CN106917093A - Protection product enable its can anti-sulphates corrosive method and the product with improved Sulfate corrosion resistance - Google Patents
Protection product enable its can anti-sulphates corrosive method and the product with improved Sulfate corrosion resistance Download PDFInfo
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- CN106917093A CN106917093A CN201510982865.7A CN201510982865A CN106917093A CN 106917093 A CN106917093 A CN 106917093A CN 201510982865 A CN201510982865 A CN 201510982865A CN 106917093 A CN106917093 A CN 106917093A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/185—Refractory metal-containing compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/187—Mixtures of inorganic inhibitors
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- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention relates to it is a kind of protect product surface protect it from due at elevated temperatures be exposed to containing sulfate material caused by sulphate corrosion method; the surface coating corrosion-resistant material is included in, the corrosion-resistant material includes noble metal decorated oxide.Wherein, the oxide includes aluminum oxide, cerium oxide, the cerium oxide of doping, stabilized zirconia or combinations thereof.The invention further relates to a kind of product including corrosion-resistant coating, it is to because sulphate corrosion has improved resistance to corrosion caused by the material of containing sulfate at elevated temperatures.
Description
Technical field
Make the method for its anti-sulphates corrosive and a kind of tool this invention relates generally to a kind of protection product
There is the product of improved Sulfate corrosion resistance energy, in particular it relates to one kind enables product to resist be exposed to
The method of produced corrosion and this corrosion is resistant to during the material of the containing sulfate at elevated temperature
Product.
Background technology
In aviation and power industry, for the gold in fuel and material containing corrosive contaminants
For category component, heat erosion is a typical problem.Heat erosion be in the environment exist containing sodium, magnesium, potassium,
A kind of accelerated corrosion occurred in the case of the salt and sulfate of the elements such as calcium, vanadium and various halide.Heat
Corrosion may damage the oxide surface or oxide coating with protectiveness of hardware.Relatively
At temperature high, at such as greater than about 850 DEG C, the temperature that heat erosion occurs is higher than most of sulfate and letter
The fusing point of mono-salt.The sulfate and salt may form liquid deposition in element surface, and the liquid is heavy
Product may be by fusion mechanism (fluxing mechanism) corrosion element surface.So, the protection of element
Property oxide surface may occur melt (fluxing).At relatively low temperature, for example about
At 650-800 DEG C, sulfate may be by spot corrosion mechanism corrosion element surface.At relatively low temperature,
For example at about 650-800 DEG C, sulfate may be by spot corrosion mechanism corrosion element surface.Protected on surface
Vulcanization and oxidation reaction may be triggered at sheath existing defects, then partly spread and come, form spot corrosion.
Point corrosion pit may be produced with unpredictable speed, trigger crack and extend to the alloy substrate of element,
Cause sudden failure.Result reduces the bearing capacity of element and ultimately results in catastrophe failure.
The characteristics of industry is devoted to research heat erosion for a long time and principle, and continue to develop distinct methods
To mitigate heat erosion.But still solve heat erosion without ripe technology at present.Industry is for a long time all
The characteristics of being devoted to research heat erosion and principle, and continue to develop distinct methods and mitigate heat erosion.But mesh
It is preceding to solve heat erosion still without ripe technology.Concentrated particularly to most research so far
In the High Temperature Hot-corrosion Behaviorof that the fused salt with conductance high causes, but have no idea to be effectively reduced relatively low
Temperature, such as the heat erosion problem caused by spot corrosion at a temperature of 650-800 DEG C, and such temperature
It is probably very universal in operating condition in aviation and power industry.Accordingly, it would be desirable to develop new method
Such sulphate corrosion is prevented with material.
The content of the invention
On the one hand, a kind of surface for protecting product is protected it from due to being exposed to sulfur-bearing at elevated temperatures
The method of sulphate corrosion caused by the material of hydrochlorate, is included in the surface coating corrosion-resistant material,
The corrosion-resistant material includes noble metal decorated oxide.Wherein, the oxide includes aluminum oxide, oxygen
Change cerium, the cerium oxide of doping, stabilized zirconia or combinations thereof.
