CN103114267A - Preparation method of steel substrate surface aluminum oxide coat - Google Patents
Preparation method of steel substrate surface aluminum oxide coat Download PDFInfo
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- CN103114267A CN103114267A CN2013100481064A CN201310048106A CN103114267A CN 103114267 A CN103114267 A CN 103114267A CN 2013100481064 A CN2013100481064 A CN 2013100481064A CN 201310048106 A CN201310048106 A CN 201310048106A CN 103114267 A CN103114267 A CN 103114267A
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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 the aluminum oxide coating layer preparation method on a kind of steel matrix surface, belong to metal material surface functional coating preparing technical field.
Background technology
Advantages such as that aluminum oxide coating layer has is high temperature resistant, corrosion-resistant, erosion resistant and be widely used in the fields such as the energy, chemical industry.In Accelerator Driven Subcritical system (ADS) due to utilize liquid lead bismuth alloy (LBE) as the spallation target of ADS system hold concurrently LBE that refrigerant causes temperature flowing by dissolve, wash away, the series of physical such as erosion and chemical process corrode structural steel, finally affect the 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 problems such as LBE and structured material consistency.
Different components structure iron sample is found in the research of LBE mechanism of corrosion, in low temperature LBE the structural steel corrosion not obvious, temperature rising oxidation corrosion and dissolved corrosion aggravation cause structural steel to lose efficacy.Austenitic steel is compared with martensitic steel, more easily is corroded owing to containing more Ni.For the ADS system of operation more than 500 ℃, must be in the protection of structured material surface coating.
Prepare one deck aluminium at stainless steel surface, the stainless steel surface that is diffused in by aluminium causes a concentration gradient that contains aluminium, forms the aluminum based metal compound layer, and the surface forms Al
2O
3Layer.The aluminum based metal compound layer has guaranteed adhesion property good between coating and stainless steel, the Al on surface
2O
3Layer can effectively stop the diffusion of positively charged ion and negatively charged ion, has guaranteed that namely long-time running can not cause stainless over oxidation again simultaneously.When this layer oxide compound was damaged, inner positively charged ion can be diffused into defective locations and carry out selfreparing.Prepare the aluminium of different thickness at stainless steel surface by methods such as hot aluminizing, surface parcel aluminium foil, embedding co-penetratings, but research finds that the corrosion resistance of coating is closely related with the aluminium content in preparation method and coating.The aluminium lamination of hot aluminizing preparation is often thicker, even can't stand the corrosion of 420 ℃ of LBE; For martensitic steel, because aluminium rapid diffusion in the aluminium lamination of hot aluminizing preparation enters the diffusion layer that causes occurring 100 micron thickness in stainless steel, therefore, hot aluminizing adds subsequent heat treatment technique and is not suitable for martensitic steel.The aluminium lamination that the parcel aluminium foil forms can stand 600 ℃ of corrosion, and the content of aluminium can be realized by the thickness of controlling aluminium foil, but this method also is 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 very high spread coefficient of aluminium.
Utilize vacuum-evaporation to aluminize and have distinctive advantage.Thermal evaporation is as physical vapor deposition (Physical Vapor Deposition, PVD) a kind of in, that a kind of nanometer that can obtain is to micron order film and free of contamination environment-friendly type surface film preparation method, in the situation that do not affect the matrix size, improve surface strength, strengthen the performances such as rotproofness and frictional wear.In recent years, the PVD technology has been widely used in the fields such as aerospace, automobile, chemical industry, the energy and biotechnology and has prepared functional coating.The preparation that thermal evaporation techniques is used for aluminum oxide coating layer has following advantage: 1) can obtain fine and close aluminium film on stainless steel, the aluminium film is attached to film forming in substrate by diffusion in coating process, 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 can be controlled instrument by crystalline substance and accurately controls, and this helps to optimize the thickness of transition layer, the concentration of aluminium and the thickness of 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 matrix alumina coating on surface is provided, its objective is and control the aluminium content in coating under the prerequisite that guarantees coating density and bonding strength, realize good corrosion resistance.
The objective of the invention is to be achieved through the following technical solutions: 1, a kind of preparation method of steel matrix alumina coating on surface is characterized in that performing step is as follows:
(1) the steel matrix workpiece is carried out after cleaning surfaces processes, put into the thermal evaporation chamber, adopt vacuum-evaporation at steel matrix surface preparation one deck even compact, the good aluminium coat of being combined with steel matrix;
(2) the steel matrix workpiece after aluminizing is put into protective atmosphere thermal treatment, and the mutual diffusion by aluminium coat and steel matrix makes between the aluminum oxide coating layer of surface crystallization and steel matrix and produces the middle layer.Show that by thermal shock experiment coating has good adhesion property.
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, is no more than 15% with the weight percent that guarantees aluminium in coating.
