CN1291070C - Thermal growth Cr203 film type M Cr nano composite plating and producing process and application - Google Patents
Thermal growth Cr203 film type M Cr nano composite plating and producing process and application Download PDFInfo
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- CN1291070C CN1291070C CN 200410069556 CN200410069556A CN1291070C CN 1291070 C CN1291070 C CN 1291070C CN 200410069556 CN200410069556 CN 200410069556 CN 200410069556 A CN200410069556 A CN 200410069556A CN 1291070 C CN1291070 C CN 1291070C
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- 238000007747 plating Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title abstract description 9
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- 239000011253 protective coating Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 2
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- 229910002544 Fe-Cr Inorganic materials 0.000 abstract description 6
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 abstract description 6
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Abstract
The present invention discloses thermal growth Cr203 film type M-Cr nano composite plating, a preparing method and applications. The composite plating is composed of M plating of nanocrystals and nano metal Cr particles; the nano metal Cr particles are dispersed and distributed in the M plating, wherein M represents Ni, Fe or Co; measured by mass percent, Cr is nano particles, the minimum content of Cr can be from 7.3 to 13%, and the maximum content can be maximum compound quantity; at present, the Cr content can be 25%, and the rest is M. The preparation method comprises the following steps: the metal Ni, Fe or Co, and carbon steel or low alloy steel are used as base materials; a composite electroplating technique is adopted on the base materials to coelectrodeposit the metal M and the Cr plating, and Ni-Cr, Fe-Cr or Co-Cr nano composite plating is manufactured. The present invention has the advantages of simple and mature technology, easy popularization, and low cost for production and maintenance; the present invention has the characteristics of high compound quantity, controllable ingredient, compact plating, no need for vacuum diffusion treatment of nano composite plating, favorable hardness and good wear resisting properties; a protective Cr2O3 oxidation film can directly and thermally grow on the plating at high temperature.
Description
Technical field
The present invention relates to coating technology, specifically a kind of heat growth Cr
2O
3Membranous type M-Cr (M=Ni, Fe, Co) nano-composite plate and preparation method and application.
Background technology
The composite deposite for preparing oxidation-resistance with metal M (common Ni) and metal powder is reported to some extent.Its ultimate principle is by composite electric plating method, with metal powder and M coelectrodeposition, forms M-metal powder type composite deposite.Since under hot environment, the Cr of heat growth
2O
3Have protective value, so the Cr powder was suggested once as powder stock and M coelectrodeposition and prepared composite deposite, in the hope of forming Cr when the high-temperature oxydation
2O
3Protective oxide film.But progress in this respect is little at present, and the report of success is not also arranged at present, and its key factor is that added metal powder alloy powder is micron-sized.The composite deposite of the metal that this usefulness is traditional-micron order metallic particles coelectrodeposition preparation has the following disadvantages: (1) Cr distribution of particles is inhomogeneous, and compound quantity does not reach formation protectiveness Cr
2O
3The critical value that oxide-film is required, (2) porosity height.
Summary of the invention
For these deficiencies, the object of the invention be to provide a kind of porosity low, can direct heat growth Cr in hot environment
2O
3M-Cr nano-composite plate and the preparation method and application of membranous type.
Technical scheme of the present invention is as follows:
Heat growth Cr
2O
3The M-Cr nano-composite plate of membranous type, its composition is the nanocrystalline metal M of deposition and the combination of Cr nano particle, and wherein M can be Ni, Fe or Co, and the present invention adopts the Cr powder of nano-scale, can form continuous protectiveness Cr
2O
3The minimum Cr content (critical content) of the corresponding composite deposite of film by mass percentage, is 7.3～13%, and surplus is M, and high-load is all 25% (present maximum compound quantity), and surplus is M; The CeO that also can add trace (quality of coating 0.5～3%)
2, Y
2O
3, La
2O
3Or Gd
2O
3Rare earth oxide particles.