On the other hand, a kind of product, it is to the material due to being exposed to containing sulfate at elevated temperatures
Caused by sulphate corrosion there is improved resistance to corrosion.The product includes metallic matrix and described
Corrosion-resistant coating on metallic matrix, the coating includes aluminum oxide, cerium oxide, the cerium oxide of doping, steady
Surely zirconium oxide or combinations thereof are changed.
Brief description of the drawings
When reading described in detail below referring to the drawings, these and other features of the invention, aspect and excellent
Point will become better understood, and in the accompanying drawings, identical element numbers are used to represent identical in whole accompanying drawings
Part, wherein：
Fig. 1 shows that the measured material in example 1 is used to decompose the sulfur dioxide strength signal of sulfate generation
(arbitrary unit) relative to temperature function, for assessing the catalysis activity of the measured material in the example 1.
Fig. 2 shows that the measured material in example 2 (is appointed for decomposing the sulfur dioxide concentration of sulfate generation
Meaning unit) relative to the function of temperature, for assessing the catalysis activity of the measured material in the example 2.
Fig. 3 shows that the measured material in example 3 (is appointed for decomposing the sulfur dioxide concentration of sulfate generation
Meaning unit) relative to the function of temperature, for assessing the catalysis activity of the measured material in the example 3.
Fig. 4 A are the scanning electron microscope image of the cross section of sample 1, and Fig. 4 B are shown in Fig. 4 A
The component of marked region.
Fig. 5 A are the scanning electron microscope image of the cross section of sample 2, and Fig. 5 B are shown in Fig. 5 A
The component of marked region.
Fig. 6 A are the scanning electron microscope image of the cross section of sample 3, and Fig. 6 B are shown in Fig. 6 A
The component of marked region.
Fig. 7 A are the scanning electron microscope image of the cross section of sample 4, and Fig. 7 B are shown in Fig. 7 A
The component of marked region.
Fig. 8 A are the scanning electron microscope image of the cross section of sample 5, and Fig. 8 B are shown in Fig. 8 A
The component of marked region.
Fig. 9 A are the scanning electron microscope image of the cross section of sample 6, and Fig. 9 B are shown in Fig. 9 A
The component of marked region.
Figure 10 A are the scanning electron microscope image of the cross section of sample 7, and Figure 10 B show Figure 10 A
The component of middle marked region.
Figure 11 A are the scanning electron microscope image of the cross section of sample 8, and Figure 11 B show Figure 11 A
The component of middle marked region.
Figure 12 A are the scanning electron microscope image of the cross section of sample 9, and Figure 12 B show Figure 12 A
The component of middle marked region.
Specific embodiment
Unless otherwise defined, the technical term for using in the present specification and claims or section are academic
Language should be the ordinary meaning that the personage with general technical ability is understood in the technical field of the invention.This
" first " or " second " and similar word used in specification and claims are not offered as
Any order, quantity or importance, and be used only to distinguish different parts." one " or
The similar word such as " one " is not offered as quantity limitation, but expression has at least one.It is used herein
The language of approximation can be used for quantitative expression, show that number can be allowed in the case where basic function is not changed
Amount has certain variation.Therefore, the numerical value corrected with the language such as " about ", " left and right " is not limited to the standard
Exact figures value is in itself.Additionally, in the statement of " the about first numerical value to second value ", " about " is while amendment the
One numerical value and second value two values.In some cases, approximating language may be with measuring instrument
Precision is relevant.Numerical value mentioned in the present invention includes the increased institute of one unit of a unit from low to high
There is numerical value, it is assumed herein that being spaced Unit at least two between any lower value and high value.
The all of numerical value between minimum to peak enumerated herein, refers to when minimum and most
Differed when more than two units between high level, obtained by increment of a unit between minimum and peak
All numerical value.Such as, the quantity and the numerical value of process of the component being similar to as temperature, air pressure, time etc.
