CN104388930B - Preparation method of coating structure with sandwich nano ceramic layer - Google Patents

Preparation method of coating structure with sandwich nano ceramic layer Download PDF

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Publication number
CN104388930B
CN104388930B CN201410751142.1A CN201410751142A CN104388930B CN 104388930 B CN104388930 B CN 104388930B CN 201410751142 A CN201410751142 A CN 201410751142A CN 104388930 B CN104388930 B CN 104388930B
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nano
ceramic layer
ceramic
sandwich
powder
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CN104388930A (en
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高雪松
肖猛
张涛
刘建涛
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Naijing Zhongke Shenguang Technology Co Ltd
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Naijing Zhongke Shenguang Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00Coating starting from inorganic powder
    • C23C24/08Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to the field of material surface engineering, and particularly relates to a coating structure with a sandwich nano ceramic layer and a preparation method of the coating structure. The coating structure with the sandwich nano ceramic layer disclosed by the invention comprises a transition layer and a ceramic layer, wherein one surface of the transition layer and a base body are in metallurgical bonding; the other surface of the transition layer and the ceramic layer are in metallurgical bonding; the ceramic layer is a sandwich structure ceramic layer; common ceramic layers are arranged on the upper and lower layers; and the nano ceramic layer is arranged in the middle layer. The coating with the sandwich nano ceramic layer has excellent high temperature resistance and relatively good tenacity and malleability, and is wide in use and long in service life. According to the preparation method of the coating structure disclosed by the invention, different coating structures with the sandwich nano ceramic layers can be prepared on various high-temperature alloy surfaces; the method is simple and efficient, and is contributed to reserving the nano characteristics of the coating.