Its preparation method is with metal Ni, Fe, Co, the metallic substance of resistance to high temperature corrosion performance differences such as carbon steel or low alloy steel is a base material, realize the coelectrodeposition of M and nanometer Cr powder, preparation metal M-Cr type nano-composite plate, i.e. Ni-Cr, Fe-Cr or Co-Cr nano-composite plate; By mass percentage, the content of Cr be 7.3～25%, surplus is M; Plating bath is sulfate system (MSO
4).
When coelectrodeposition, can in plating bath, add in addition the trace rare earth oxides particle, this rare earth oxide enters in the coating, is expected further to improve the Cr of coating growth
2O
3The antioxygenic property of film; Rare earth oxide particles can be CeO
2, Y
2O
3, La
2O
3Or Gd
2O
3Deng; Described trace is 0.5～3% of quality of coating; Keep nano particle to be suspended in the tank liquor during plating; It is conventional equipment that the present invention prepares the used various composite plating equipment of above-mentioned nano-composite plate.
The M-Cr nano-composite plate of the present invention's preparation, wherein: under 800～900 ℃ of high temperature, guarantee the continuous protectiveness Cr of heat growth
2O
3Oxide-film.Cr grows under the high temperature
2O
3The oxide-film basic principle is as follows: because nanometer Cr powder of the present invention is evenly distributed in the nanocrystalline M coating, the metal M that obtains-Cr nano-composite plate is compared with the composite deposite of the micron-sized Cr that contains same amount, has greatly improved the particle number of Cr in the unit are.These particles can be used as Cr at the oxidation initial stage
2O
3The nucleating center, thereby greatly improved Cr in the unit are
2O
3Number of nuclei; Simultaneously, the nano powder on inferior top layer can be used as " source " of Cr, and it dissolves fast and diffuses to the surface, because after the coating nanometer, the Cr of coating inside can rapidly along the Grain-Boundary Phase diffusion into the surface, impel established Cr
2O
3The continuous Cr that examines Fast Growth and form
2O
3Film causes the nucleation and growth of the oxide of coated metal base to be suppressed, thereby prevents from peeling off oxidation, raising oxidation susceptibility.Rare earth oxide further improves the antioxygenic property of oxide-film, is mainly manifested in: 1) reduce Cr
2O
3The speed of growth of film; 2) improve Cr
2O
3Film is to the adhesiveness of coating matrix.
Compare with traditional composite deposite with metal-micron order metal powder preparation, advantage of the present invention and positively effect are as follows:
1. can form Cr
2O
3Protective oxide film.The present invention is by Nano metal powder, and adopts the nano-composite plate of the method preparation of metal-metal nano particle coelectrodeposition, has 1) compounding quantity height and the controllable component of Cr; 2) coating densification; 3) nano-composite plate does not need by high-temperature vacuum diffusion and pressure treatment, and coating such as directly can use at characteristics, particularly in air 800～900 ℃ shown good antioxidant property.
2. improved coating performance greatly.Compare with metal Ni in the prior art and single Ni coating; the raising of the relevant performance of composite deposite of the present invention (take metal Ni-Cr nano-composite plate by example) shows: as long as compound nanometer Cr powder is in corresponding content range, nano-composite plate just can the continuous protectiveness Cr of heat growth
2O
3Film, thus make the raising of the coating high temperature oxidation resistance order of magnitude.For example: during oxidation, compare with Ni base material and single Ni coating in 900 ℃ of air, the oxidation rate of Ni-Cr nano-composite plate can be hanged down respectively 40 times and nearly 60 times.
3. technology is simple, ripe, cost is low: because plating is ripe technology, utilize existing electroplating device, add the nanometer Cr powder of aequum in tank liquor, just can be made into this novel nano composite deposite, do not need other too much investment.
