CN1296512C - Chromizing coating modified by rare earth oxide and preparation method and application thereof - Google Patents
Chromizing coating modified by rare earth oxide and preparation method and application thereof Download PDFInfo
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- CN1296512C CN1296512C CNB031339417A CN03133941A CN1296512C CN 1296512 C CN1296512 C CN 1296512C CN B031339417 A CNB031339417 A CN B031339417A CN 03133941 A CN03133941 A CN 03133941A CN 1296512 C CN1296512 C CN 1296512C
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- 238000005254 chromizing Methods 0.000 title claims abstract description 119
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000576 coating method Methods 0.000 title claims description 124
- 239000011248 coating agent Substances 0.000 title claims description 122
- 230000003647 oxidation Effects 0.000 claims abstract description 73
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 73
- 239000011651 chromium Substances 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000007747 plating Methods 0.000 claims abstract description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910000975 Carbon steel Inorganic materials 0.000 claims abstract description 9
- 239000010962 carbon steel Substances 0.000 claims abstract description 9
- 229910000851 Alloy steel Inorganic materials 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000009713 electroplating Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 6
- 239000011253 protective coating Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000003961 penetration enhancing agent Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 229910052702 rhenium Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract 6
- 239000010410 layer Substances 0.000 abstract 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- 239000002344 surface layer Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 56
- 238000012986 modification Methods 0.000 description 21
- 230000004048 modification Effects 0.000 description 20
- 229910000831 Steel Inorganic materials 0.000 description 15
- 239000010959 steel Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 10
- 125000004122 cyclic group Chemical group 0.000 description 9
- 238000012876 topography Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
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- 238000009413 insulation Methods 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 102000005262 Sulfatase Human genes 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention discloses a rare-earth oxide modified chromizing coating layer, a preparation method and application. The modified chromizing coating layer is composed of the components of permeant chromium, metal M from a composite plating layer and a small amount of rare-earth oxide, wherein the rare-earth oxide Re<x>O<y> is Re=Ce, Y, La, etc.; a chromium content in a surface layer in the chromizing coating layer is 35 to 55 portions by mass percent, and the rest is the M and a tiny amount of rare-earth element oxide; the M in the present invention comes from an M-Re<x>O<y> composite plating layer. A preparation course comprises the following procedures: metal Ni, Fe or Co, carbon steel or low-alloy steel is used as base materials so as to prepare the M-Re<x>O<y> composite plating layer on the base materials by adopting a composite electroplating method; then, the composite plating layer is diffused and chromized so as to obtain the rare-earth oxide modified chromizing coating layer. The present invention has the advantages of simple and mature technology, easy popularization, capability of thermally growing a protective compact Cr2O3 oxide film at a high temperature by the coating layer, great adhesion with a coating layer matrix and good oxidation resistance and corrosion resistance.
Description
Technical field
The present invention relates to coat preparing technology, specifically a kind of chromizing coating of rare-earth oxide modified and preparation method and application.
Background technology
The chromizing coating of preparing oxidation-resistance with the solid powder method chromising early has report.Its ultimate principle is that workpiece is imbedded in the penetration enhancer for preparing, and in argon gas atmosphere and under the certain temperature, the insulation certain hour by reaction, makes chromium infiltrate workpiece surface.Since under the high temperature oxidation stability corrosive environment, the Cr of heat growth
2O
3Therefore have protective value, on iron-based, metal such as Ni-based, develop chromizing coating usually, in the hope of forming Cr when the high temperature oxidation
2O
3Protective oxide film.Rare earth oxide improves the Cr of heat growth
2O
3The existing report of the performance of film, it mainly shows two aspects: (1) reduces Cr
2O
3The growth velocity of film; (2) improve Cr
2O
3Film is to the sticking power of matrix.Though chromizing coating is a kind of common high-temperature protection coating in the prior art, yet add the Cr that rare earth oxide further improves its heat growth therein
2O
3The research of film reports seldom that also it mainly is to mix a certain amount of rare earth oxide in chromizing coating have certain difficulty.
Summary of the invention
At above-mentioned deficiency, the purpose of this invention is to provide a kind of chromizing coating and preparation method and application of rare-earth oxide modified.It is by composite plating in advance, and the two-stage process of chromising then is with rare earth oxide Re
xO
y(Re=Ce, Y or La) joins the chromizing coating that forms rare-earth oxide modified in the chromizing coating, and it can significantly improve its high temperature oxidation resistance, the protectiveness Cr of can hotly grow under 700 ℃～1000 ℃ high temperature successive, densification
2O
3Oxide film.