Description

A kind of preparation method of the coating structure with sandwich nano-ceramic layer
Technical field
The present invention relates to material surface engineering field and in particular to a kind of coating structure with sandwich nano-ceramic layer and Preparation method.
Background technology
In high-temperature material industry, due to the heat resistant requirements more and more higher to material for the working environment, simple metal material Material can not meet requirement.And simultaneously, ceramic material has excellent wear-resisting, anti-corrosion, heat-resisting and high temperature oxidation resistance, but by In its fragility larger, fatigue performance is poor, to stress and crack-sensitivity, and be difficult to be restricted so as to apply.So Ceramic coating is gradually prepared in metal surface formation metal/ceramic composite as sealer by people, by matrix gold Belong to and the feature of surface ceramic coat organically combines, play the comprehensive advantage of two class materials.
Compared with conventional ceramic coatings, nano ceramic coat not only has the advantages that wear-resisting, anti-corrosion, heat-resisting, more overcomes The big shortcoming of ceramic material fragility, and may show with class of metal materials as plasticity so as to be increasingly becoming industry-by-industry Goal in research.But because nano material specific surface area is big, surface-active is high, easily grows up during prepares coating, and lose The characteristic of nano material.So preparing nano ceramic coat on high-temperature material surface also there is certain difficulty.Prepare at present Most of nano ceramic coat be not nano ceramic coat in pure meaning in fact, typically can be assumed that be in micron or Person is to there is nano-particle phase in sub-micron grain matrix phase.
Currently, the method such as plasma spraying nano ceramics aggregate, laser melting coating nano-ceramic powder is usually used in preparing nanometer Ceramic coating.Because laser has heating, cooling velocity soon, it is the Perfected process preparing nano coating, but its controllable ability Poor, so the nano ceramics structure diversification obtaining, and surface stress is larger, easily peels off.Through electron beam physical vapor What deposition (EB-PVD) method processing obtained aoxidizes yttrium partially stabilized zirconium oxide heat barrier ceramic coating (YPSZ) although coating is whole Body is nano-structure, but preparation efficiency is low and cost is very high.Due to above reason, high-temperature nano ceramic coating is not still substantive The technological break-through of property, limits its range of application.Therefore, develop that a kind of manufacturing cost is relatively low and painting that have nano ceramics characteristic Layer becomes a problem demanding prompt solution.
Content of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of coating structure with sandwich nano-ceramic layer and Preparation method.
The coating structure with sandwich nano-ceramic layer of the present invention, including transition zone and ceramic layer, the one of transition zone Face and matrix metallurgical binding, another side with ceramic layer metallurgical binding it is characterised in that:Described ceramic layer is sandwich structure pottery Layer, its upper and lower two-layer is conventional ceramic layer, and intermediate layer is nano-ceramic layer.
Preferably, described ceramic layer thickness is 150~600 μm, and wherein conventional ceramic layer thickness is respectively 50~200 μm, receives Rice ceramic layer thickness is 50~200 μm.
Preferably, described nano-ceramic layer is made up with nano-ceramic powder mixing scorification of binding agent.It is furthermore preferred that it is described viscous Knot agent is PVC or PVA.
Preferably, described matrix includes iron-based, Ni-based, cobalt base superalloy structural member.
Preferably, described transition zone is by the Al of pure Ti powder, Al powder and granularity 20nm2O3Nano-ceramic powder is according to mass ratio (3.8~4.5):(4.5~5.0):The ratio composition of (0.8~1.2).
Preferably, described transition region thickness is 100~200 μm.
A kind of preparation method of coating structure with sandwich nano-ceramic layer of the present invention is it is characterised in that be somebody's turn to do Method comprises the following steps:
(1) matrix surface is carried out purifying, activation process;
(2) choose and meet self-propagating reaction alloy requirement and the powder systems of transition zone performance requirement, uniformly mix conduct Transition zone powder;
(3) transition zone powder is dried, and be pressed into the thin slice of 100~200 μ m thick;
(4) nano-ceramic powder and binding agent are carried out mixing, dry, finally carry out ball milling dispersion;
(5) transition zone suppressing thin slice is placed on matrix, then coats 50~200 μm on transition zone thin slice successively The nano-ceramic powder of thickness, the nanometer of the nano-ceramic powder and 50~200 μ m thick that are mixed with binding agent of 50~200 μ m thick are made pottery Porcelain powder;
(6) laser scanning is carried out to the bisque on matrix, matrix generates transition zone and ceramic layer simultaneously, is had The coating structure of sandwich nano-ceramic layer.
Preferably, described laser adopts CO2 laser or Nd:YAG laser.
Preferably, the scan power of described laser is 200~2000W, is focused into the hot spot of diameter 1~5mm, sweep speed 0.1~3m/min.
The invention provides a kind of coating structure with sandwich nano-ceramic layer and preparation method.This has sandwich nanometer The coating structure of ceramic layer has outstanding high temperature resistance and preferable toughness and ductility, of many uses, long service life.This The preparation method of the coating structure with sandwich nano-ceramic layer that invention provides, using laser melting and coating technique and laser self- propagating Synthetic technology can prepare different nano ceramic coats in various high-temperature alloy surfaces, and so that its transition zone and ceramic layer is given birth to simultaneously Become, reduce preparation process, improve production efficiency, reduce production cost.Meanwhile, the present invention uses sandwich ceramic layer structure, will make pottery Enamel coating is divided into three layers of powdering, and the nano-ceramic powder mixing through binding agent is clipped in the middle of the common nano-ceramic powder of two-layer.Commonly receive Rice ceramic powder can be filled into middle nano-ceramic layer in cladding process, reduces due to cavity produced by binding agent sintering, Make coating densification, flawless defect;It is tiny that the conventional ceramic layer that it generates has crystal grain again, is of close texture, high temperature resistant property is excellent Different feature, can be with the nanometer phase in effective protection intermediate layer in cladding process.And the excellent characteristics of conventional ceramic layer are in coating Use during can with effective protection nano-ceramic layer, improve coating service life.The addition of binding agent can hinder Nano-ceramic particle nucleation again, has ensured that the nano-ceramic layer generating has the nanometers such as preferable toughness, ductility further Property.
Brief description
Fig. 1 has the structural representation of the coating structure of sandwich nano-ceramic layer for the present invention;
Fig. 2 is nanometer Al used in the embodiment of the present invention2O3Micro-structure diagram;
Fig. 3 is the micro-structure diagram of prepared coating in the embodiment of the present invention.
Fig. 4 is the heterogeneous microstructure figure of nano-ceramic layer in prepared coating in the embodiment of the present invention.
In figure label:
1- matrix;2- transition zone;3- ceramic layer;31- conventional ceramic layer;32- nano-ceramic layer.
Specific embodiment
The invention provides a kind of coating structure with sandwich nano-ceramic layer and preparation method, right below in conjunction with the accompanying drawings The present invention is described further.As shown in figure 1,1 is matrix, 2 is transition zone, and 3 is ceramic layer, and ceramic layer 3 is sandwich structure, folder The two-layer up and down of the heart is conventional ceramic layer 31, and intermediate layer is nano-ceramic layer 32.
According to one embodiment of present invention, Al is prepared on TiAl alloy matrix 12O3Nano ceramic coat.Concrete operations As follows:
(1) acetone and alcohol washes are used totally to matrix 1, then sandblasting is standby;
(2) by the Al of pure Ti powder, Al powder and granularity 20nm2O3Nano-ceramic powder (as shown in Figure 2) example 4.3 in mass ratio: 4.7:1 is configured, and obtains transition zone powder through ball mill mixing 50min;
(3) transition zone powder is dried at 100 DEG C 1h, the thin slice of re-compacted one-tenth 150 μ m thick;
(4) by Al2O3Nano-ceramic powder is put into high energy ball mill and is pulverized, it is to avoid its reunion;Latter one will be pulverized simultaneously Divide Al2O3Nano-ceramic powder carries out mixing with PVC binding agent, dries, and finally carries out ball milling;
(5) transition zone suppressing thin slice is placed on matrix 1, then 100 μ m-thick are coated successively on transition zone thin slice The Al of degree2O3Nano-ceramic powder, the Al being mixed with PVC binding agent of 100 μ m thick2O3Nano-ceramic powder and the Al of 100 μ m thick2O3 Nano-ceramic powder;
(6) adopt continuous CO2Laser, laser power is 1300W, is focused into the hot spot of a diameter of 2mm, 1.5m/min's Under sweep speed, cladding is carried out to the bisque on matrix 1, transition zone 2 and ceramic layer 3 are generated on matrix 1 simultaneously, is had Sandwich Al2O3The coating of nano-ceramic layer.
According to what above-mentioned steps obtained, there is sandwich Al2O3The coating of nano-ceramic layer, its coating layer thickness is 450 μm, wherein Transition zone 2 is about 150 μm, and ceramic layer 3 is about 300 μm, and in the sandwich structure of ceramic layer 3, upper and lower two-layer conventional ceramic layer 31 is each about For 100 μm, intermediate layer nano-ceramic layer 32 is about 100 μm.As shown in figure 3, being metallurgical binding, no between each bed boundary of coating Crackle, and the nano particle in nano-ceramic layer 32 is respectively less than 100nm (as shown in Figure 4), remains nano particle distinctive Characteristic, its performance testing index is above equivalent material coating.
Above content be only to specific embodiment example and the explanation of the present invention it should be pointed out that, according to According to the conception of the present invention, above-mentioned embodiment is modified or supplement or substituted using similar mode, function produced by it Effect still without departing from specification and accompanying drawing covered spiritual when, all should be within protection scope of the present invention.