4. applied widely.Since nano-composite plate of the present invention in air 800～900 ℃ shown good antioxygenic property, therefore, adopt the alternative diffusion chromizing coating of the present invention (chromium compounds coating) or with other technology preparation at the said temperature scope internal heat Cr that grows
2O
3The protective coating of membranous type can also be used for carbon steel, the high temperature protection of low-alloy steel.
Description of drawings
Fig. 1 is the surface topography of Ni-9.6Cr (mass percent, the as follows) nano-composite plate of one embodiment of the invention.
The XRD analysis comparison diagram of the nanometer Cr powder of Fig. 2 one embodiment of the invention, Ni coating and Ni-9.6Cr coating.
Fig. 3 is transmission electron microscope (TEM) bright field image of the Ni-9.6Cr nano-composite plate of one embodiment of the invention.
Fig. 4-1 for the nano-deposit of the nanometer Cr powder of the compound different size of the present invention at 800 ℃ of growth Cr
2O
3The content range of film;
Fig. 4-2 for the nano-deposit of the nanometer Cr powder of the compound different size of the present invention at 900 ℃ of growth Cr
2O
3The content range of film.
Fig. 5 is the oxidation kinetics comparison diagram that exposes 24h in 900 ℃ of air of one embodiment of the invention.
Fig. 6-1 is the zone of oxidation surface topography comparison diagram (the NiO zone of oxidation of growing on the Ni base) behind the exposure 24h in 900 ℃ of air of one embodiment of the invention.
Fig. 6-2 is the zone of oxidation surface topography comparison diagram (the NiO zone of oxidation of growing on the Ni coating) behind the exposure 24h in 900 ℃ of air of one embodiment of the invention.
Fig. 6-3 is the oxide layer surface topography comparison diagram (Cr that grows on the Ni-Cr nano-composite plate behind the exposure 24h in 900 ℃ of air of one embodiment of the invention
2O
3Oxide layer).
Fig. 7 is the XRD analysis comparison diagram as a result that exposes the zone of oxidation behind the 24h in 900 ℃ of air of one embodiment of the invention.
Fig. 8-1 is for exposing the zone of oxidation cross section pattern comparison diagram (the NiO zone of oxidation of growing on the Ni base) of 24h in 900 ℃ of air of one embodiment of the invention.
Fig. 8-2 is for exposing the zone of oxidation cross section pattern comparison diagram (the NiO zone of oxidation of growing on the Ni coating) of 24h in 900 ℃ of air of one embodiment of the invention.
Fig. 8-3 is for exposing the oxide layer Cross Section Morphology comparison diagram (Cr that grows on the nano-composite plate of 24h in 900 ℃ of air of one embodiment of the invention
2O
3Oxide layer).
Fig. 9 contains for one of the present invention and does not contain CeO
2Expose the oxidation kinetics comparison diagram of 24h in 900 ℃ of air of nano-composite plate embodiment.
Figure 10 is one embodiment of the invention Ni-11Cr-0.9CeO
2Expose the oxide layer surface topography (Cr that grows on the Ni-Cr nano-composite plate of 24h in 900 ℃ of air of nano-composite plate
2O
3Oxide layer)
Figure 11 is one embodiment of the invention Ni-11Cr-0.9CeO
2Expose the zone of oxidation cross section pattern of 24h in 900 ℃ of air of nano-composite plate
Figure 12 contains for one of the present invention and does not contain CeO
2900 ℃ of air of Ni-10.9Cr nano-composite plate embodiment in expose the cyclic oxidation kinetics comparison diagram of 120h.
Figure 13-1 is one embodiment of the invention Ni-11Cr-0.9CeO
2In 900 ℃ of air of nano-composite plate cyclic oxidation 120h the zone of oxidation surface topography.
Figure 13-2 be in 900 ℃ of air of one embodiment of the invention Ni-10.9Cr nano-composite plate cyclic oxidation 120h the zone of oxidation surface topography.
Figure 14-1 is one embodiment of the invention Ni-11Cr-0.9CeO
2In 900 ℃ of air of nano-composite plate cyclic oxidation 120h zone of oxidation cross section pattern.