Technical scheme of the present invention is as follows:
The chromizing coating of modification, its composition are M and the rare earth oxide in the coelectrodeposition layer, and the chromium element that infiltrates, and wherein M can be Ni, Fe, Co; The content of each element of coating, by mass percentage, the content of upper layer chromium is 35～55 parts in the chromizing coating, 1～4 part of rare earth oxide, all the other are M.
Its preparation method is to be base material with metal Ni, Fe, Co, carbon steel or low alloy steel, at first, adopts routine techniques, realizes the coelectrodeposition of M and rare earth oxide, prepares composite deposite, i.e. M-Re
xO
yCompound coating (Re=Ce, Y or La) wherein recommend to select M consistent with the main component of body material, to avoid or to be reduced in the chromizing coating that causes under the high temperature Service Environment and the mutual diffusion of matrix.The plating bath of composite plating is sulfate system (MSO
4), stirring up and down with 150rpm by porous plate in the coelectrodeposition process rare earth oxide particles is suspended in the plating bath, uniform deposition is at specimen surface; Bath temperature is 25～35 ℃, and current density is 2～5A/dm
2, electroplating time is 1.5～2 hours, the CeO in the coating
2Content is 2～7 mass percents.Secondly, solid powder method chromising; By mass percentage, diffusion agent formulation is: 45～50 parts of chromium powders (100～200 order), 46～50 parts of Al
2O
3Powder (100～200 order), 4～5 parts of NH
4Cl.Technology is: is warmed up to 1100～1150 ℃, is incubated 4～5 hours, and furnace cooling, the speed with 400～500ml/min in the whole chromising process feeds argon gas, and with anti-oxidation, the rare earth oxide content after the chromising in the coating is 1～4 part of mass percent.
Ultimate principle of the present invention is as follows: the rare earth oxide in the coating is as " storehouse " that produce rare earth element ion, and during high temperature oxidation, the rare earth element ion of generation is mixed the Cr of into growth
2O
3In the film, and poly-partially, suppress oxidation mechanism that Cr is dominant to external diffusion and change into by the O ion and spread the oxidation mechanism that is dominant inwards, thereby reduce rate of oxidation, and improve Cr to its crystal boundary
2O
3Film is to the sticking power of coated substrate.The chromizing coating of the rare-earth oxide modified of the present invention's preparation, wherein: under 700～1000 ℃ of high temperature, guarantee heat growth successive protectiveness Cr
2O
3Oxide film.Simultaneously, owing to mix rare earth oxide, it at high temperature can significantly improve the Cr of growth in the coating
2O
3The protective value of oxide film.
Advantage of the present invention is as follows:
1. can form Cr
2O
3Protective oxide film.With Cr of the prior art
2O
3Protective oxide film is compared, and the Cr content in the chromizing coating of the present invention reaches 35～55 parts in mass percent.This content guarantee coating beginning during oxidation with regard to growth protecting Cr
2O
3Oxide film, and have enough chromium elements to keep Cr in the coating to external diffusion
2O
3The stable growth of oxide film.Add rare earth oxide, can make oxide film finer and close, the speed of growth obviously reduces, and oxide film strengthens the adhesivity of coated substrate, thereby has improved the antioxidant property of coating greatly.Adopt the chromizing coating of the rare-earth oxide modified of the present invention's preparation can be under 700 ℃～1000 ℃ high temperature can heat growth successive, fine and close protectiveness Cr
2O
3Oxide film.With a kind of CeO of the present invention
2The chromizing coating of modification is an example, with make comparisons in the direct chromising of a kind of surface of low-carbon steel and chromising under the same conditions obtains after depositing single Ni coating on this soft steel in advance two kinds of oxidation susceptibilities that do not contain the chromizing coating of rare earth oxide respectively, test-results shows: CeO of the present invention
2The chromizing coating of modification, is compared with the coating of not adding rare earth oxide after 120 hours 840 ℃ of oxidations, and oxidation weight gain is low more than 2 times; When being interrupted oxidation for 940 ℃, the zone of oxidation of not adding the coating of rare earth oxide takes place seriously to peel off, and causes the oxidation susceptibility variation, and CeO
2The Cr of the growth on the chromizing coating of modification
2O
3Film does not have peeling phenomenon, thereby antioxidant property sharply improves.