In described step (2), the thickness of alumina layer is adjustable in the 2-20 micrometer range according to the coating performance requirement, exists the middle layer of 1-5 micron to have good adhesion property to realize coating between aluminum oxide and steel matrix simultaneously; The thickness of described aluminium coat is accurately controlled by crystalline substance control instrument, helps to optimize the thickness of transition layer, the concentration of aluminium and the thickness of outermost layer aluminum oxide.
Steel matrix in described step (1) is all base steel materials, comprises the austenitic steel 316 that different industrial trades are commonly used, low activation ferrite/martensite steel and T91 steel that 316L 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 can be controlled instrument by crystalline substance and accurately controls, and this helps to optimize the thickness in middle layer, the concentration of aluminium and the thickness of outermost layer aluminum oxide.Simultaneously, coating dense non-porous hole, thickness is adjustable and uniformity, has overcome the methods such as hot aluminizing to thickness of coating and the unmanageable shortcoming of homogeneity.
(2) by protective atmosphere thermal treatment, not only formed fine and close middle layer between aluminum oxide coating layer and steel matrix, and avoided the over oxidation of steel matrix.Anti-thermal shock and the shock resistance of coating have effectively been improved in the middle layer, and overcome conventional coatings easy to crack, easily the problem such as peel off.
(3) process stabilizing is reliable, produces without the waste gas waste residue, and is free from environmental pollution.
(4) based on the aluminum oxide coating layer preparation method's of base steel material surface of the present invention broad applicability and excellent coating performance performance, can solve well the ADS nuclear power system to the difficult problem such as structural steel is corrosion-resistant, wear-resistant, and also can be used on the industrial circles such as the energy, chemical industry.
Description of drawings
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is the coating structure schematic diagram that the present invention prepares, and wherein 1 is steel as matrix material, and 2 is the 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 ℃, 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
With the structural steel such as martensitic steel T91, austenitic stainless steel 316,316L surface through 400,600,800,1000 order sand paperings after, successively put into the solution ultrasonic cleaning of ethanol and acetone after 5-10 minute, taking-up dries up.The steel that clean up are put on the substrate support of thermal evaporation apparatus, treated that vacuum reaches 2 * 10
-3Begin to deposit the simple substance aluminium lamination after Pa.A certain amount of aluminium wire is put into tungsten crucible, and the distance of steel and crucible is 30 centimetres.Begin thermal evaporation process after slowly improving electric current to 200 ampere, after aluminium wire all is evaporated, electric current is reduced to zero.Pass into nitrogen in vacuum chamber, open vacuum chamber, the steel of aluminium coat that taken out surface coverage, the thickness of aluminium coat is 3 microns.
The structural steel that the surface is pure aluminum is put into atmosphere furnace, pass into high pure nitrogen, slowly be warming up to 700 ℃ simultaneously, be incubated after 2 hours, be cooled to room temperature and take out under the nitrogen atmosphere protection.
Embodiment 2
With the structural steel such as martensitic steel T91, austenitic stainless steel 316,316L surface through 400,600,800,1000 order sand paperings after, successively put into the solution ultrasonic cleaning of ethanol and acetone after 5-10 minute, taking-up dries up.The steel that clean up are put on the substrate support of thermal evaporation apparatus, treated that vacuum reaches 2 * 10
-3Begin to deposit the simple substance aluminium lamination after Pa.A certain amount of aluminium wire is put into tungsten crucible, and the distance of steel and crucible is 30 centimetres.Begin thermal evaporation process after slowly improving electric current to 200 ampere, after aluminium wire all is evaporated, electric current is reduced to zero.Pass into nitrogen in vacuum chamber, open vacuum chamber, the steel of aluminium coat that taken out surface coverage, the thickness of aluminium coat is 7 microns.
The structural steel that the surface is pure aluminum is put into atmosphere furnace, pass into high pure nitrogen, slowly be warming up to 750 ℃ simultaneously, be incubated after 2 hours, be cooled to room temperature and take out under the nitrogen atmosphere protection.
Embodiment 3
With the structural steel such as martensitic steel T91, austenitic stainless steel 316,316L surface through 400,600,800,1000 order sand paperings after, successively put into the solution ultrasonic cleaning of ethanol and acetone after 5-10 minute, taking-up dries up.The steel that clean up are put on the substrate support of thermal evaporation apparatus, treated that vacuum reaches 2 * 10
-3Begin to deposit the simple substance aluminium lamination after Pa.A certain amount of aluminium wire is put into tungsten crucible, and the distance of steel and crucible is 30 centimetres.Begin thermal evaporation process after slowly improving electric current to 200 ampere, after aluminium wire all is evaporated, electric current is reduced to zero.Pass into nitrogen in vacuum chamber, open vacuum chamber, the steel of aluminium coat that taken out surface coverage, the thickness of aluminium coat is 10 microns.
