CN106399968A - Preparation method for oxide ceramic coating on surface of wave-absorbing material powder - Google Patents
Preparation method for oxide ceramic coating on surface of wave-absorbing material powder Download PDFInfo
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- CN106399968A CN106399968A CN201610665560.8A CN201610665560A CN106399968A CN 106399968 A CN106399968 A CN 106399968A CN 201610665560 A CN201610665560 A CN 201610665560A CN 106399968 A CN106399968 A CN 106399968A
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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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
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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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
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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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
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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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
Abstract
Disclosed is a preparation method for an oxide ceramic coating on the surface of wave-absorbing material powder. The preparation method comprises the following steps that the wave-absorbing material powder is put into a porous container; the porous container is put into an ALD reaction chamber, and repeated vacuumizing and three times of nitrogen displacement are conducted; the powder is subjected to fluidization at the atmosphere of nitrogen or argon, or the porous container is rotated to achieve the powder dispersion effect; according to the kind of the deposited oxide ceramic coatings, a reaction precursor is selected, and deposition process parameters are set; under carrying of nitrogen or argon, precursor vapor is led into the ALD reaction chamber; the reaction chamber is blown and swept by nitrogen or argon; and the steps are repeated until the needed thickness of the coating is obtained through deposition. Through the preparation method, the uniform and compact oxide ceramic coating with few impurities and precisely controllable thickness can be prepared out on the surface of the wave-absorbing material powder, and thus the oxidation resistance and corrosion resistance of the wave-absorbing material powder are promoted.
Description
Technical field
The present invention relates to fire-resistant oxidation resistant and antiacid alkali salt mist corrosion resistant coating field, more particularly, to a kind of absorbing material
The preparation method of powder surface oxide ceramic coating.
Background technology
So-called absorbing material, refers to absorb a class material of the electromagnetic wave energy projecting its surface.On engineer applied,
Except requiring absorbing material in addition to having high absorptivity to electromagnetic wave in broad frequency band, it is also required to have light weight, heatproof, resistance to
The performance such as wet, anticorrosive.
The rule propagated from low magnetic steering high magnetic conductance direction in media as well according to electromagnetic wave, using high magnetic permeability absorbing material
Guide electromagnetic waves, by resonance, the emittance of a large amount of electromagnetic wave absorptions, then are become the energy conversion of electromagnetic wave by coupling
Heat.
Existing other absorbing material is primarily present following problem:Be not suitable for working in the environment of high temperature, easily
Oxidized；High humility, salinity or sour environment are easily corroded.
Oxide ceramics has good anti-oxidant and corrosion resistance, therefore, coats oxygen in absorbing material powder surface
Compound pottery is to improve its anti-oxidant and corrosive nature effective way, can also improve the enhancing of absorbing material powder compound simultaneously
The interfacial combined function of material.At present, the method preparing oxide ceramic coating in absorbing material powder surface mainly has colloidal sol
Gel method (Sol-Gel) and chemical vapour deposition technique (CVD).
Sol-gal process is with the organic alkoxide of object element or inorganic salts as raw material, makes colloidal sol under certain condition,
By absorbing material powder impregnation, the gelation due to volatilization and the polycondensation reaction of solvent, then drying and heat treatment inhaling ripple material
Material surface obtains oxide ceramic coating.If Baklanova etc. is using stablizing berkelium oxide colloidal sol in Nicalon SiC fiber surface
Be prepared for zirconia coating (J.Eur.Ceram.Soc., 2006,26:1725).But the coating that sol-gal process is obtained is uneven,
Not fine and close, dry run is also easy to produce contraction crack and hole, typically adopts multiple impregnation, drying and heat treatment, process complexity
All greatly increase with preparation cost, simultaneously after coating absorbing material with good adherence of together.
Chemical vapour deposition technique is several gaseous materials to be delivered to the material surface of heating and occurs chemistry anti-in this place
Should, reactant is deposited on reaction-ure surface and forms coating.If Li etc. is with ZrCl4、CO2And H2For presoma, using chemical vapor deposition
Area method is prepared for ZrO in Hi-Nicalon SiC fiber surface2Coating (J.Am.Ceram.Soc., 2002,85 (6):1561).