2. technology is simple, ripe, and cost is low.The present invention adopts the solid powder method chromising, and penetration enhancer can reuse, and cost is lower, and simple to operate, and is very low to the requirement of workpiece shape, therefore, is of wide application.
Description of drawings
Fig. 1-a is the section structure of an embodiment of chromizing coating on the prior art middle low carbon steel.
Fig. 1-b is the section structure of an embodiment of chromizing coating on single nickel coating in the prior art.
Fig. 1-c is the section structure of chromizing coating on the Ni-rare earth oxide composite deposite of the present invention.
Fig. 2 is the content distribution of chromium element in coating of one embodiment of the invention.
Fig. 3-a is the Ni-CeO of one embodiment of the invention
2The CeO that obtains on the composite deposite
2The cross section pattern of the chromising layer of modification.
Fig. 3-b is that the face of the pairing Ce element of Fig. 3-a distributes.
Fig. 3-c is that the face of the pairing Cr element of Fig. 3-a distributes.
Fig. 3-d is that the face of the pairing Ni element of Fig. 3-a distributes.
Fig. 3-e is that the face of the pairing Fe element of Fig. 3-a distributes.
Fig. 4 is chromising layer and Ni-CeO of the present invention on soft steel chromising, the single nickel coating
2Three embodiment's of chromising layer at 120 hours weight changing curve of 840 ℃ of cyclic oxidations on the composite deposite.
Fig. 5 is chromising layer and Ni-CeO of the present invention on soft steel chromising, the single nickel coating
2The X-ray diffraction result of three embodiment of chromising layer on the composite deposite 840 ℃ of cyclic oxidation surperficial facies analyses after 120 hours.
Fig. 6-a be in the prior art embodiment soft steel chromizing coating at the surface topography of 840 ℃ of cyclic oxidations after 120 hours.
Fig. 6-b is that chromizing coating on the single nickel coating of an embodiment in the prior art is at the surface topography of 840 ℃ of cyclic oxidations after 120 hours.
Fig. 6-c is the Ni-CeO of one embodiment of the invention
2The CeO that obtains on the composite deposite
2Modification chromizing coating at the surface topography of 840 ℃ of cyclic oxidations after 120 hours.
Fig. 7-a is that the soft steel chromizing coating of an embodiment in the prior art is at the cross section pattern of 840 ℃ of cyclic oxidations after 120 hours.
Fig. 7-b be on the single nickel coating of an embodiment in the prior art chromizing coating at the cross section pattern of 840 ℃ of cyclic oxidations after 120 hours.
Fig. 7-c is the Ni-CeO of one embodiment of the invention
2The CeO that obtains on the composite deposite
2The chromizing coating of modification is at the cross section pattern of 840 ℃ of cyclic oxidations after 120 hours.
Fig. 8-a is the Ni-CeO of one embodiment of the invention
2The CeO that obtains on the composite deposite
2The chromizing coating of modification is at the cross section pattern of 840 ℃ of cyclic oxidations after 120 hours.
Fig. 8-b is that the face of the chromium element of correspondence on Fig. 6-a cross section distributes.
Fig. 8-c is that the face of the Ce element of correspondence on Fig. 6-a cross section distributes.
Fig. 8-d is that the face of the Ni element of correspondence on Fig. 6-a cross section distributes.
Fig. 8-e is that the face of the Fe element of correspondence on Fig. 6-a cross section distributes.
Fig. 9 is Ni-CeO of the present invention
2And Ni-Y
2O
3Chromizing coating on the composite deposite is at 90 hours weight changing curve of 940 ℃ of discontinuity oxidations.
Figure 10-a be on the prior art middle low carbon steel chromizing coating at 90 hours low power surface topography of 940 ℃ of discontinuity oxidations.
Figure 10-b be in the prior art on single nickel coating chromizing coating at 90 hours surface topography of 940 ℃ of discontinuity oxidations.
Figure 10-c is Ni-CeO of the present invention
2The CeO that obtains on the composite deposite
2The chromizing coating of modification is at 90 hours surface topography of 940 ℃ of discontinuity oxidations.
Figure 10-d is Ni-Y of the present invention
2O
3The Y that obtains on the composite deposite
2O
3The chromizing coating of modification is at 90 hours surface topography of 940 ℃ of discontinuity oxidations.
Figure 11-a is that prior art middle low carbon steel matrix chromizing coating is at 90 hours cross section pattern of 940 ℃ of discontinuity oxidations.
