CN103114267B - Preparation method of steel substrate surface aluminum oxide coat - Google Patents
Preparation method of steel substrate surface aluminum oxide coat Download PDFInfo
- Publication number
- CN103114267B CN103114267B CN201310048106.4A CN201310048106A CN103114267B CN 103114267 B CN103114267 B CN 103114267B CN 201310048106 A CN201310048106 A CN 201310048106A CN 103114267 B CN103114267 B CN 103114267B
- Authority
- CN
- China
- Prior art keywords
- steel
- aluminum oxide
- coating
- aluminium
- coat
- 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
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a preparation method of steel substrate surface aluminum oxide coat; the preparation method is characterized in that aluminum plating in a certain thickness is deposited at a structural steel surface by using the thermal evaporation method, and then the aluminum oxide coat is obtained after being annealed under a protective atmosphere. The preparation method has the following main advantages: the coat prepared by the thermal evaporation method is controllable in thickness, is compact, is low in aperture rate, is excellent in combining strength with the steel substrate, and has an excellent anti-corrosion property, thus being an excellent protection coat capable of meeting the anti-corrosion requirement of structural steel surface in an ADS (adaptive damping system).
Description
Technical field
The present invention relates to a kind of aluminum oxide coating layer preparation method of steel matrix surface, belong to metal material surface functional coating preparing technical field.
Background technology
Aluminum oxide coating layer has the advantages such as high temperature resistant, corrosion-resistant, erosion resistant and is widely used in the field such as the energy, chemical industry.Owing to utilizing to hold concurrently as the spallation target of the ADS system series of physicals such as refrigerant causes the LBE of temperature flowing by dissolving, washing away, erosion and chemical process of liquid lead bismuth alloy (LBE) to corrode structural steel in accelerator-driven sub-critical system (ADS), finally affect structured material performance, cause certain potential safety hazard.Therefore, the plumbous bismuth cooled reactor system of actual motion must solve crucial science and the Practical Project problem such as LBE and structured material consistency.
Find the research of different components structure iron sample in LBE mechanism of corrosion, in low temperature LBE, structural steel corrosion is not obvious, and temperature raises oxidation corrosion and dissolved corrosion aggravation causes structural steel to lose efficacy.Austenitic steel compared with martensitic steel, owing to being more easily corroded containing more Ni.For the ADS system that more than 500 DEG C are run, must in the protection of structured material surface coating.
Prepare one deck aluminium at stainless steel surface, cause one containing the concentration gradient of aluminium by the stainless steel surface that is diffused in of aluminium, form aluminum based metal compound layer, surface forms Al
2o
3layer.Aluminum based metal compound layer ensure that adhesion property good between coating and stainless steel, the Al on surface
2o
3not only layer effectively can stop the diffusion of positively charged ion and negatively charged ion, ensure that long-time running simultaneously but also can not cause stainless over oxidation.When this layer of oxide compound is damaged, inner positively charged ion can be diffused into defective locations and carry out selfreparing.Prepared the aluminium of different thickness at stainless steel surface by hot aluminizing, surface method such as parcel aluminium foil, embedding co-penetrating etc., but research finds that the corrosion resistance of coating is closely related with the aluminium content in preparation method and coating.Aluminium lamination prepared by hot aluminizing is often thicker, even cannot stand the corrosion of 420 DEG C of LBE; For martensitic steel, because in aluminium lamination prepared by hot aluminizing, aluminium rapid diffusion enters in stainless steel the diffusion layer causing appearance 100 micron thickness, therefore, hot aluminizing adds subsequent heat treatment technique and is not suitable for martensitic steel.The aluminium lamination that parcel aluminium foil is formed can stand 600 DEG C of corrosion, and the content of aluminium can be realized by the thickness controlling aluminium foil, but this method is also not suitable for the complex components such as inside pipe wall, and this technique is not suitable for Martensite Stainless Steel, because the high temperature in heat treatment process can cause the spread coefficient that aluminium is very high.