The structural steel that the surface is pure aluminum is put into atmosphere furnace, pass into high-purity argon gas, slowly be warming up to 800 ℃ simultaneously, be incubated after 2 hours, be cooled to room temperature and take out under the nitrogen atmosphere protection.
With scanning electron microscope, the combination of surface, Cross Section Morphology, coating and the body material of coating is analyzed; Adopt energy dispersion spectrum EDS to analyze the composition in coatingsurface, cross section; Adopt the porosity of metallography microscope sem observation coating; Adhesion property by the 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 of aluminium-iron-three kinds of oxygen 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 is without significantly hole appearance.
The liquid lead bismuth of coating sample being put into 550 ℃ corrodes the corrosion resistance of examining coating in 1000 hours.Utilize the ethanol of 1:1:1 after corrosion finishes: hydrogen peroxide: the acetic acid mixed solution is removed the plumbous bismuth of remained on surface, to the corrosion after sample adopt equally scanning electron microscope, EDS, metaloscope test its component, pattern and coating and steel matrix in conjunction with situation, found that and utilize the aluminum oxide coating layer of thermal evaporation preparation to have good high temperature resistance liquid lead bismuth corrosive nature, as shown in Figure 4.
Need to prove, 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 fully, implementation procedure and method same the various embodiments described above; And the non-elaborated part of the present invention belongs to techniques well known.
The above; only be part embodiment of the present invention, but protection scope of the present invention is not limited to this, any those skilled in the art are in the technical scope that the present invention discloses; the variation that can expect easily or replacement are within all should being encompassed in protection scope of the present invention.
Claims (3)
1. the preparation method of a steel matrix alumina coating on surface is characterized in that performing step is as follows:
(1) the steel matrix workpiece is carried out after cleaning surfaces processes, put into the thermal evaporation chamber, adopt vacuum-evaporation at steel matrix surface preparation one deck even compact, the good aluminium coat of being combined with steel matrix; 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, and the mutual diffusion by aluminium coat and steel matrix makes between the aluminum oxide coating layer of surface crystallization and steel matrix and produces the middle layer, realizes 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, is no more than 15% with the weight percent that guarantees aluminium in coating; The thickness of described alumina layer requires adjustable in the 2-20 micrometer range according to coating performance, exist the middle layer of 1-5 micron to have good adhesion property to realize coating between aluminum oxide and steel matrix simultaneously.
2. the preparation method of steel matrix alumina coating on surface according to claim 1 is characterized in that: in described step (2), the thickness of aluminium coat is accurately controlled by crystalline substance control instrument.
3. the preparation method of steel matrix alumina coating on surface according to claim 1, it is characterized in that: the steel matrix in described step (1) is all base steel materials, comprise the austenitic steel 316 that different industrial trades are commonly used, low activation ferrite/martensite steel and T91 steel that 316L and nuclear power system use.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104046954A (en) * | 2014-06-13 | 2014-09-17 | 中国科学院金属研究所 | Method for improving liquid metal corrosion resistance of martensitic heat-resistant steel |
| CN105177505A (en) * | 2015-09-05 | 2015-12-23 | 苏州宏久航空防热材料科技有限公司 | Method for growing aluminium oxide coating on surface of silicon carbide fiber |
| CN108179400A (en) * | 2017-12-28 | 2018-06-19 | 淮安和通汽车零部件有限公司 | A kind of surface treatment method of extrusion die |
| CN108580886A (en) * | 2018-04-20 | 2018-09-28 | 江西保德电子材料有限公司 | A kind of method of surface of metal particles coated aluminum oxide |
| 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 |
| CN108977759A (en) * | 2018-09-20 | 2018-12-11 | 中国科学院近代物理研究所 | A kind of spallation target target ball surface metal Plasma Immersion Ion Implantation and deposition compound hardening treatment method |
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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104046954A (en) * | 2014-06-13 | 2014-09-17 | 中国科学院金属研究所 | Method for improving liquid metal corrosion resistance of martensitic heat-resistant steel |
| CN105177505A (en) * | 2015-09-05 | 2015-12-23 | 苏州宏久航空防热材料科技有限公司 | Method for growing aluminium oxide coating on surface of silicon carbide fiber |
| 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 |
| CN108179400A (en) * | 2017-12-28 | 2018-06-19 | 淮安和通汽车零部件有限公司 | A kind of surface treatment method of extrusion die |
| CN108580886A (en) * | 2018-04-20 | 2018-09-28 | 江西保德电子材料有限公司 | A kind of method of surface of metal particles coated aluminum oxide |
| 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 |
| CN108977759A (en) * | 2018-09-20 | 2018-12-11 | 中国科学院近代物理研究所 | A kind of spallation target target ball surface metal Plasma Immersion Ion Implantation and deposition compound hardening treatment method |
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