Figure 11-b be in the prior art on single nickel coating chromizing coating at 90 hours cross section pattern of 940 ℃ of discontinuity oxidations.
Figure 11-c is Ni-CeO of the present invention
2The CeO of the acquisition on the composite deposite
2The chromizing coating of modification is at 90 hours cross section pattern of 940 ℃ of discontinuity oxidations.
Figure 11-d is Ni-Y of the present invention
2O
3The Y of the acquisition on the composite deposite
2O
3The chromizing coating of modification is at 90 hours cross section pattern of 940 ℃ of discontinuity oxidations.
Embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Embodiment
Present embodiment is with first Ni-CeO on soft steel
2And Ni-Y
2O
3Composite plating spreads chromising then and prepares CeO
2And Y
2O
3The chromizing coating of modification is an example:
The composition of the chromizing coating of rare-earth oxide modified: upper layer chromium content is 35-55 part, and its composition is the changes in distribution state that reduces gradually from the surface to inside.Oxide compound CeO
2Or Y
2O
3Be 1-4 part, surplus is M (Ni among Ni, Fe or the Co), from composite deposite;
Its preparation method is: adopt conventional composite plating technology to prepare M-rare earth oxide compound coating.M is Ni, Fe or Co, the general choosing element identical with the body material major components.Body material is the relatively poor Fe of antioxidant property, Ni, Co, carbon steel, steel alloy, sulfate system (MSO commonly used
4) plating bath.Present embodiment is selected Ni low temperature neutral sulfatase plating bath for use, preparation Ni-CeO
2And Ni-Y
2O
3Compound coating, chromising thereon then prepares CeO respectively
2And Y
2O
3The chromizing coating of modification.Its flow process is as follows:
Substrate metal carbon steel-surface finish to 800
#Waterproof abrasive paper-surperficial ultrasonic cleaning-containing CeO
2Nickel plating bath in carry out composite plating-acquisition Ni-CeO
2Composite deposite-chromising-acquisition CeO
2The chromizing coating of modification.
When being plating, key of the present invention keeps CeO
2Or Y
2O
3Particle suspension is in tank liquor, and control is filled a prescription and technology during chromising.Present embodiment adopts traditional composite plating facility and solid powder method chromising facility to prepare.Specific as follows:
1) getting carbon steel is base material, is processed into the sample of 15 * 10 * 2mm size, is milled to 800 through silicon carbide paper
#Sand paper, ultrasonic cleaning in acetone;
The CeO of the nano-scale of 2) selecting for use
2Powder is a nano-scale, 5～50 nanometers, Y
2O
3Powder is of a size of micron order, 1～5 micron.Particle is immersed in the sodium dodecyl sulfate solution earlier, so that particles dispersed is avoided reuniting;
3) electroplate liquid adopts the low temperature modification plating bath, and composition is as follows: NiSO
47H
2O 150g/l, NH
4Cl 15g/l, H
3BO
315g/l, sodium lauryl sulphate 0.1g/l; The solution of configuration was placed 24 hours through fully stirring after-filtration; The solution pH value can use in 5.4～5.6 scopes;
4) electrodeposition process adopts plate pump formula device to stir plating bath, is suspended in the plating bath to guarantee plating bath middle-weight rare earths oxide particle, and uniform deposition is at specimen surface; Bath temperature is 30 ℃, and current density is 2A/dm
2, stirring velocity is 150rpm.Electroplating time is 1.5 hours, and the sample mean thickness of coating is 30 μ m, CeO
2Or Y
2O
3Compounding quantity is 2～7 parts of mass percents;
5) chromising then.The prescription of chromizing agent is (by mass percentage): 50 parts of chromium powders (200 order), 46 parts of Al
2O
3Powder (200 order), 4 parts of NH
4Cl (reagent size).Technology is: be warmed up to 1120 ℃ of insulations 4 hours with stove, furnace cooling feeds argon gas, CeO in the chromizing coating with 400ml/min speed in the whole chromising process
2Or Y
2O
3Content is 1～4 part of mass percent;
6) sample boiled in distilled water 20 minutes after taking out.