Deng when we say 1 to 90, reference is such as 15 to 85,22 to 68,43 to 51,30 to arrive
The similar enumerated value of 32 grades.When numerical value is less than 1, a unit can be 0.0001,0.001,0.01
Or 0.1.Merely just illustrated as particular examples.The numeral for including herein refers to use similar
The all possible combinations of values between a minimum value and a maximum value that method is obtained.
Embodiments of the invention are related to a kind of corrosion-resistant material, it can be used to generating electricity, aviation and other relate to
And the field of heat erosion environment, for protecting metallic article, such as element of gas turbine or engine,
In order to avoid it is by sulphate corrosion, so as to significantly improve the service life of these products.
The unique corrosion resistance of this corrosion-resistant material may be urged the height of sulphate decomposition in itself with material
Change performance is relevant, and this may change the interfacial interaction between corrosive agent and coating.In some implementations
In example, the corrosion-resistant material and the coating (being alternatively referred to as below " coating ") that is made up of the material are no
It is only capable of making sulphate decomposition, for example, in the temperature decomposed in itself less than sulfate, such as at about 750 DEG C
Make sulphate decomposition, it is also possible to by by sulfur trioxide (SO3) be converted to sulfur dioxide (SO2) hinder
Only SO3Or the generation of sulfate.Wherein, sulfate decomposable asymmetric choice net generates corresponding metal oxide, SO2
And oxygen:
2MSO4→2MO+2SO2+O2,
Wherein M represents a kind of metal.
By by SO3It is converted into SO2And oxygen, SO can be prevented3Or the generation of sulfate：
2SO3→2SO2+O2
Additionally, the corrosion-resistant material also has high chemical stability, it is in the material exposed to containing sulfate
It is also very stable during material (corrosive agent of containing sulfate), therefore can be used to provide a kind of multi-functional coatings use
In anticorrosive.
This corrosion-resistant material or coating include a kind of noble metal decorated oxide." your gold as herein described
Belong to the oxide of modification " refer to the oxide for being loaded with least one noble metal, wherein, at least one
The nanoscale or micron particles of noble metal are scattered in the oxide.Can allow described by any
Be incorporated into at least one noble metal described by the method that noble metal granule is scattered in the oxide
In oxide.The specific example of feasible method includes wet impregnation method and is co-mulled and made into method.In some embodiments
In, in oxide impregnated in into precious metal salt solution, noble metal is incorporated into oxide.
In some embodiments, mix and carry out ball milling together by by oxide particle and noble metal granule, will
Noble metal is introduced into oxide.
The oxide may include aluminum oxide (oxide of aluminium), cerium oxide (oxide of cerium), doping
Cerium oxide, stabilized zirconia or combinations thereof." stabilized zirconia " as herein described refers to one
Ceramic material is planted, wherein causing the crystal knot of zirconium oxide (oxide of zirconium) by the chemical substance added
Structure is stablized at room temperature.Some examples of the stabilized zirconia include the zirconium oxide of ceria stabilization
(CZO), the zirconium oxide (SSZ) of the zirconium oxide (YSZ) of stabilized with yttrium oxide and scandium stabilization.In some realities
Apply in example, the stabilized zirconia is CZO, its simplified expression is CeaZrbO2, wherein 1>a>0,
1>b>0, and a+b=1.In some specific embodiments, the oxide includes cerium oxide, doping oxygen
Change cerium, stabilized zirconia or combinations thereof.
" noble metal " as herein described refers to platinum family element, including platinum (Pt), palladium (Pd), osmium (Os),
Iridium (Ir), ruthenium (Ru) and rhodium (Rh).The noble metal of the modification oxide can provide for oxide or
Person improves its catalysis activity to sulphate decomposition.And because noble metal has good ductility, can
So that the pattern or mechanical performance of its oxide modified are improved.Therefore, the modification
The noble metal of oxide can be conducive to improving the catalysis activity and lifting corrosion-resistant material to sulphate decomposition
Physical property.