Figure 14-2 be in 900 ℃ of air of one embodiment of the invention Ni-10.9Cr nano-composite plate cyclic oxidation 120h zone of oxidation cross section pattern.
Figure 15 is that the microhardness of base material Ni, Ni coating and the Ni-9.6Cr coating of one embodiment of the invention is analyzed comparison diagram.
Figure 16 is that the wear resistance of base material Ni, Ni coating and the Ni-9.6Cr coating of one embodiment of the invention is analyzed comparison diagram.
Embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Present embodiment is introduced the preparation and the performance (Fe-Cr and Co-Cr nano-composite plate are little in preparation and aspect of performance difference) of Ni-Cr nano-composite plate, and its preparation method is to adopt conventional coelectrodeposition (being composite plating) technology to prepare Ni-Cr, Fe-Cr or Co-Cr nano-composite plate; Plating bath is above-mentioned sulfate system (MSO commonly used
4), the Cr powder is a nano-scale.Present embodiment will with the preparation of Ni-Cr nano-composite plate and as a result example elaborate, the nanometer Cr powder particle mean size of employing is 20,39 and 80nm.
Present embodiment prepares Ni-Cr nano-composite plate flow process:
Substrate metal Ni (but also Fe, Co, carbon steel or low alloy steel is a base material)-surface finish is to 800# waterproof abrasive paper-surperficial ultrasonic cleaning-carry out in containing the plating Ni tank liquor of nanometer Cr powder coelectrodeposition-acquisition Ni-Cr nano-composite plate.The preparation key of nano-deposit of the present invention is to keep nano particle to be suspended in the tank liquor when electroplating, and present embodiment prepares with reciprocating machine stirring composite plating facility up and down.Specific as follows:
The electrolysis Ni plate of getting purity 99.96% is a base material, is processed into the small sample of 15 * 10 * 2mm size, is milled to 800 through silicon carbide paper
#, ultrasonic cleaning in acetone;
The nanometer Cr powder that the mean particle size that adopts is respectively 20nm, 39nm and 80nm is immersed in the sodium dodecyl sulfate solution earlier, so that the dispersion of nano particle is avoided reuniting;
Electroplate liquid adopts the low temperature modification plating bath, and composition is as follows: NiSO
4.7H
2O 150g/l, NH
4Cl 15g/l, H
3BO
315g/l, C
12H
25NaO
4S 0.1g/l; The solution of preparation is placed 24h through fully stirring after-filtration; The solution pH value can use (present embodiment can be 5.5) in the 5.4-6.0 scope.
Adopt plate pump formula device to stir plating bath in the electrodeposition process, to guarantee the suspension of nano particle in the plating bath, uniform deposition is at specimen surface; Bath temperature is 30 ℃, current density I=3A/dm
2, mixing speed is 110rpm.Electroplating time is 2h, and sample mean thickness is 50 μ m.
The compounding quantity of the nanometer Cr powder in the coating increases with the increase of Cr in the plating bath.Utilize this experimental technique, maximum Cr compound quantity is found with Cr change in size relation not quite in the 20-80nm scope that the present invention adopts, and its value is 25% (mass percent meter, lower with).
Introducing the The Nomenclature Composition and Structure of Complexes feature of nano-composite plate below, is that 39nm is example (feature of the nano-composite plate of compound other size is similar) with compound Cr particle mean sizes.Fig. 1 is the surface topography of the Ni-9.6Cr nano-composite plate of acquisition.Show by energy spectrum analysis: the shape particle that looses is rich Cr nano particle, and the particle that white is island is a Ni bag Cr structure.The grain-size of nanometer Cr powder, single Ni coating and Ni-9.6Cr composite deposite is by XRD determining, and the result as shown in Figure 2.Wherein, a is the XRD diffractogram of nanometer Cr powder, and the average grain size that is calculated by Scherrer according to the peak width at half height of the diffraction peak that obtains is 39nm; B is the XRD diffractogram of single Ni coating, and average grain size is 42nm; C is the XRD diffractogram of composite deposite, and recording coating is the Ni crystal grain of 31nm and the Cr granulometric composition that mean particle size is 39nm by mean sizes.Fig. 3 is that (the Cr nano particle is distributed in the nanocrystalline Ni base Ni-9.6%Cr composite deposite for the microstructure under the transmission electron microscope, visible coating densification, and particle and Ni base interface tight or crackle produce.