Section structure after the chromising
Section structure after the chromising such as Fig. 1-a, 1-b, 1-c, on chromising on soft steel chromising, the single nickel coating, the Ni-rare earth oxide composite deposite after the chromising three kinds of samples all thicken.Coating was to outgrowth when chromising was described.Find out that from Fig. 1-a, 1-b, 1-c it is two-layer that three kinds of infiltration layers all are divided into, but its pattern, structure, thickness are all closely related with matrix.In Fig. 1-a, about 75～80 μ m of chromizing layer thickness, skin is 35 μ m.In Fig. 1-b, about 55～60 μ m of chromising layer, skin is 12 μ m.In Fig. 1-c, about 50～55 μ m of chromising layer, skin is 38 μ m.For Fig. 1-a, Fig. 1-b, skin mainly causes to outgrowth.And some is that interior growth causes in the skin of Fig. 1-c, this be with prior art in the thickness of original coating relatively draw.From pattern, some carbide (Cr are arranged in the top layer of soft steel chromising layer
23C
6), on single nickel coating in the chromising layer crystal grain thicker.And at Ni-CeO
2Chromising layer mesectoderm on the composite deposite is fine crystalline structure (Fig. 1-c).
Fig. 2 is that chromium is along the concentration distribution on the cross section after the chromising on chromising on soft steel chromising, the single nickel coating, the Ni-rare earth oxide composite deposite, because the diffusibility of chromium in ferrite is more intense, content is higher.But on nickel coating, added CeO
2The chromium content of infiltration layer be higher than chromium content on single nickel coating, and successively decrease slowly.This is CeO
2Change the result of infiltration level structure.Fig. 3-a, 3-b, 3-c, 3-d, 3-e are the electron probe microanalysis of each element on the cross section.Chromising layer skin formed fine crystalline structure (3-a), simultaneously, by Fig. 3-b as seen, CeO
2Disperse is distributed in the chromizing coating, and it not only influences the chromising process, makes chromium content in the infiltration layer be higher than chromium content on single nickel coating, also can play strengthened coat simultaneously.
840 ℃ antioxidant property
Oxidation experiment carries out under laboratory environment, and oxidizing temperature is 840 ℃, circulation in 2 hours, air cooling 30 minutes, totally 60 circulations, oxidation 120 hours.Three kinds of samples all do not peel off after the oxidation.Fig. 4 wherein adds CeO for the weight changing curve of oxidation
2The coating oxidation gain in weight minimum, antioxidant property is best.Fig. 5 is the surperficial facies analysis after the oxidation, and zone of oxidation is Cr
2O
3Protective membrane.Yet Cr on single nickel coating
2O
3Along [202] crystal orientation preferential growth, CeO
2There is not tangible preferential growth phenomenon after the chromizing coating oxidation of modification, thus oxide film pattern even compact more.And the peak of matrix has appearred, illustrate that oxide film is thinner.Fig. 6-a, 6-b, 6-c are the surface topography (wherein the right is the subregional enlarged view of left lateral) of sample after the oxidation, and three kinds of coatingsurfaces all have wrinkling.Compare with soft steel chromizing coating oxidized surface that (Fig. 6-a), thicker (Fig. 6-b), and big flats crystal grain is arranged, Here it is along the result of [202] crystal orientation growth for the crystal grain of oxide film on single nickel coating.Opposite, CeO
2The chromising layer oxidation rear surface crystal grain of modification tiny (Fig. 6-c), this presentation of results CeO
2Existence the growth of oxide film is had a significant effect.The cross section pattern of three kinds of coatings is (wherein the right is the subregional enlarged view of left lateral) shown in Fig. 7-a, 7-b, 7-c.With the cross section (Fig. 7-a) compare after the oxidation of soft steel chromising layer, hole appears in single nickel coating chromizing coating zone of oxidation and substrate interface, they during by oxidation cationvacancy at oxide film-coating interface formation of deposits, that the zone of oxidation that these two kinds of coatings are described and combining of matrix are not is fine (Fig. 7-b).In addition, after Fig. 7-b showed the oxidation of single nickel coating chromizing coating, γ ' phase (Ni separated out in the bottom of oxide film
2Cr), in coating and substrate interface hole appears simultaneously.Wherein, Ni
2The Cr precipitate is because the local dilution of Cr causes, and " Ke Kendaer " effect that hole is because the external diffusion of Fe during oxidation (by carbon steel to coating) causes causes.This coating of this presentation of results is obviously degenerated when oxidation.Yet for Ni-CeO
2(Fig. 7-c), zone of oxidation combines with coated substrate closely, does not have hole and precipitate in the coating after the chromizing coating oxidation on the composite deposite.But, many pittings are arranged, CeO in the coating
2Particle is in the pitting, and this is the corrosion pit that stays after the etching.Because CeO
2Particle generally is in crystal boundary and triangle crystal boundary place, and these local corrosion speeds are very fast, caused the appearance of corrosion pit.Still keeping the preceding fine crystalline structure of oxidation behind the coating oxidation (as Fig. 8-a), corresponding electron probe microanalysis shows that the surface has formed the successive protection and touched Cr
2O
3(Fig. 8-b).Ce (can think CeO
2) (Fig. 8-c) to before the oxidation be in similar position distributes.During oxidation, CeO
2In coating, not only can stop the degeneration of coating, and it also serves as the Ce ionic source that produces.The Ce ion is at Cr
2O
3In the film process of growth, can mix in the oxide film and poly-partially, thereby reduce the speed of growth of oxide film, improve the antioxidant property of coating to crystal boundary.