Utilize vacuum-evaporation to aluminize and there is distinctive advantage.Thermal evaporation is as physical vapor deposition (Physical Vapor Deposition, PVD) one in, that one can obtain nanometer to micron order film and free of contamination environment-friendly type surface film preparation method, when not affecting matrix size, improving surface strength, strengthening the performance such as rotproofness and frictional wear.In recent years, PVD technology has been widely used in the fields such as aerospace, automobile, chemical industry, the energy and biotechnology and has prepared functional coating.Preparation thermal evaporation techniques being used for aluminum oxide coating layer has following advantage: 1) can obtain fine and close aluminium film on stainless steel, in coating process, aluminium film is attached to film forming in substrate by diffusion, to be conducive in last handling process aluminium to stainless diffusion, between outermost pellumina and substrate, bonding force is strong simultaneously; 2) in evaporate process, the thickness of aluminium film accurately can be controlled by brilliant control instrument, and this contributes to the thickness optimizing the thickness of transition layer, the concentration of aluminium and outermost layer aluminum oxide, is expected to for the preparation of the erosion shield in high quality LBE.
Summary of the invention
The present invention is just for above-mentioned the deficiencies in the prior art, a kind of preparation method of steel substrate surface aluminum oxide coat is provided, its objective is under the prerequisite ensureing coating density and bonding strength, control the aluminium content in coating, realize excellent corrosion resistance.
The object of the invention is to be achieved through the following technical solutions: 1, a kind of preparation method of steel substrate surface aluminum oxide coat, is characterized in that performing step is as follows:
(1), after surface cleaning process being carried out to steel matrix workpiece, put into thermal evaporation chamber, adopt vacuum-evaporation steel matrix surface prepare one deck even compact, with steel matrix in conjunction with good aluminium coat;
(2) the steel matrix workpiece after aluminizing is put into protective atmosphere thermal treatment, make to produce middle layer between the aluminum oxide coating layer of surface crystallization and steel matrix by the mutual diffusion of aluminium coat and steel matrix.Show that coating has good adhesion property by thermal shock experiment.
The vacuum tightness in the vacuum-evaporation chamber of described step (1) is 10
-4-10
-3pa.
Thermal treatment temp in described step (2) is 700-800oC, and heat-treating atmosphere is nitrogen or argon gas, and heat treatment time is 2-5 hour, to ensure that in coating, the weight percent of aluminium is no more than 15%.
In described step (2), the thickness of alumina layer requires adjustable in 2-20 micrometer range according to coating performance, and the middle layer that simultaneously there is 1-5 micron between aluminum oxide and steel matrix has good adhesion property to realize coating; The thickness of described aluminium coat is accurately controlled by brilliant control instrument, contributes to the thickness optimizing the thickness of transition layer, the concentration of aluminium and outermost layer aluminum oxide.
Steel matrix in described step (1) is all base steel materials, comprises low activation ferrite/martensite steel and the T91 steel of the conventional austenitic steel 316,316L of different industrial trade and nuclear power system use.
The present invention compared with prior art has the following advantages:
(1) the present invention utilizes thermal evaporation method at structural steel surface deposition aluminium coat, and its thickness accurately can be controlled by brilliant control instrument, and this contributes to the thickness optimizing the thickness in middle layer, the concentration of aluminium and outermost layer aluminum oxide.Meanwhile, coating dense non-porous hole, thickness is adjustable and uniformity, overcomes the methods such as hot aluminizing to thickness of coating and the unmanageable shortcoming of homogeneity.
(2) by N2shielded heat-treatment, between aluminum oxide coating layer and steel matrix, not only define fine and close middle layer, and avoid the over oxidation of steel matrix.Middle layer effectively improves anti-thermal shock and the shock resistance of coating, and overcome conventional coatings easy to crack, easily the problem such as to peel off.
(3) process stabilizing is reliable, produces without waste gas waste residue, free from environmental pollution.
(4) based on the broad applicability of the aluminum oxide coating layer preparation method of base steel material surface of the present invention and the coating performance performance of excellence, the difficult problems such as ADS nuclear power system is corrosion-resistant to structural steel, wear-resistant can be solved well, and also can be used on the industrial circle such as the energy, chemical industry.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is coating structure schematic diagram prepared by the present invention, and wherein 1 is steel as matrix material, and 2 is middle layer, and 3 is alumina layer;
Fig. 3 is the EDS result of thermal treatment rear surface in aluminum oxide coating layer nitrogen on 316;
Fig. 4 is that on 316, aluminum oxide coating layer corrodes section S EM photo and EDS line sweep result after 1000 hours in the liquid lead bismuth of 550 DEG C, and wherein the left side is the SEM photo of coating section, and the right is the EDS line sweep result of coating section.
