloy surface C rN coating | |
| CN109207953A (en) | Resistance to high temperature oxidation ZrNx/ (ZrAlFe) N/ (ZrAlFeM) N complex gradient coating preparation process | |
| CN109913771A (en) | A kind of VAlTiCrSi high-entropy alloy film and its application under briny environment | |
| CN103590002A (en) | Preparation method for Al-Cr coating on nickel-based superalloy | |
| Chen et al. | Microstructure and corrosion characteristics of CrCuFeMoNi HEA coatings with different compositions in high-temperature and high-pressure water | |
| Qi et al. | Role of the nitrogen ratio on mechanical properties and wear resistance of CrN/Fe functionally graded coating produced by double glow plasma alloying | |
| CN103014621B (en) | Preparation method of Cr-Si-C-N nanoscale composite coating | |
| 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 | |
| Li et al. | Effect of buffer layer on oxidation and corrosion resistance of CrN coatings on Zr alloy prepared by FCVAD technology | |
| CN109234694B (en) | High-temperature steam corrosion resistant nano gradient composite multilayer coating and preparation method and application thereof | |
| CN110499494A (en) | It is a kind of using Zr as Cr/Al monofilm of substrate and preparation method thereof | |
| Wang et al. | Effect of Al content on 1200° C steam oxidation behavior of Cr-based coatings on TZM alloy | |
| CN113512710A (en) | 45 steel surface CrN-Cr gradient coating and preparation method and application thereof |
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 |