Claims (3)

1. a kind of preparation method of the coating structure with sandwich nano-ceramic layer is it is characterised in that the method includes following step Suddenly:
(1) matrix surface is carried out purifying, activation process;
(2) choose and meet self-propagating reaction alloy requirement and the powder systems of transition zone performance requirement, uniformly mixing is as transition Layer powder;
(3) transition zone powder is dried, and be pressed into the thin slice of 100 ~ 200 m thickness;
(4) nano-ceramic powder and binding agent are carried out mixing, dry, finally carry out ball milling dispersion;
(5) transition zone suppressing thin slice is placed on matrix, then 50 ~ 200 m thickness are coated successively on transition zone thin slice Nano-ceramic powder, 50 ~ 200 m thickness be mixed with the nano-ceramic powder of binding agent and the nano-ceramic powder of 50 ~ 200 m thickness;
(6) laser scanning is carried out to the bisque on matrix, matrix generates transition zone and ceramic layer simultaneously, obtains with folder The coating structure of heart nano-ceramic layer.
2. the preparation method of a kind of coating structure with sandwich nano-ceramic layer according to claim 1, its feature exists In:Described laser adopts CO2Laser or Nd:YAG laser.
3. the preparation method of a kind of coating structure with sandwich nano-ceramic layer according to claim 2, its feature exists In:The scan power of described laser is 200 ~ 2000W, is focused into the hot spot of diameter 1 ~ 5mm, sweep speed 0.1 ~ 3m/min.
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