The catalysis activity that decomposition of these noble metal decorated oxides to sulfate has had, and its
It is also very stable when at elevated temperature exposed to the corrosive agent of containing sulfate and dust, therefore can be used to
The corrosion related to sulphur is prevented at a temperature of rising." elevated temperature " as herein described is commonly referred to as than just
Normal temperature temperature high, for example, higher than the temperature of room temperature.In certain embodiments." elevated temperature "
Refer in particular in generating, aviation or other running temperatures in being related to the field of heat erosion environment.For example, rising
Temperature high can refer to gas turbine or engine, such as running temperature of jet engine.It is specific at some
In embodiment, the elevated temperature can refer to the temperature higher than 500 DEG C.Especially, the elevated temperature
Spend the scope at about 500 DEG C to about 800 DEG C.
In certain embodiments, it is described modification oxide noble metal may include platinum (Pt), palladium (Pd),
Or combinations thereof.In certain embodiments, in the noble metal decorated oxide noble metal quality
Scope of the percentage composition about 0.01% to about 50%.In some specific embodiments, this model
Enclose is 0.01% to 15%.
In certain embodiments, the corrosion-resistant material or coating include a kind of noble metal decorated oxide,
Oxide therein includes cerium oxide, doped cerium oxide, stabilized zirconia or combinations thereof.And
And the corrosion-resistant material or coating still further comprise nickel oxide (NiO), aluminum oxide or combinations thereof,
As additive, for adjusting the thermal coefficient of expansion of material.The additive is relative to the anticorrosive material
The mass percent of material or coating is smaller than 50%.In some specific embodiments, the additive phase
For the scope of the mass percent about 10% to about 30% of the corrosion-resistant material or coating.
The embodiment of the present invention further relates to a kind of surface for protecting product and protects it from due in elevated temperature
Down caused by the material of containing sulfate sulphate corrosion method, it is included in the surface and applies
The corrosion-resistant material is covered, to form corrosion-resistant coating.
In certain embodiments, the corrosion-resistant material can directly be coated on the corruption needed in face of containing sulfate
Lose the surface (i.e. target surface) of agent.In certain embodiments, the corrosion-resistant material can be by a gold
Category or intermediate oxide layer, for example, such as tack coat of CoNiCrAlY, is coated with target surface.
Tack coat can improve the adhesive force of corrosion-resistant coating and matrix alloy.The corrosion-resistant material can be by each
Plant coating process or method is coated on target surface, for example spraying or sedimentation etc..In certain embodiments,
The corrosion-resistant material can be by hot-spraying technique (thermal spray process), water-laid film technique
(wet-chemical deposition process) or combinations thereof are coated on target surface.This paper institutes
" thermal spraying " stated refers to the material spraying that will melt (or heating) in a kind of coating side of body surface
Method." water-laid film " refers to the coating process based on liquid operation, before being related to apply liquid on matrix
Body layer is driven, then the precursor layer of the liquid is transformed into desired coating by subsequent treatment.Some are wet
The example of method film-forming process includes dip-coating method (dip coating methods), spin coating method (spin
Coating methods), spraying process (spray coating methods), mould cladding process (die coating
Methods), silk screen print method (screen printing methods).
In certain embodiments, before the corrosion-resistant material is coated into target surface, it can be entered
Row calcination processing, for example, being calcined at a temperature of about 400-1000 DEG C about 1-3 hours.In some implementations
In example, before target surface is applied to, also the corrosion-resistant material after the calcining can further be entered
Row sintering processes.For example, temperature that can be by the corrosion-resistant material after the calcining at about 1000-1300 DEG C
Lower sintering about 1-5 hours.Corrosion-resistant material after the sintered treatment can become more stable, can be more
The corrosion of the erosion of containing sulfate is resisted well.
Because sulfate is broken down into sulfur dioxide on the coating, can be driven with one or more method
Dissipate the sulfur dioxide that sulphate decomposition is produced.For example, sulfur dioxide can be dispersed with pressure air-flow.One
In a little embodiments, the above method can further include to disperse the sulfur dioxide produced on the coating.Example
Such as, the pressure air stream of 100sccm (standard state cc/min) is about by volume flow rate
To disperse sulfur dioxide.
Corrosion-resistant coating described herein has lasting sulfur resistance, can be resistance under for a long time in elevated temperature
By sulphate corrosion.For example, it can resist the corrosion at least 500 of sulphur at a temperature of higher than 500 DEG C
Hour.