But chemical vapour deposition technique complex process, it usually needs carry out at relatively high temperatures, can deteriorate the mechanical property of fiber itself, with
When reaction mechanism complicated, easily impure in coating, exhaust-gas treatment is difficult in addition, and environment can be polluted.
Technique for atomic layer deposition (ALD) is by vaporous precursors pulse is alternately passed through reative cell, in depositing base
Upper chemisorbed, and react a kind of method forming deposition film, the reaction of its surface has from restricted.ALD has depositing temperature
Low, no particle contamination, impurity is few, extensive, the accurate THICKNESS CONTROL of reactant selection, the equal property of deposit thickness and uniformity etc.
Feature.At present, Wang Jun etc. proposes to carry out cladding using the method for ALD in SiC fiber surface and reach oxidation resistant effect.But,
The method can only be coated it is impossible to carry out ald cladding in the form of powder in the fiber cloth of SiC fiber composition,
Seriously limit the use technique of absorbing material.
Content of the invention
The technical problem to be solved is to overcome existing sol-gal process, chemical vapour deposition technique and atomic layer deposition
The deficiency of area method, provides one kind using technique for atomic layer deposition in the oxide coated pottery of absorbing material powder surface even compact
Method.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is：A kind of absorbing material powder surface oxidation
The preparation method of thing ceramic coating, comprises the following steps：
Step (1)：Absorbing material powder is put in the container of porous；
Step (2)：Porous container is put into ALD reaction indoor, then repeatedly vacuumize, replace nitrogen at least three times；
Step (3)：Powder is fluidized under the atmosphere of nitrogen or argon gas, fluidized pressure 1-1000torr, or logical
Cross and porous container is rotated up to powder dispersion effect；
Step (4)：According to the species of deposition oxide coating, select precursors, the parameter of setting ALD reative cell：
25 DEG C -400 DEG C of depositing temperature, deposition pressure is 0.01torr-500torr；
Step (5)：Nitrogen or argon gas carry lower described precursor vapor is incorporated in ALD reative cell, the retention time
The 10-300 second；
Step (6)：Purge reative cell with nitrogen or argon gas, take away remaining presoma；
Step (7)：Nitrogen or argon gas carry lower oxygen source steam is incorporated in ALD reative cell, retention time 10-300
Second；
Step (8)：Purge reative cell with nitrogen or argon gas, take away excessive oxygen source and accessory substance；
Step (9)：Repeat step (5) is to step (8), until depositing to required coating layer thickness.
Preferably, described absorbing material powder is carbonyl iron, carbonyl nickel, carbonyl cobalt, carborundum, iron sial, or can conduct
The metal dust of absorbing material.
Described powder is particle, sheet or chopped strand.
Preferably, described presoma is volatile metal alkylamino salt, metallo-organic compound, halide, alkoxide, gold
Belong to the mixture of one or more of beta-diketon complex compound, described metal alkylamino salt, metallo-organic compound, halide,
Metal ion in alkoxide, metal p-diketonates complex compound is aluminium, hafnium, yttrium, zirconium, titanium, zinc, silicon ion.
Described oxygen source is water, hydrogen peroxide, oxygen, ozone or elemental oxygen.
The gas flow rate that carries in described step (5) and step (7) is 5-8000sccm, in step (6) and step (8)
Purge gas flow velocity is 10--5000sccm.
Fluidized pressure in described step (3) is 10-100torr.
Compared with existing sol-gal process, the invention has the advantages that：Coating uniform is fine and close；The defects such as crackle, hole
Few；Thickness energy precise control；Simple to operate, reproducible.
Compared with existing chemical vapour deposition technique, the invention has the advantages that：Depositing temperature is low, powder is damaged little；
Reaction mechanism is simple, and coating impurity is few；It is easy to depositing multi-component and mixed oxide coatings；Evenly, THICKNESS CONTROL is smart for coating
Du Genggao；Simple to operate it is not necessary to control reactant flow homogeneity；Tail gas is disposable, and environmental pollution is little.