940 ℃ antioxidant property
Fig. 9 is 90 hours a weight changing curve of 940 ℃ of interruption oxidations, and its middle low carbon steel chromizing coating rises after 68 hours in rain in oxidation, in conjunction with Figure 10-a, as can be known, because oxide skin is peeled off and is caused.CeO
2, Y
2O
3The rate of oxidation of the chromizing coating of modification is well below the rate of oxidation of the coating of not adding rare earth oxide.This has just illustrated that rare earth oxide has participated in the oxidising process of coating, has improved the antioxidant property and the antistrip performance of coated substrate greatly.Compare CeO simultaneously
2, Y
2O
3The chromizing coating of modification finds that both rate of oxidation are more or less the same.The size difference that also is these two kinds of rare earth oxide particles is little to the oxidation kinetics influence.Figure 10-a, 10-b, 10-c, 10-d are chromising on soft steel chromising, the single nickel coating, Ni-rare earth oxide CeO
2Composite deposite and Ni-rare earth oxide Y
2O
3Surface topography after four kinds of sample oxidations after the chromising on the composite deposite, wherein Figure 10-b, 10-c, 10-d the right are the subregional enlarged view of left lateral.Soft steel peels off after 68 hours in oxidation.(Figure 10-b) has wrinkling, and crystal grain is thicker in single nickel coating chromising oxidation rear surface.Ni-CeO
2(Figure 10-c), Ni-Y
2O
3(Figure 10-d) the oxidized surface crystal grain of compound coating is tiny, particularly Ni-Y
2O
3Compound coating oxidation rear surface crystal grain is uniformly dispersed, smooth.Figure 11-a, 11-b, 11-c, 11-d are described four kinds of pairing cross sections of oxidised samples, and wherein the right is the enlarged view of square frame subregion, the left side.(Figure 11-a) middle oxide film is thicker, and porous, loose in cross section after the soft steel chromising oxidation.Chromising oxidation rear oxidation film on single nickel coating (Figure 11-b) is following many holes to occur, they during by oxidation cationvacancy at oxide film-coating interface formation of deposits.And Ni-CeO
2(Figure 11-c), Ni-Y
2O
3(Figure 11-d) the oxidation cross section oxide film of compound coating is thin and fine and close, the interface hole do not occur.
CeO of the present invention
2The chromizing coating of modification can be used as resistance to high temperature oxidation or corrosive protective coating, is used for relatively poor ferrite of antioxidant property below 900 ℃ and 900 ℃ or austenite steel, and the anti-oxidant or corrosive coating of metal Ni, Co, Fe etc.And, this modified coating be expected to use with coal firing boiler, vapourizing furnace, incinerator in the associated components envrionment temperature at the protective coating of the pipeline made from carbon steel and low alloy steel (for example water wall tube, generating tube, heat transfer tube etc.) below 900 ℃.
Claims (7)
1. the chromizing coating of a rare-earth oxide modified is characterized in that: its composition is by the chromium that infiltrates composite deposite with from composite deposite M-Re
xO
yMetal M and a small amount of rare earth oxide form, wherein M is Ni, Fe or Co, rare earth oxide Re
xO
yBe CeO
2, Y
2O
3Or La
2O
3By mass percentage, upper layer chromium content is 35～55 parts in the chromizing coating, 1～4 part of rare earth oxide, and all the other are M.