Embodiment
Below with reference to embodiment, technical solution of the present invention is described in further detail.
Embodiment 1
By structural steel surfaces such as martensitic steel T91, austenitic stainless steel 316,316L after 400,600,800,1000 order sand paperings, successively put into the solution ultrasonic cleaning of ethanol and acetone after 5-10 minute, taking-up dries up.The steel cleaned up are put on the substrate support of thermal evaporation apparatus, treats that vacuum reaches 2 × 10
-3start after Pa to deposit simple substance aluminium lamination.A certain amount of aluminium wire is put into tungsten crucible, and the distance of steel and crucible is 30 centimetres.Start thermal evaporation process after slow raising electric current to 200 ampere, after aluminium wire is all evaporated, electric current is reduced to zero.Pass into nitrogen in the vacuum chamber, open vacuum chamber, take out the surface coverage steel of aluminium coat, the thickness of aluminium coat is 3 microns.
Be that the structural steel of pure aluminum puts into atmosphere furnace by surface, pass into high pure nitrogen, be slowly warming up to 700 DEG C simultaneously, be incubated after 2 hours, under nitrogen atmosphere protection, be cooled to room temperature taking-up.
Embodiment 2
By structural steel surfaces such as martensitic steel T91, austenitic stainless steel 316,316L after 400,600,800,1000 order sand paperings, successively put into the solution ultrasonic cleaning of ethanol and acetone after 5-10 minute, taking-up dries up.The steel cleaned up are put on the substrate support of thermal evaporation apparatus, treats that vacuum reaches 2 × 10
-3start after Pa to deposit simple substance aluminium lamination.A certain amount of aluminium wire is put into tungsten crucible, and the distance of steel and crucible is 30 centimetres.Start thermal evaporation process after slow raising electric current to 200 ampere, after aluminium wire is all evaporated, electric current is reduced to zero.Pass into nitrogen in the vacuum chamber, open vacuum chamber, take out the surface coverage steel of aluminium coat, the thickness of aluminium coat is 7 microns.
Be that the structural steel of pure aluminum puts into atmosphere furnace by surface, pass into high pure nitrogen, be slowly warming up to 750 DEG C simultaneously, be incubated after 2 hours, under nitrogen atmosphere protection, be cooled to room temperature taking-up.
Embodiment 3
By structural steel surfaces such as martensitic steel T91, austenitic stainless steel 316,316L after 400,600,800,1000 order sand paperings, successively put into the solution ultrasonic cleaning of ethanol and acetone after 5-10 minute, taking-up dries up.The steel cleaned up are put on the substrate support of thermal evaporation apparatus, treats that vacuum reaches 2 × 10
-3start after Pa to deposit simple substance aluminium lamination.A certain amount of aluminium wire is put into tungsten crucible, and the distance of steel and crucible is 30 centimetres.Start thermal evaporation process after slow raising electric current to 200 ampere, after aluminium wire is all evaporated, electric current is reduced to zero.Pass into nitrogen in the vacuum chamber, open vacuum chamber, take out the surface coverage steel of aluminium coat, the thickness of aluminium coat is 10 microns.
Be that the structural steel of pure aluminum puts into atmosphere furnace by surface, pass into high-purity argon gas, be slowly warming up to 800 DEG C simultaneously, be incubated after 2 hours, under nitrogen atmosphere protection, be cooled to room temperature taking-up.
Analyze with the combination of scanning electron microscope to the surface of coating, Cross Section Morphology, coating and body material; Energy dispersion spectrum EDS is adopted to analyze the composition in coatingsurface, cross section; Adopt the porosity of metallography microscope sem observation coating; By the adhesion property of thermal shock experiment testing coating.Result shows: coating is fine and close, and surface and cross section are without obvious hole and tiny crack; Coating is made up of aluminium-iron-oxygen three kinds elemental composition, and coatingsurface is aluminum oxide, and wherein the weight content of aluminium is between 13-15%, as shown in Figure 3.The combination of coating and matrix is good, and bonding surface occurs without obvious hole.