Present embodiment defines the nanometer Cr powder of compound different size, and continuous Cr can grow
2O
3The content range of oxide-film.
The dash area of Fig. 4-1 and Fig. 4-2 is respectively 800 ℃ and 900 ℃ of lower nano-composite plates Cr that can grow
2O
3The Cr content range of film.As seen from the figure, the lower limit of the compound Cr of institute particle and minimum content (also being critical content) not only have relation with institute composite particles size, also with envrionment temperature relation are arranged.For example, when institute's composite particles mean sizes was 20nm, 29nm and 80nm, critical content required in the time of 800 ℃ was respectively 7.3%, 9.6% and 11.2% in mass percent, and corresponding value becomes 7.5%, 10.9% and 13% in the time of 900 ℃.Presentation of results reduces with the composite nanoparticle size, growth Cr
2O
3The required critical Cr content of film increases; When one timing of institute's composite nanoparticle size, raise with environment temperature, corresponding critical content also increases.Here be noted that, the upper limit that Fig. 4-1 and Fig. 4-2 provides (high-load) by among the present invention the compound maximum level of energy, according to aforesaid design theory of the present invention basis, if compound quantity can further improve, this nano-composite plate Cr that can grow fully
2O
3Film, and the service life that might further improve coating.
Fig. 5 is the Ni matrix, single Ni coating, and the Ni-10.9Cr nano-composite plate is at 24 hours oxidation kinetics curve of 900 ℃ of oxidations.On scheming, can see that the nano oxidized speed of Ni-10.9Cr sharply reduces.Three kinds of oxidation para-curve constants that sample calculated are respectively 6.9 * 10
-11, 9.7 * 10
-11, 1.7 * 10
-12g
2/ cm
4.s.Wherein, the oxidation rate of nano-composite plate is lower 40 times than Ni base material, near Cr
2O
3Hot growth rate.Fig. 6 is corresponding zone of oxidation surface topography picture.As seen, at the NiO that is all coarse grains of single Ni coating (Fig. 6-1) and base material Ni (Fig. 6-2) growth, and oxide (Fig. 6-3) crystal grain of growing at nano-composite plate is tiny, is typical Cr
2O
3The film feature.The above results also can be confirmed from corresponding XRD analysis result (Fig. 7) and zone of oxidation cross section pattern (Fig. 8-1, Fig. 8-2).Among Fig. 7, a shows that not adding the oxidation of Cr powder Ni coating forms the NiO oxide layer; B shows that the oxide layer of Ni-Cr nano-composite plate is mainly by Cr
2O
3Form, wherein contain a small amount of NiO and NiCr
2O
4Can find out from Fig. 8-1, Fig. 8-2, after the 24h oxidation the growth of Ni base material (referring to Fig. 8-1) and Ni coating (referring to Fig. 8-2) be the NiO oxide layer, and grow thin and uniform Cr at Ni-10.9Cr nano-composite plate (referring to Fig. 8-3)
2O
3Oxide layer.
As everyone knows, rare earth oxide can obviously improve the antioxidant property of metal.The present invention finds to add 0.5～3% CeO
2, Y
2O
3, La
2O
3Or Gd
2O
3Oxide layer to nano-composite plate is useful to the adhesiveness of matrix.Present embodiment is with CeO
2Example, difference from Example 3 is: add a certain amount of CeO in nano-composite plate
2Embodiment 4 is not to contain CeO
2The Ni-Cr nano-composite plate close with the Cr compounding quantity and contain CeO
2The nano-composite plate oxidation susceptibility contrast.