Compared with existing atomic layer deposition method, the invention has the advantages that：Micron or even nanometer grade powder can be coated,
Several kilograms to hundreds of kilogram can be coated every time.
The present invention can prepare, in absorbing material powder surface, the oxygen that uniform, fine and close, impurity is few, thickness is accurately controlled
Compound ceramic coating, thus lift absorbing material powder resistance to oxidation and anticorrosive.
Brief description
With reference to the accompanying drawings and detailed description technical scheme is further described in detail.
Fig. 1 is the TEM microscopic appearance figure that embodiment 4 gained aluminum oxide titanium white coats carbonyl iron；
Fig. 2 is the SEM shape appearance figure that embodiment 4 gained aluminum oxide titanium white coats carbonyl iron；
Fig. 3 is the EDX energy spectrum diagram that embodiment 4 gained aluminum oxide titanium white coats carbonyl iron；
Fig. 4 comprises 2.48% Al, 0.44% Ti and 97.08% iron for the carbonyl iron after embodiment 4 gained cladding
Table figure.
Fig. 5 is that embodiment 4 gained aluminum oxide titanium white coats the thermal weight loss survey in air of carbonyl iron and uncoated carbonyl iron
Examination contrast curve chart；
Fig. 6 is that embodiment 4 gained aluminum oxide titanium white coats carbonyl iron and uncoated carbonyl iron resisting in hydrochloric acid solution
Corrosion change.
Specific embodiment
The preparation method of absorbing material powder surface oxide ceramic coating is it is characterised in that comprise the following steps：
Step (1), by absorbing material, including carbonyl iron, carbonyl nickel, carbonyl cobalt, metal dust, carborundum, iron sial
Powder is put in the container of porous；Powder is particle, sheet or chopped strand.
Step (2), that porous container puts into ALD reaction is indoor, then repeatedly vacuumizes, replaces nitrogen at least three times；
Step (3), powder is fluidized under the atmosphere of nitrogen or argon gas, fluidized pressure 1-1000torr, or logical
Cross and porous container is rotated up to powder dispersion effect；Fluidized pressure is preferably 10-100torr；
Step (4), the species according to deposition oxide coating, select precursors, arrange deposition process parameters：Deposition
25 DEG C -400 DEG C of temperature, deposition pressure is 0.01torr-500torr；Presoma is volatile metal alkylamino salt, metal has
The mixture of one or more of machine compound, halide, alkoxide, metal p-diketonates complex compound.Gold in described presoma
Belong to for one or more of aluminium, hafnium, yttrium, zirconium, titanium, zinc, silicon.
Step (5), carry in nitrogen or argon gas and lower precursor vapor is incorporated in ALD reative cell；
Step (6), purge reative cell with nitrogen or argon gas；
Step (7), carry in nitrogen or argon gas and lower oxygen source steam is incorporated in ALD reative cell；Oxygen source is water, dioxygen
Water, oxygen, ozone or elemental oxygen.
Step (8), purge reative cell with nitrogen or argon gas；
Step (9), repeat step (5) are to step (8), until depositing to required coating layer thickness.
Embodiment 1
The present embodiment comprises the following steps：(1) carbonyl nickel powder is put into a porous container with micropore size；(2)
Porous container is put in ALD reative cell, vacuumizes, replace nitrogen three times, reative cell is warming up to 200 DEG C, and reative cell maintains
The pressure of 5torr；(3) rotating porous container is so that powder is sufficiently mixed in porous cavity；(4) presoma Zr [N (CH3)2]4
N in 50sccm flow velocity2Carry lower pulse and enter reative cell, absorption, on carbonyl nickel powder, until 6torr, and keeps 60 seconds, so
Use 50sccm N afterwards2Purge and take away remaining Zr [N (CH3)2]4, N2 flushing times are 30s, same H2O is in 5Osccm N2's
Carry lower pulse and enter reative cell until air pressure reaches 6torr and keeps 60 seconds, and be chemisorbed on carbonyl nickel powder
Zr[N(CH3)2]4Reaction, generates ZrO2, the time is 60s, and subsequently excessive water and accessory substance are by 50sccm N2Purging takes reaction out of
Room, flushing times are 30s, this completes an ALD deposition cycle；(5) repeat step (4) 100 times, obtain ZrO2Cladding
Thickness is the carbonyl nickel powder of 10nm.