Liquid lead bismuth coating sample being put into 550 DEG C corrodes the corrosion resistance examining coating for 1000 hours.Corrosion terminates to utilize the ethanol of 1:1:1 afterwards: hydrogen peroxide: the plumbous bismuth of acetic acid mixture removing remained on surface, to the sample after corrosion adopt equally scanning electron microscope, EDS, metaloscope test its component, pattern and coating and steel matrix in conjunction with situation, found that the aluminum oxide coating layer utilizing thermal evaporation to prepare has good high temperature resistance liquid lead bismuth corrosive nature, as shown in Figure 4.
It should be noted that, according to the various embodiments described above of the present invention, those skilled in the art are the four corners that can realize independent claim of the present invention and appurtenance completely, implementation procedure and the same the various embodiments described above of method; And non-elaborated part of the present invention belongs to techniques well known.
The above; be only part embodiment of the present invention, but protection scope of the present invention is not limited thereto, any those skilled in the art are in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
Claims (3)
1. a preparation method for steel substrate surface aluminum oxide coat, is characterized in that performing step is as follows:
(1), after surface cleaning process being carried out to steel matrix workpiece, put into thermal evaporation chamber, adopt vacuum-evaporation steel matrix surface prepare one deck even compact, with steel matrix in conjunction with good aluminium coat; The vacuum tightness in described vacuum-evaporation chamber is 10
-4-10
-3pa;
(2) the steel matrix workpiece after aluminizing is put into protective atmosphere thermal treatment, make to produce middle layer between the aluminum oxide coating layer of surface crystallization and steel matrix by the mutual diffusion of aluminium coat and steel matrix, realize the adhesion property that coating is good; Described thermal treatment temp is 700-800 ° of C, and heat-treating atmosphere is nitrogen or argon gas, and heat treatment time is 2-5 hour, to ensure that in coating, the weight percent of aluminium is no more than 15%; The thickness of described alumina layer requires adjustable in 2-20 micrometer range according to coating performance, and the middle layer that simultaneously there is 1-5 micron between aluminum oxide and steel matrix has good adhesion property to realize coating.
2. the preparation method of steel substrate surface aluminum oxide coat according to claim 1, is characterized in that: in described step (2), the thickness of aluminium coat is accurately controlled by brilliant control instrument.
3. the preparation method of steel substrate surface aluminum oxide coat according to claim 1, it is characterized in that: the steel matrix in described step (1) is all base steel materials, comprise low activation ferrite/martensite steel and the T91 steel of the conventional austenitic steel 316,316L of different industrial trade and nuclear power system use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310048106.4A CN103114267B (en) | 2013-02-06 | 2013-02-06 | Preparation method of steel substrate surface aluminum oxide coat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310048106.4A CN103114267B (en) | 2013-02-06 | 2013-02-06 | Preparation method of steel substrate surface aluminum oxide coat |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103114267A CN103114267A (en) | 2013-05-22 |
| CN103114267B true CN103114267B (en) | 2015-01-07 |
Family
ID=48412684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310048106.4A Expired - Fee Related CN103114267B (en) | 2013-02-06 | 2013-02-06 | Preparation method of steel substrate surface aluminum oxide coat |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103114267B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104046954B (en) * | 2014-06-13 | 2017-02-15 | 中国科学院金属研究所 | Method for improving liquid metal corrosion resistance of martensitic heat-resistant steel |
| CN105177505B (en) * | 2015-09-05 | 2018-03-23 | 苏州宏久航空防热材料科技有限公司 | A kind of method in silicon carbide fibre superficial growth aluminum oxide coating layer |
| CN108179400B (en) * | 2017-12-28 | 2019-10-29 | 淮安和通汽车零部件有限公司 | A kind of surface treatment method of extrusion die |
| CN108580886B (en) * | 2018-04-20 | 2021-01-26 | 江西艾科控股有限公司 | Method for coating aluminum oxide on surface of metal particle |
| CN108677164A (en) * | 2018-05-28 | 2018-10-19 | 滁州国凯电子科技有限公司 | A kind of steel substrate surface A l2O3The atomic layer deposition preparation method of coating |