Fig. 9 is the CeO of 0.9mass% for the Ni-11Cr nano-composite plate adds quality
2With do not contain CeO
2But the oxidation kinetics curve ratio of the Ni-10.9Cr nano-composite plate that Cr content is close.As seen, the rate of oxidation behind the interpolation rare earth oxide is compared with the rate of oxidation that does not contain rare earth oxide, slightly reduce, but difference is not obvious.Oxide layer surface topography (seeing Figure 10) and the Cross Section Morphology (seeing Figure 11) of growing after the corresponding 24h oxidation can see, do not contain the thin and even compact of growth in the oxide layer of rare earth oxide Cr
2O
3Oxide layer is compared with Cross Section Morphology (seeing Fig. 8-3) with the oxide layer surface of growing under identical oxidizing condition (seeing Fig. 6-3) of Ni-10.9Cr nano-composite plate, is more or less the same.
Figure 12 is changes in weight situation (the each circulation: oxidation 1h+ air cooling 30min) of cyclic oxidation 120h in 900 ℃ of air of several nano-composite plates.Wherein, Ni-11Cr-0.9CeO
2Compare with single plating Ni coating with the anti-cyclic oxidation performance of Ni-10.9Cr nano-composite plate and to significantly improve; Compare the Ni-11Cr-CeO that Cr content is close with the Ni-10.9Cr nano-composite plate
2The composite deposite antioxidant property omits, but effect is not clearly.Can find out that from Figure 13-1 and the corresponding sample surface morphology of 13-2 these two kinds of nano-composite plate surface topographies are more or less the same, all give birth to continuous Cr
2O
3Film.Show pattern from corresponding oxide layer, Ni-11Cr-0.9CeO
2The corresponding oxide layer Cross Section Morphology feature of (seeing Figure 14-1) and Ni-10.9Cr nano-composite plate (seeing Figure 14-2) can find out that also thin and fine and close Cr both grows
2O
3Oxide-film.Therefore, in Fig. 4-1 and Fig. 4-2 dash area Cr content range, add rare earth oxide the nano-composite plate oxidation susceptibility is made moderate progress, but its effect not clearly.
Here to point out, no matter oxidizing temperature is 800 ℃ or 900 ℃, as long as the content of the nanometer Cr powder of different size is in the shadow region of Fig. 4-1 and Fig. 4-1, the nano-composite plate Cr that just can grow
2O
3Film, the Oxidation Law of 800 ℃ of nano-composite plates (comprise and contain rare earth oxide) and characteristic and 900 ℃ are more or less the same, just Cr in the time of 800 ℃
2O
3The speed of growth of film is slower than 900 ℃, and for this reason, 800 ℃ oxidation is described in detail no longer one by one.
Consider at the more medium military service materials of Industrial Boiler, not only be subjected to the influence of high temperature oxidation, influenced by erosion or abrasive simultaneously.For this reason, the hardness of present embodiment nano-composite plate and wear resisting property data are as a supplement.
Experiment of hardness:
Adopt DATALETTY 150 microhardness machines, carry out the microhardness experiment at matrix and coating surface through polishing.Experiment load is chosen 15g deadweight counterweight, and the load time is 5 seconds.Each specimen surface keeps at a certain distance away and measures 4 points, gets its mean value, obtains comparative microhardness experimental result, as shown in figure 15.As seen, compare with metal Ni and single Ni coating, the microhardness of Ni-Cr nano-composite plate can improve respectively more than 2.5 and 2 times.