Embodiment 2
The present embodiment comprises the following steps：(1) iron sial powder is put into a porous container with micropore size；
(2) porous container is put in ALD reative cell, vacuumize, replace nitrogen three times, reative cell is warming up to 300 DEG C, reative cell maintains
Pressure in 10torr；(3) using nitrogen streaming mode so that powder suspends in porous cavity and is sufficiently mixed, fluidisation pressure
Power 10torr, nitrogen flow rate 5000sccm；(3) presoma Hf [N (CH3)(C2H5)]4Carry lower pulse in stream of nitrogen gas to enter instead
Answer room, on iron sial powder, the burst length is 30s, then uses N for absorption2Purge and take away remaining Hf [N (CH3)
(C2H5)]4,N2Flushing times are 60s, the O that same ozone generator produces3In 5sccm N2Carrying under pulse enter reaction
Room, and with the Hf [N (CH being chemisorbed on iron sial powder3)(C2H5)]4Reaction, generates HfO2, the time is 30s, with
Excessive O afterwards3And accessory substance is by N2Purging takes reative cell out of, and flushing times are 5s, this completes an ALD deposition cycle；
(5) repeat step (4) 1000 times, obtain ZrO2Cladding thickness is the iron aluminum silicon powder of 120nm.
Embodiment 3
The present embodiment comprises the following steps：(1) carborundum chopped strand powder is put into one and there are the many of micropore size
Pore volume device；(2) porous container is put in ALD reative cell, vacuumize, replace nitrogen three times, reative cell is warming up to 100 DEG C, instead
Room is answered to maintain the pressure of 100mtorr；(3) adopt nitrogen streaming mode so that powder suspends and fully mixed in porous cavity
Close, fluidized pressure 1000torr, nitrogen flow rate 1000sccm；(3) precursor A l (CH3)3N in 15sccm flow velocity2Take pulse refering to leukorrhea
Rush in into reative cell, on carborundum chopped strand powder, the burst length is 10s, then uses 1000sccmN for absorption2Purging is simultaneously
Take away remaining Al (CH3)3,N2Flushing times are 10s, same H2O2In N2Carrying under pulse enter reative cell, and with change
Learn Al (CH on carborundum chopped strand powder for the absorption3)3Reaction, generates Al2O3, the time is 20s, subsequently excessive H2O2And it is secondary
Product is by N2Purging takes reative cell out of, and flushing times are 60s, this completes an ALD deposition cycle；(5) repeat step
(4) 500 times, obtain Al2O3Cladding thickness is the carborundum chopped strand powder of 50nm.
Embodiment 4
The present embodiment comprises the following steps：(1) carbonyl iron dust is put into a porous container with micropore size；(2)
Porous container is put in ALD reative cell, vacuumizes, replace nitrogen three times, reative cell is warming up to 400 DEG C, and reative cell maintains
The pressure of 0.01torr；(3) rotating porous container is so that powder is sufficiently mixed in porous cavity；(4)AlCl3Presoma exists
Under the carrying of N2 of 30sccm flow velocity, pulse enters reative cell, and on carbonyl iron dust, the burst length is 60s, until air pressure for absorption
Reach 20torr, then use 500sccm N2Purge and take away remaining AlCl3,N2Flushing times are 90s, same O3?