Embodiments of the invention further relate to a kind of product with foregoing corrosion-resistant coating.The product can be wrapped
Include metallic matrix and the foregoing corrosion-resistant coating on the metallic matrix.The metallic matrix can be by any conjunction
Suitable metal or alloy is made, including but not limited to ferrous alloy, cobalt-base alloys, nickel-base alloy or it
Combination.The corrosion-resistant coating can have the commonly required suitable thickness of acquisition corrosion resistance.
In some embodiments, the thickness of the corrosion-resistant coating is about 1-200 microns.
Embodiments of the invention can be illustrated by referring to some non-limiting examples.Following example meanings
Figure is to elaborate on how to carry out the material and method described in claim to those skilled in the art
Assessment, its should not be taken as any angle for limitation of the invention.
Example one
In example one, commented by contrasting the catalysis activity of the oxide containing palladium (Pd) and without Pd
Pd is estimated as noble metal to the role of catalysis activity of sulphate decomposition.Tested in example 1 and contrasted
：Aluminum oxide (Al2O3) and Pd (5wt%) modification Al2O3.Tested in example 2 and contrasted
：With mass ratio 1:The CZO and Al of 10 mixing2O3Mixture (CZO-Al2O3Mixture), with
And the CZO-Al of Pd (5wt%) modifications2O3Mixture.Test and compared in example 3：Gadolinium
The GDC of cerium oxide (GDC) and Pd (10wt%) modification of doping.In the every of the example 1-3
In one example, measured material (is contained into the powder of 45wt% sulfate with the sulphate corrosion agent of simulation respectively
Dirt) with 1:1 mass ratio mixing, obtains mixture, and the mixture then is put into thermogravimetric analyzer
In (thermo-gravimetric analyzer, purchased from Mettler-Toledo companies, Switzerland), in flow velocity
In for the air stream of 80 ml/mins, it is heated to from about 100 DEG C with about 10 DEG C/min of firing rate
1000℃.(purchased from Hiden Analytical companies, irrigated with the mass spectrograph for being connected to the thermogravimetric analyzer
Spirit, Britain) come the sulfur dioxide of decomposition in the discharge gas for monitoring the thermogravimetric analyzer.It is relatively early to start
Producing the material of sulfur dioxide is considered as having stronger catalytic action to the decomposition of sulfate.
For the oxide that the Pd being tested in example 1-3 is modified, including the Al that Pd is modified2O3, Pd modification
CZO-Al2O3Mixture and the GDC of Pd modifications, are by with dense Pd (NO)3Solution impregnation
Be introduced into Pd in each oxide by the mode of each oxide.
Al in example 12O3The Al modified with Pd2O3It is respectively used to decompose the titanium dioxide produced during sulfate
Sulphur intensity is as shown in Figure 1 relative to the curve of temperature.CZO-Al in example 22O3Mixture and Pd are modified
CZO-Al2O3Mixture is respectively used to decompose the sulfur dioxide intensity produced during sulfate relative to temperature
Curve it is as shown in Figure 2.The GDC of GDC and the Pd modification in example 3 is respectively used to decompose sulfate
When the sulfur dioxide intensity that produces it is as shown in Figure 3 relative to the curve of temperature.Be can be seen that from Fig. 1-3
Pd can lift catalysis activity of the oxide to sulphate decomposition, with the corresponding oxidation modified without Pd
Thing is compared, and decomposition of the oxide that Pd is modified to sulfate has catalysis activity higher.