Wear test:
Adopt the reciprocating type sliding friction wear test of MT8-002 type machine to carry out the wear resistance experiment.Experiment condition is dry friction, carries out in the air at room temperature.Friction pair is selected the GCr15 steel ball of φ 6mm for use, and load is chosen 180g, and the reciprocation cycle number of times is 6000 times, and stroke is 23mm, and the slippage distance is 138m.The experiment front and back are 10 with sensibility reciprocal
-4The Sartorius analytical balance of g is weighed to the sample before and after the wearing and tearing, and calculates abrasion loss with this, and experimental result is compared with metal Ni and single Ni coating, and wear resistance can improve respectively more than 4 and 3 times.Figure 16 is that the wear resistance of base material Ni, Ni coating and Ni-9.6Cr coating is analyzed comparison diagram.
Can be found out that by top result the mechanical performances such as the hardness of nano-composite plate of the present invention and wearability also obtain very big raising.
As from the foregoing, the nano-composite plate of the present invention's preparation is made up of Ni base and the Cr nano metal particles that contains dispersed therein of nanometer structure, and it produces significantly " nano effect " in high-temperature oxydation or corrosive environment, can Fast Growth protectiveness Cr
2O
3The mechanism that produces " nano effect " can be expressed as follows: on the one hand, the compound Ni of entering base coating and the Cr particle that contains dispersed therein can be used as seed, growth Cr when oxidation
2O
3When the metallic compound quantity is certain, the particle of composite Nano size can greatly improve the population (compare with micron order, two more than the order of magnitude) that distributes in the unit are, namely increases the density of seed in the unit are, reduces Cr
2O
3Internuclear spacing, thus reduce the required time of dinuclear healing, also namely shorten protective oxide film healing required time.On the other hand, have highdensity crystal boundary in the coating of nanometer structure, they can serve as the rapid diffusion passage of Cr, further impel the rapid transverse growth of above-mentioned nascent oxide core, form the successive protective oxide layer in very short transient state oxidising process.According to this principle, can infer: when nanometer Cr particle size one timing of adding, as long as compound quantity reaches a critical value and above value thereof, nano-composite plate of the present invention is the hot continuous protectiveness Cr that grows of energy just
2O
3Oxide-film; And when the Cr particle size that adds is more little, form continuous Cr
2O
3The content of film will decrease (littler than 7.3% value).This deduction can fully be verified by example of the present invention.The present invention has provided by compound different size Cr particle preparation growth protecting Cr
2O
3The corresponding Cr content range that the composite deposite of film needs.
Fe, Co are the same with Ni to be the main matrix element of high temperature metallic material commonly used.Because the basic principle of nano-composite plate Fe-Cr, Co-Cr is identical with the preparation of Ni-Cr, and according to the oxidation behaviors of this composite deposite, protectiveness Cr
2O
3Growth only relevant with the structure (crystallite dimension) of size, compound quantity and the matrix element of nano particle, and do not have direct relation with the matrix pivot.Therefore, select the electrolyte of plating Fe or plating Co, adopt the experimental technique identical with preparation Ni-Cr nano-composite plate, can prepare respectively heat growth Cr
2O
3The Fe-Cr of membranous type, Co-Cr and nano composite plating coating systems.Because the preparation scheme roughly the same, and anti-oxidation characteristics is similar, does not do at this and repeats.When coelectrodeposition, can also in plating bath, add in addition Y
2O
3, La
2O
3Or Gd
2O
3Deng rare earth oxide particles.Because of they impact and CeO to the nano-composite plate antioxygen property in oxidizing process
2Similar, say so also no longer go to live in the household of one's in-laws on getting married here.
Ni-Cr nano-composite plate of the present invention can be used as the protective coating of resistance to high temperature oxidation (or corrosion), is used for the relatively poor steel of antioxidant property below 900 ℃ and 900 ℃, for example, and anti-oxidant (or corrosion) coating of metal Ni, Co, Fe etc.And this nano-composite plate is expected to be used for the protective coating at the pipeline made from carbon steel and low alloy steel below 900 ℃ (for example water wall tube, generating tube, heat transfer tube etc.) of associated components envrionment temperature in coal firing boiler, vapourizing furnace, the incinerator.