30sccm N2Carrying under pulse enter reative cell, and with the AlCl being chemisorbed on carbonyl iron dust3Reaction, generates
Al2O3, the time is 60s, subsequently excessive O3And accessory substance is by 700sccm N2Purging takes reative cell out of, and flushing times are 45s,
This completes an ALD deposition cycle；(5) repeat step (4) 10 times, obtain Al2O3Cladding thickness is the carbonyl iron of 1nm
Powder powder；(6)TiCl4Presoma is in the N of 30sccm flow velocity2Carrying under pulse enter reative cell, absorption on carbonyl iron dust,
Burst length is 60s, until air pressure reaches 6torr, then uses 500sccm N2Purge and take away remaining TiCl4,N2During purging
Between be 90s, same O3In 30sccm N2Carrying under pulse enter reative cell, and be chemisorbed on carbonyl iron dust
TiCl4Reaction, generates TiO2, the time is 60s, subsequently excessive O3And accessory substance is by 700sccm N2Purging takes reative cell out of, blows
Time of washing is 45s, this completes an ALD deposition cycle；(7) repeat step (6) 10 times, obtaining TiO2 cladding thickness is
0.4nm；(8) repeat step (4)-(7) 10 times, obtain Al2O3And TiO2Nano combined cladding thickness is respectively 10nm and 4nm.
The Al that the present embodiment is obtained2O3-TiO2Compound coating carbonyl iron dust, surface is visibly homogeneous smooth, as shown in Figure 1.Apply
Layer is made up of Al, Ti and element, no other impurity, transmission electron microscope TEM show particle surface define uniformly, cause
Close, imperforate clad.
As shown in Figure 2,3, 4, EDX energy spectrum diagram show coat after carbonyl iron comprise 2.48% Al, 0.44% Ti and
97.08% iron.And surface coating layer is uniform and fine and close, completely cut off the reaction of oxygen and carbonyl iron well.After showing cladding
Carbonyl iron powder has high-temperature oxidation resistance well.
As shown in figure 5, mark 1 is not do the carbonyl iron dust that cladding is processed, mark 2 is cladding 5nm Al2O3Carbonyl iron
Powder, mark 3 is cladding 5nm ZrO2Carbonyl iron dust, mark 4 be cladding 5nm HfO2Carbonyl iron dust, mark 5 be cladding 10nm
Al2O3With 4nm TiO2Carbonyl iron dust.See from Fig. 5, the carbonyl iron oxidizing temperature not doing the carbonyl iron dust that cladding is processed is
200--210 DEG C, the carbonyl iron oxidizing temperature after cladding then rises to 400--420 DEG C.
As shown in table Fig. 6, the carbonyl iron dust doing cladding process has intercepted hydrochloric acid and the reaction of carbonyl iron dust itself very well, tool
There is the antiacid corrosiveness being obviously improved.
Embodiment 5
The present embodiment comprises the following steps：(1) chopped iron fiber powder is put into many pore volumes with micropore size
Device；(2) porous container is put in ALD reative cell, vacuumize, replace nitrogen three times, reative cell is warming up to 300 DEG C, reative cell
Maintain the pressure of 500torr；(3) using nitrogen streaming mode so that powder suspends in porous cavity and is sufficiently mixed, stream
Change pressure 100torr, nitrogen flow rate 8000sccm；(4)Al(CH3)3With SiCl4Mixing presoma is in the N of 8000sccm flow velocity2
Carrying under pulse enter reative cell, absorption on chopped iron fiber powder, the burst length be 120s, then use 8000sccm
N2Purge and take away remaining Al (CH3)3With SiCl4,N2Flushing times are 90s, same O2In 5000sccm N2Take pulse refering to leukorrhea
Rush in into reative cell, and with the Al (CH being chemisorbed on chopped iron fiber powder3)3And SiCl4Reaction, generates Al2O3With
SiO2, the time is 45s, and subsequently excessive water and accessory substance are by 8000sccm N2Purging takes reative cell out of, and flushing times are 90s,
This completes an ALD deposition cycle；(5) repeat step (4) 800 times, obtain the Al that coating thickness is 120nm2O3-
SiO2Composite bed.