Example two
In example two, have various or without noble metal decorated oxide (Al2O3、CZO-Al2O3
Mixture, Ce0.15Zr0.85O2、CeO2And GDC) be tested and compare.The powder of these oxides
End is prepared respectively by procedure below：Using metal nitrate precursor, citric acid (as organic chelated
Agent) and triethylene glycol (as surfactant) be raw material, by sol-gel process be obtained precursor solution,
And the solution is dried on hot plate, then that at about 550 DEG C dried material is calcined into about 2 is small
When.For without noble metal decorated oxide, by the powder after roasting directly in cylinder pressing mold
Disk is shaped in (cylindrical pressing mold), then at a temperature of about 1200 DEG C, in sky
Sintered in gas about 2 to 4 hours.For there is noble metal decorated oxide, with including precious metal element
Dense saline solution, such as dense Pd (NO)3Or HPtCl8Solution impregnates the oxidate powder after the roasting
End, oxide is introduced by noble metal.After dipping, the mixture that will be obtained is stirred on hot plate
Dry, the material obtained after drying is then obtained into mixed-powder in about 550 DEG C of about 2 hours of roasting.
The mixed-powder is pressed into disk in cylinder pressing mold, then at a temperature of 1200 DEG C, is burnt in atmosphere
Knot about 2 to 4 hours.
In order to assess the resistance to corrosion of these materials, the disk to being made up of these materials respectively carries out mould
Intend corrosion test.In simulative corrosion test, by Na2SO4、K2SO4、MgSO4、CaSO4, dust
After the sintering being coated to the mixture of paste vehicle (paste vehicle) as sulphate corrosion agent
The surface of disk, is then maintained at the disk for being coated with sulphate corrosion agent one and is prone to corrosion
Test temperature under.After the simulative corrosion test, disk is cut, the Cross section polishing that will be cut is simultaneously
It is analyzed, to analyze the elements diffusion situation between disk and corrosive agent.Prevention sulphur is penetrated into disk
Ability be treated as weigh measured material Sulfate corrosion resistance can an index.Circle is penetrated into sulphur
The biggest quality percentage composition (S wt%) of sulphur in depth (sulphur penetration depth) and sulphur penetration depth in piece
To represent the performance of measured material anti-sulphates corrosive.
Specifically, Al is used respectively2O3, Pt modification Al2O3、CZO-Al2O3(mass ratio is mixture
1:10 Al2O3And Ce0.6Zr0.4O2Mixture), Pt modification the CZO-Al2O3Mixture,
Ce0.15Zr0.85O2, Pd modification Ce0.15Zr0.85O2, Pt modification Ce0.15Zr0.85O2, Pt modification CeO2
The GDC modified with Pt is prepared for nine disks.Then, about 100 are carried out at a temperature of about 704 DEG C
The aforementioned analog corrosion test of hour or 500 hours, obtains sample 1-9.For 9 described samples,
Wherein be used for prepare disk material, simulation corrosion condition (including test temperature and duration) and
Observed result (including sulphur penetration depth, S wt%) is as shown in the following chart.
As can be seen from the table, all of noble metal decorated oxide (sample 2,4 and 6-9) all shows
The ability for preventing sulphur from penetrating into disk is shown.Noble metal is served and lifted to the catalysis activity of sulphate decomposition
Effect.For example, in 704 DEG C, the simulation corrosion of 100 hours, Al2O3Can be penetrated into by sulphur, but Pt is repaiied
Decorations Al2O3But the infiltration of sulphur can be prevented.In 704 DEG C, the simulation corrosion of 100 hours, CZO-Al2O3
Mixture can be penetrated into by sulphur, but the CZO-Al that Pt is modified2O3Mixture can but prevent the infiltration of sulphur.
704 DEG C, in the corrosion of the simulation of 500 hours, Ce0.15Zr0.85O2Can be penetrated into (although Siemers exists by sulphur
U.S.Pat.No.4, says that CZO can resist the corrosion of molten sulfate in 328,285, but it is actually
Can not be in longer time, for example, the corrosion of resistance sulfate in 500 hours), but Pt or Pd repair
The Ce of decorations0.15Zr0.85O2But the infiltration of sulphur can be prevented.
In order to observe this 9 microscopic appearances of sample, this 9 scanning electrons in the section of sample are obtained
Microscope (SEM) image, is shown in Fig. 4 A, 5A ... 12A.Additionally, in order to further
The spread condition across disk surfaces (interface i.e. between measured material and corrosive agent) in each sample is analyzed,
(EDX) is analyzed by X-ray energy spectrum and has measured sample area (mark in each sample near disk surfaces
Remember in the SEM image of each sample) mass percent composition.The composition difference measured in sample 1-9
As shown in Fig. 4 B, 5B ... 12B.