Claims (9)
1. heat growth Cr
2O
3Membranous type M-Cr nano-composite plate is characterized in that: coating is made up of nanocrystalline M coating and nano metal Cr particle dispersed therein, i.e. M-Cr, wherein M can be Ni, Fe or Co, by mass percentage, the content of Cr is 7.3～25%, and surplus is M.
2. by the described heat growth of claim 1 Cr
2O
3Membranous type M-Cr nano-composite plate is characterized in that: by mass percentage, also can add 0.5～3% CeO of quality of coating
2, Y
2O
3, La
2O
3Or Gd
2O
3Rare earth oxide particles.
3. heat growth Cr
2O
3The preparation method of membranous type M-Cr nano-composite plate, it is characterized in that: with metal Ni, Fe or Co, carbon steel or low alloy steel is base material, adopt composite plating technology coelectrodeposition nano-composite plate at base material, it is made up of nanocrystalline metal M primitive and nanodispersion of particles Cr, and wherein: M can be Ni, Fe or Co, by mass percentage, the content of Cr is 7.3～25%, and surplus is M.
4. by the described heat growth of claim 3 Cr
2O
3The preparation method of membranous type M-Cr nano-composite plate is characterized in that: the continuous protectiveness Cr of control heat growth under 800～900 ℃ of high temperature
2O
3Oxide-film.
5. by the described heat growth of claim 3 Cr
2O
3The preparation method of membranous type M-Cr nano-composite plate is characterized in that: keep nano particle to be suspended in the tank liquor during plating.
6. by claim 3,4 or 5 described heat growth Cr
2O
3The preparation method of membranous type M-Cr nano-composite plate is characterized in that: when coelectrodeposition, can add in addition the trace rare earth oxides particle in plating bath.
7. by the described heat growth of claim 6 Cr
2O
3The preparation method of membranous type M-Cr nano-composite plate is characterized in that: rare earth oxide particles is CeO
2, Y
2O
3, La
2O
3Or Gd
2O
3
8. by the described heat growth of claim 6 Cr
2O
3The preparation method of membranous type M-Cr nano-composite plate is characterized in that: described trace is 0.5～3% of quality of coating.
9. press the described heat growth of claim 1 Cr for one kind
2O
3The application of membranous type M-Cr nano-composite plate, it is characterized in that: described nano-composite plate can be used as the protective coating of resistance to high temperature oxidation or corrosion, and metal Ni, Co, Fe is anti-oxidant or corrosion resistant coating, and the associated components environment temperature is at the protective coating of the pipeline made from carbon steel and low alloy steel below 900 ℃ in coal-burning boiler, gasification furnace, the incinerator.
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| CN100445430C (en) * | 2004-12-03 | 2008-12-24 | 中国科学院金属研究所 | Anti-chlorine ion corrosion Ni-Cr nano composite coating and preparing method and use |
| CN1880513B (en) * | 2005-06-15 | 2010-07-21 | 中国科学院金属研究所 | Thermally-grown Cr2O3 or Al2O3 film type M-Cr-Al nano composite coating and method for preparing same and application thereof |
| CN101967669A (en) * | 2010-11-15 | 2011-02-09 | 沈阳工业大学 | Wear-resistance Ni-Cr nano composite plating, and preparation method and use thereof |
| CN106087003A (en) * | 2016-06-13 | 2016-11-09 | 中国科学院金属研究所 | A kind of improve the method for Cr nano-particle content in Ni Cr nano-composite plate |
| TW201925093A (en) * | 2017-08-04 | 2019-07-01 | 美商博隆能源股份有限公司 | Cerium oxide treatment of fuel cell components |
| CN109680313B (en) * | 2019-02-18 | 2021-02-05 | 中国恩菲工程技术有限公司 | Flue gas pipeline, preparation method thereof and waste incineration flue gas recovery device |
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