Embodiment 6
The present embodiment comprises the following steps：(1) carbonyl cobalt sheet or particle powder are put into one and there is micropore size
Porous container；(2) porous container is put in ALD reative cell, vacuumizes, replaces nitrogen four times, reative cell is warming up to 400 DEG C,
Reative cell maintains the pressure of 0.01torr；(3) adopt argon gas streaming mode so that powder suspends and abundant in porous cavity
Mixing, fluidized pressure 80torr, argon gas flow velocity 5sccm；(4)Hf(ONEt2)4With Zr (OC (CH3)3)4Close presoma to exist
The N of 8000sccm flow velocity2Carrying under pulse enter reative cell, absorption on chopped iron fiber powder, the burst length be 120s,
Then use 8000sccm N2Purge and take away remaining Hf (ONEt2)4With Zr (OC (CH3)3)4,N2Flushing times are 90s, equally
H2O is in 8000sccm N2Carrying under pulse enter reative cell, and with the Hf being chemisorbed on chopped iron fiber powder
(ONEt2)4With Zr (OC (CH3)3)4Reaction, generates HfO2And ZrO2, the time is 45s, subsequently excessive water and accessory substance by
8000sccm N2Purging takes reative cell out of, and flushing times are 90s, this completes an ALD deposition cycle；(5) repeat to walk
Suddenly (4) 800 times, obtain the HfO that coating thickness is 120nm2-ZrO2Composite bed.
Embodiment 7
The present embodiment comprises the following steps：(1) carbonyl nickel particle powder is put into many pore volumes with micropore size
Device；(2) porous container is put in ALD reative cell, vacuumize, replace nitrogen three times, reative cell is warming up to 200 DEG C, reative cell
Maintain the pressure of 10torr；(3) adopt nitrogen streaming mode, fluidized pressure 500torr is so that powder is outstanding in porous cavity
Float and be sufficiently mixed, nitrogen flow rate 10sccm；(4)(CH3Cp)3Y presoma is in the N of 8000sccm flow velocity2Carrying under pulse enter
Enter reative cell, on carbonyl nickel particle powder, the burst length is 120s, then uses 5000sccm N for absorption2Purge and take away surplus
Remaining (CH3Cp)3Y,N2Flushing times are 90s, same H2O is in 8000sccm N2Carrying under pulse enter reative cell, and with
It is chemisorbed on (the CH on carbonyl nickel particle powder3Cp)3Y reacts, and generates Y2O3, the time is 45s, subsequently excessive water and pair
Product is by 8000sccm N2Purging takes reative cell out of, and flushing times are 90s, this completes an ALD deposition cycle；(5)
Repeat step (4) 800 times, obtains the Y that coating thickness is 120nm2O3Composite bed.
Embodiment 8
The present embodiment comprises the following steps：(1) carborundum chopped strand powder is put into one and there are the many of micropore size
Pore volume device；(2) porous container is put in ALD reative cell, vacuumize, replace nitrogen three times, reative cell is warming up to 300 DEG C, instead
Room is answered to maintain the pressure of 500torr；(3) adopt nitrogen streaming mode so that powder suspends and fully mixed in porous cavity
Close, nitrogen flow rate 8000sccm；(4)Zn(C2H5)2With TiCl4Mixing presoma 8000sccm flow velocity N2 take pulse refering to leukorrhea
Rush in into reative cell, on chopped iron fiber powder, the burst length is 120s, then uses 10sccm N for absorption2Purge and take away
Remaining Zn (C2H5)2With TiCl4,N2Flushing times are 90s, and hydrogen peroxide is in 5sccm N2Carrying under pulse enter reative cell,
And with the Zn (C being chemisorbed on chopped iron fiber powder2H5)2And TiCl4Reaction, generates ZnO and TiO2, the time is 45s,
Subsequently excessive water and accessory substance are by 1000sccm N2Purging takes reative cell out of, and flushing times are 90s, this completes one
Individual ALD deposition cycle；(5) repeat step (4) 800 times, obtain the ZnO-TiO that coating thickness is 150nm2Composite bed.