For example, the sample 1 for SEM image as shown in Figure 4 A, has measured four tab areas, i.e.,
The mass percent of spectral regions 11-14 (spectrums 11-14) is constituted and is shown in Fig. 4 B.Specifically
For, spectral regions 11-14 along a direction for being basically perpendicular to bead surface, from measured material side
(i.e. disk side) is arranged in order to the order of corrosive agent side, and wherein spectral regions 11 and 12 are located at tested
Material side, spectral regions 13 and 14 are located at corrosive agent side.For remaining sample 2-9, also use similar
Method measure and show four tab areas (two in measured material side, two in corrosive agent one
Side；Or four all in measured material side) mass percent composition.
Your gold the table shown in the SEM image and Fig. 4 B-12B that are shown in Fig. 4 A-12A all demonstrates
The oxide (sample 2,4 and 6-9) for belonging to modification can prevent sulphur from penetrating into disk, and it is applied to alloy table
Face can prevent heat erosion.Fig. 5 A, 7A, 9A, 10A, 11A and 12A (correspondence sample 2,4 and 6-9)
A clean disk cross-sectional image is respectively shown, not across the cross staining of disk surfaces.Fig. 4 B-12B
Show there is the infiltration of sulphur in without noble metal decorated oxide (sample 1,3 and 5), but
Having in noble metal decorated oxide (sample 2,4 and 6-9) does not have the infiltration of sulphur.
This specification describes invention, including optimal mode with specific embodiment, and can help any
The people for being familiar with present invention process carries out experimental implementation.These operation include use any device and system and
Use the method for any materialization.The scope of the claims of the invention is defined by claims, and may be wrapped
Include example of other generations in the art.If described other examples in structure with claims
Written language without difference, or they have with claims describe suitable structure, all by
It is considered in the scope of claim of the invention.
Claims (10)
1. a kind of surface for protecting product is protected it from due to being exposed to containing sulfate at elevated temperatures
Material caused by sulphate corrosion, be included in surface coating corrosion-resistant material, the anticorrosive material
Material includes noble metal decorated oxide, wherein, the oxide includes aluminum oxide, cerium oxide, doping
Cerium oxide, stabilized zirconia or combinations thereof.
2. noble metal in the method for claim 1, wherein described noble metal decorated oxide
Scope of the weight/mass percentage composition 0.01% to 15%.
3. the method for claim 1, wherein the noble metal includes platinum, palladium or their group
Close.
4. the method for claim 1, wherein the oxide include cerium oxide, doping cerium oxide,
Stabilized zirconia or combinations thereof.
5. method as claimed in claim 4, wherein, the corrosion-resistant material further includes additive, should
Additive includes nickel oxide, aluminum oxide or their combination.
6. method as claimed in claim 5, wherein, matter of the additive relative to the corrosion-resistant material
Amount percentage is less than 50%.
7. method as claimed in claim 6, wherein, matter of the additive relative to the corrosion-resistant material
Scope of the amount percentage 10% to 30%.
8. the method for claim 1, wherein the corrosion-resistant material be by hot-spraying technique,
Water-laid film technique or combinations thereof are coated to the surface.
9. a kind of product, it to due to being exposed to sulfuric acid caused by the material of containing sulfate at elevated temperatures
Salt corrosion has improved resistance to corrosion, and the product includes：
Metallic matrix；And
Corrosion-resistant coating on the metallic matrix, the corrosion-resistant coating includes noble metal decorated oxide,
Wherein, the oxide include aluminum oxide, cerium oxide, doping cerium oxide, stabilized zirconia or
Person's combinations thereof.
10. product as claimed in claim 9, wherein, the oxide include cerium oxide, the cerium oxide of doping,
Stabilized zirconia or combinations thereof.
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| CN116265130A (en) * | 2021-12-17 | 2023-06-20 | 通用电气公司 | Corrosion resistant material and method of application |
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