2. according to the preparation method of the chromizing coating of the described rare-earth oxide modified of claim 1, be prepared as " the two step process methods " that it is characterized in that coating, promptly be divided into latter two flow process earlier: 1) with metal Ni, Fe or Co, carbon steel or low alloy steel is a base material, is passing through to add rare earth oxide Re with the method for coelectrodeposition in plating bath in advance on the base material
xO
yPreparation M-Re
xO
yComposite deposite; Wherein flow process 1) M-Re
xO
yIn the composite deposite, M is Ni, Fe or Co, Re
xO
yBe rare earth oxide CeO
2, Y
2O
3Or La
2O
3The mass percent meter, 2～7 parts of rare earth oxides, all the other are M; 2) use the pressed powder entrapping method at M-Re
xO
yChromising on the composite deposite makes the chromizing coating of rare-earth oxide modified.
3. according to the preparation method of the chromizing coating of the described rare-earth oxide modified of claim 2, it is characterized in that: by stirring rare earth oxide particles is suspended in the plating bath in the electrodeposition process, uniform deposition is at specimen surface; Bath temperature is 25～35 ℃, and current density is 2～5A/dm
2, electroplating time is 1.5～2 hours.
4. according to the preparation method of the chromizing coating of the described rare-earth oxide modified of claim 2, it is characterized in that: the penetration enhancer that adopts in the chromising process by mass percentage, diffusion agent formulation is: 45～50 parts of chromium powders, 46～50 parts of Al
2O
3Powder, 4～5 parts of NH
4Cl; Processing parameter is: be warmed up to 1100～1150 ℃, be incubated 4～6 hours, furnace cooling gets final product; In argon shield atmosphere, carry out in the whole chromising process.
5. according to the preparation method of the chromizing coating of the described rare-earth oxide modified of claim 2, it is characterized in that: select M consistent with the main component of body material.
6. according to the application of the chromizing coating of the described rare-earth oxide modified of claim 1, it is characterized in that: the chromizing coating of described rare-earth oxide modified can be used as temperature carbon steel, low alloy steel under the oxidisability corrosive environment below 1000 ℃, stainless protective coating.
7. according to the application of the chromizing coating of the described rare-earth oxide modified of claim 1, it is characterized in that: the chromizing coating of described rare-earth oxide modified can be used as resistance to high temperature oxidation or corrosive protective coating, is used for the protective coating of the pipeline that associated components envrionment temperature in the coal firing boiler, vapourizing furnace, incinerator makes at the carbon steel and low alloy steel below 1000 ℃.
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| CN101775599B (en) * | 2010-02-22 | 2011-04-13 | 山东电力研究院 | Pretreatment method for improving oxidation resistance of T91/P91 steel in high temperature water steam |
| CN105861972A (en) * | 2016-04-15 | 2016-08-17 | 航天材料及工艺研究所 | Chromic oxide-titanium oxide based high-temperature and high-emissivity coating and preparation method thereof |
| CN105858863A (en) * | 2016-05-12 | 2016-08-17 | 浙江欧莱科机电制造有限公司 | Water purifier of washing machine |
| CN106282913A (en) * | 2016-08-30 | 2017-01-04 | 中航动力股份有限公司 | The penetration enhancer slip of a kind of slip chromising and Chromizing Layer preparation method |
| CN109136829B (en) * | 2018-10-23 | 2020-04-28 | 中国石油大学(华东) | Steel-based surface alloying-ion nitriding wear-resistant corrosion-resistant composite modified layer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045133A (en) * | 1989-02-24 | 1990-09-05 | 单际荣 | A kind of powder solid chromize pharmaceutical and preparation method thereof |
| US4963395A (en) * | 1988-06-24 | 1990-10-16 | Combustion Engineering, Inc. | Method of chromizing large size articles |
| CN1038052C (en) * | 1991-05-13 | 1998-04-15 | 中国科学院金属腐蚀与防护研究所 | Preparation process of high-temperature oxidation resistant coating |
-
2003
- 2003-09-10 CN CNB031339417A patent/CN1296512C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4963395A (en) * | 1988-06-24 | 1990-10-16 | Combustion Engineering, Inc. | Method of chromizing large size articles |
| CN1045133A (en) * | 1989-02-24 | 1990-09-05 | 单际荣 | A kind of powder solid chromize pharmaceutical and preparation method thereof |
| CN1038052C (en) * | 1991-05-13 | 1998-04-15 | 中国科学院金属腐蚀与防护研究所 | Preparation process of high-temperature oxidation resistant coating |
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