The absorbing material powder of the oxide coated ceramic coating that above example is obtained, respectively through transmission electron microscope
TEM detection shows that absorbing material powder surface defines uniform, fine and close, free from admixture, imperforate clad.
Absorbing material powder oxidizing temperature after cladding is risen to after 420 DEG C of oxidation tests by 210 DEG C, and surface coating layer is still
So uniform and fine and close, completely cut off the reaction of oxygen and carbonyl iron well.Show cladding after carbonyl iron powder have high well
Warm antioxygenic property.And oxide ceramic coating has intercepted hydrochloric acid and the reaction of of absorbing material powder itself well, has
The antiacid corrosiveness being obviously improved.Can in the environment of high temperature, high humidity, high salinity Long-Time Service.
It should be noted last that, above specific embodiment only in order to technical scheme to be described and unrestricted,
Although being described in detail to the present invention with reference to preferred embodiment, it will be understood by those within the art that, can be right
Technical scheme is modified or equivalent, and without deviating from the spirit and scope of technical solution of the present invention, it is equal
Should cover in the middle of scope of the presently claimed invention.
Claims (7)
1. a kind of preparation method of absorbing material powder surface oxide ceramic coating is it is characterised in that comprise the following steps：
Step (1)：Absorbing material powder is put in the container of porous；
Step (2)：Porous container is put into ALD reaction indoor, then repeatedly vacuumize, replace nitrogen at least three times；
Step (3)：Powder is fluidized under the atmosphere of nitrogen or argon gas, fluidized pressure 1-1000torr, or by inciting somebody to action
Porous container is rotated up to powder dispersion effect；
Step (4)：According to the species of deposition oxide coating, select precursors, the parameter of setting ALD reative cell：Deposition
25 DEG C -400 DEG C of temperature, deposition pressure is 0.01torr-500torr；
Step (5)：Nitrogen or argon gas carry lower described precursor vapor is incorporated in ALD reative cell, retention time 10-
300 seconds；
Step (6)：Purge reative cell with nitrogen or argon gas, take away remaining presoma；
Step (7)：Nitrogen or argon gas carry lower oxygen source steam is incorporated in ALD reative cell, second retention time 10-300；
Step (8)：Purge reative cell with nitrogen or argon gas, take away excessive oxygen source and accessory substance；
Step (9)：Repeat step (5) is to step (8), until depositing to required coating layer thickness.
2. absorbing material powder surface oxide ceramic coating according to claim 1 preparation method it is characterised in that：
Described absorbing material powder is carbonyl iron, carbonyl nickel, carbonyl cobalt, carborundum, iron sial, or can be used as the gold of absorbing material
Belong to powder.
3. the preparation method of absorbing material powder surface oxide ceramic coating according to claim 1 and 2, its feature exists
In：Described powder is particle, sheet or chopped strand.
4. the preparation method of absorbing material powder surface oxide ceramic coating according to claim 1 and 2, its feature exists
In：Described presoma is volatile metal alkylamino salt, metallo-organic compound, halide, alkoxide, metal p-diketonates are complexed
The mixture of one or more of thing, described metal alkylamino salt, metallo-organic compound, halide, alkoxide, metal β-two
Metal ion in ketone complex compound is aluminium, hafnium, yttrium, zirconium, titanium, zinc, silicon ion.
5. the preparation method of absorbing material powder surface oxide ceramic coating according to claim 1 and 2, its feature exists
In described oxygen source is water, hydrogen peroxide, oxygen, ozone or elemental oxygen.
6. the preparation method of absorbing material powder surface oxide ceramic coating according to claim 1 and 2, its feature exists
In the gas flow rate that carries in described step (5) and step (7) is 5-8000sccm, the purging in step (6) and step (8)
Gas flow rate is 10--5000sccm.
7. absorbing material powder surface oxide ceramic coating according to claim 1 preparation method it is characterised in that
Fluidized pressure in described step (3) is 10-100torr.
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| CN109570489A (en) * | 2018-12-27 | 2019-04-05 | 江苏博迁新材料股份有限公司 | Increase the device and method of metal powder oxygen content using ozonidation |
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