| CN108977759B (en) * | 2018-09-20 | 2020-10-02 | 中国科学院近代物理研究所 | Method for carrying out composite strengthening treatment on metal plasma immersion ion implantation and deposition on surface of spallation target ball |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08246132A (en) * | 1995-03-06 | 1996-09-24 | Kobe Steel Ltd | Method for modifying surface of steel |
| CN102310038A (en) * | 2011-09-29 | 2012-01-11 | 华东交通大学 | Method for improving surface hydrophobicity of metal film |
| CN102330095A (en) * | 2011-08-29 | 2012-01-25 | 中国科学院合肥物质科学研究院 | Preparation method of Al2O3 coating on surface of steel-matrix material |
-
2013
- 2013-02-06 CN CN201310048106.4A patent/CN103114267B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08246132A (en) * | 1995-03-06 | 1996-09-24 | Kobe Steel Ltd | Method for modifying surface of steel |
| CN102330095A (en) * | 2011-08-29 | 2012-01-25 | 中国科学院合肥物质科学研究院 | Preparation method of Al2O3 coating on surface of steel-matrix material |
| CN102310038A (en) * | 2011-09-29 | 2012-01-11 | 华东交通大学 | Method for improving surface hydrophobicity of metal film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103114267A (en) | 2013-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103114267B (en) | Preparation method of steel substrate surface aluminum oxide coat | |
| Hu et al. | Facile fabrication of superhydrophobic zinc coatings with corrosion resistance via an electrodeposition process | |
| Shao et al. | The study of electroless nickel plating directly on magnesium alloy | |
| Jamnapara et al. | Comparative analysis of insulating properties of plasma and thermally grown alumina films on electrospark aluminide coated 9Cr steels | |
| CN108796454A (en) | A kind of used by nuclear reactor zirconium cladding surface metal coating PVD preparation processes | |
| CN105671482B (en) | A kind of pack aluminizing agent and nickel base superalloy alitizing method | |
| Li et al. | Oxidation behavior and Cr-Zr diffusion of Cr coatings prepared by atmospheric plasma spraying on zircaloy-4 cladding in steam at 1300° C | |
| Chuang et al. | Electrochemical characterization of Zr-based thin film metallic glass in hydrochloric aqueous solution | |
| Kudiiarov et al. | Hydrogen sorption by Ni-coated titanium alloy VT1-0 | |
| Jiang et al. | Tungsten coating prepared on molybdenum substrate by electrodeposition from molten salt in air atmosphere | |
| Sun et al. | Preparation of tungsten coatings on graphite by electro-deposition via Na2WO4–WO3 molten salt system | |
| Qin et al. | Effect of heat treatment on the microstructure and corrosion behaviors of reactive plasma sprayed TiCN coatings | |
| Quan et al. | High temperature oxidation behavior of a novel Ni− Cr binary alloy coating prepared by cathode plasma electrolytic deposition | |
| Yang et al. | High temperature oxidation resistance of arc ion plating NiCoCrAlY coating modified via laser shock peening | |
| Barekatain et al. | High-temperature oxidation behaviors of plasma electrolytic oxidation coating on hot-dip aluminized HP40Nb alloy | |
| Yang et al. | Thermal shock behavior of YSZ thermal barrier coatings with a Ni-P/Al/Ni-P sandwich interlayer on AZ91D magnesium alloy substrate at 400° C | |
| CN106048519A (en) | Fe-Al/Al2O3 tritium-resisting coating used for tritium breeding cladding of fusion reactor and preparing method of Fe-Al/Al2O3 tritium-resisting coating | |
| Jun et al. | Preparation and properties of alumina coatings as tritium permeation barrier by plasma electrolytic oxidation | |
| Jiang | Effect of cathodic current density on performance of tungsten coatings on molybdenum prepared by electrodeposition in molten salt | |
| Zhang et al. | Direct preparation of nanostructured Ni coatings on aluminium alloy 6061 by cathode plasma electrolytic deposition | |
| Wu et al. | Effects of deposition thickness on electrochemical behaviors of AZ31B magnesium alloy with composite coatings prepared by micro-arc oxidation and electrophoretic deposition | |
| CN112725855B (en) | Preparation method of high-bonding-force high-corrosion-resistance coating on surface of neodymium iron boron magnet | |
| Huang et al. | Microstructural characterization and film-forming mechanism of a phosphate chemical conversion ceramic coating prepared on the surface of 2A12 aluminum alloy | |
| Cai et al. | Comparative hot corrosion performance of arc ion plated NiCoCrAlYSiHf coating in Na2SO4/NaCl/V2O5-media via high-current pulsed electron beam | |
| Zhen et al. | Oxidation-resistant CoCrAl coatings fabricated by electrodeposition in combination with electrophoretic deposition |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150107 Termination date: 20200206 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |