CN111910166A - Corrosion-resistant metal porous material and preparation method and application thereof - Google Patents
Corrosion-resistant metal porous material and preparation method and application thereof Download PDFInfo
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- 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
- C23C16/06—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 metallic material
- C23C16/08—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 metallic material from metal halides
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- 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
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- 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
- C23C16/06—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 metallic material
- C23C16/16—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 metallic material from metal carbonyl compounds
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- 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
- C23C16/50—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 using electric discharges
- C23C16/513—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 using electric discharges using plasma jets
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Abstract
The invention provides a corrosion-resistant metal porous material and a preparation method and application thereof, and relates to the technical field of metal porous materials. The corrosion-resistant metal porous material provided by the invention comprises a metal porous material substrate and a corrosion-resistant deposition layer metallurgically bonded on the surface of a porous framework of the metal porous material substrate through chemical vapor deposition, wherein the corrosion-resistant deposition layer is a metal Ta layer, a metal Mo layer or an alternate composite layer of the metal Ta layer and the metal Mo layer. According to the invention, the combination of the metal porous material and Ta and Mo can be realized under the condition that the melting point of Ta and Mo is far lower through chemical vapor deposition, the diffraction of the chemical vapor deposition is strong, Ta and Mo can surround the surface of the metal porous framework uniformly and compactly, and the corrosion resistance of the metal porous material is improved. The corrosion-resistant metal porous material provided by the invention has good corrosion resistance in sulfuric acid, hydrofluoric acid, hydrochloric acid, nitric acid and mixed acid of the sulfuric acid, the hydrofluoric acid, the hydrochloric acid and the nitric acid.
Description
Technical Field
The invention relates to the technical field of metal porous materials, in particular to a corrosion-resistant metal porous material and a preparation method and application thereof.
Background
The metal porous material has the excellent performances of small density, high strength, controllable pore size and pore distribution and the like, simultaneously keeps the good electric conductivity, heat conductivity and processability of metal, has good heat insulation, sound absorption and excellent filtering performance, and is a very potential structure function integrated material. The metal porous material includes metal powder sintered porous material, metal fiber porous material, foamed metal and the like. The metal porous material has wide application in the fields of textile products, filter materials, medical implants, new energy battery key materials and the like, and is one of the key points of the research on novel metal materials.
However, the metal porous material has large specific surface area and strong surface activity, reduces the activation energy of chemical reaction, and contains H2SO4And the reaction easily occurs in a corrosive medium such as HF, which leads to a drastic reduction in the service life. For example, metallic porous materials such as stainless steel, copper alloys, FeCrAl, nickel and its alloys, titanium and its alloys are all in H2SO4Or rapid corrosive dissolution in HF.
Disclosure of Invention
In view of the above, the present invention aims to provide a corrosion-resistant metal porous material, and a preparation method and an application thereof. The metal porous material provided by the invention has excellent acid corrosion resistance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a corrosion-resistant metal porous material which comprises a metal porous material substrate and a corrosion-resistant deposition layer metallurgically bonded on the surface of a porous framework of the metal porous material substrate through chemical vapor deposition, wherein the corrosion-resistant deposition layer is a metal Ta layer, a metal Mo layer or an alternate composite layer of the metal Ta layer and the metal Mo layer.
Preferably, the metal porous material substrate comprises a metal fiber sintered felt, a metal fiber sintered body, a metal fiber needle felt, a foamed metal plate, a metal powder sintered porous material or a 3D printed metal porous material; the material of the metal porous material base material comprises one or more of stainless steel, titanium alloy, nickel alloy, copper alloy and iron-chromium-aluminum alloy.
Preferably, the thickness of the corrosion-resistant deposition layer is 0.5-20 μm.
The invention provides a preparation method of the corrosion-resistant metal porous material, which comprises the following steps:
heating the metal porous material substrate, introducing precursor gas of Ta and/or Mo in a direction vertical to the surface direction of the metal porous material substrate to perform chemical vapor deposition, and forming a metal Ta layer, a metal Mo layer or an alternate composite layer of the metal Ta layer and the metal Mo layer on the surface of a porous framework of the metal porous material substrate to obtain the corrosion-resistant metal porous material;
the precursor gas is halide or an organic complex; and when the precursor gas is halide, introducing a reducing gas.
Preferably, the flow rate of the precursor gas is 0.1-50 g/min.
Preferably, the reducing gas is H2The molar ratio of the halide to the reducing gas is 1 (2-6); the flow rate of the reducing gas is 0.01-50L/min.
Preferably, when chemical vapor deposition forms a metallic Ta layer, the chemical vapor deposition is thermally activated chemical vapor deposition or plasma enhanced chemical vapor deposition;
when the chemical vapor deposition is the thermal activation chemical vapor deposition, the precursor gas for forming the metal Ta layer is TaF5Or TaCl5The deposition temperature is 800-1300 ℃, and the deposition pressure is 10-10 DEG C5Pa；
When the chemical vapor deposition is plasma enhanced chemical vapor deposition, the precursor gas for forming the metal Ta layer is TaF5、TaCl5Or TaBr5The deposition temperature is 300-500 ℃, and the deposition pressure is 10-105Pa。
Preferably, when the chemical vapor deposition forms the metal Mo layer, the chemical vapor deposition is a thermally activated chemical vapor deposition, and the precursor gas for forming the metal Mo layer is MoF6Or Mo (CO)6；
When the precursor gas for forming the metal Mo layer is MoF6The deposition temperature of the chemical vapor deposition is 600-850 ℃, and the deposition pressure is 10-10 DEG C5Pa; when the precursor gas for forming the metal Mo layer is Mo (CO)6The deposition temperature of the chemical vapor deposition is 350-700 ℃, and the deposition pressure is 10-10 DEG C5Pa。
Preferably, when the chemical vapor deposition is the thermal activation chemical vapor deposition, a carrier gas is also introduced; the carrier gas is Ar, He or N2(ii) a The flow rate of the carrier gas is 0.01-50L/min.
The invention provides application of the corrosion-resistant metal porous material prepared by the scheme or the preparation method in fuel cells, chemical reactors, filter materials and bionic implants.
The invention provides a corrosion-resistant metal porous material which comprises a metal porous material substrate and a corrosion-resistant deposition layer metallurgically bonded on the surface of a porous framework of the metal porous material substrate through chemical vapor deposition, wherein the corrosion-resistant deposition layer is a metal Ta layer, a metal Mo layer or an alternate composite layer of the metal Ta layer and the metal Mo layer. According to the invention, the metal porous material has a metal porous framework, the metal porous framework has structural strength and rigidity, and the Ta and Mo have good corrosion resistance. The corrosion-resistant metal porous material provided by the invention has excellent acid corrosion resistance, such as good corrosion resistance in sulfuric acid, hydrofluoric acid, hydrochloric acid, nitric acid and mixed acid of the acids, and can be effectively applied to fuel cells, chemical reactors, filter materials and bionic implants.
The invention provides a preparation method of the corrosion-resistant metal porous material, and precursor gas of Ta and/or Mo is introduced in the direction vertical to the surface direction of a metal porous material substrate, namely the flow direction of reaction gas is vertical to the surface direction of the metal porous material, so that the reaction gas can be ensured to flow through the internal pores of the metal porous material, and a corrosion-resistant deposition layer which completely wraps a metal porous framework is deposited; moreover, the flowing reaction gas can supplement the reaction gas consumed by the reaction in time and discharge the generated tail gas, thereby promoting the continuous proceeding of the deposition reaction.
Furthermore, the invention can give consideration to the thickness of the deposition layer and the porosity of the porous material by adjusting the process parameters of the chemical vapor deposition, and keep the good permeability and excellent filtering performance of the metal porous material. In addition, the plasma enhanced chemical vapor deposition can further reduce the reaction temperature of the vapor deposition, reduce the fiber embrittlement caused by coarse grains and phase change of the metal porous material, and reduce energy consumption.
Moreover, the preparation method provided by the invention is simple in process and convenient to operate.
Drawings
FIG. 1 is a schematic sectional view of a corrosion-resistant metal porous material provided by the present invention, wherein 1 in FIG. 1 represents metal fibers in a metal porous material substrate, and 2 represents a corrosion-resistant deposition layer;
fig. 2 is an apparatus for manufacturing a corrosion-resistant porous metal material according to the present invention, in fig. 2, 1 denotes a precursor gas generator, 2 denotes a reducing gas storage device, 3 denotes a carrier gas storage device, 4 denotes a gas control device, 5 denotes a chemical vapor deposition chamber, 6 denotes a heating device, 7 denotes a porous metal material substrate, and 8 denotes an exhaust gas treatment device.
Detailed Description
The invention provides a corrosion-resistant metal porous material which comprises a metal porous material substrate and a corrosion-resistant deposition layer metallurgically bonded on the surface of a porous framework of the metal porous material substrate through chemical vapor deposition, wherein the corrosion-resistant deposition layer is a metal Ta layer, a metal Mo layer or an alternate composite layer of the metal Ta layer and the metal Mo layer.
The corrosion-resistant metal porous material provided by the invention comprises a metal porous material substrate, wherein the metal porous material substrate is provided with a porous framework. In the present invention, the metal porous material substrate preferably comprises a metal fiber sintered felt, a metal fiber sintered body, a metal fiber needle felt, a foamed metal plate, a metal powder sintered porous material or a 3D printed metal porous material; the material of the metal porous material substrate preferably comprises one or more of stainless steel, titanium alloy, nickel alloy, copper alloy and iron-chromium-aluminum alloy. In the embodiment of the invention, the metal porous material is stainless steel fiber sintered felt, titanium fiber sintered plate, foamed nickel or powder sintered porous titanium. In the invention, the porosity of the metal porous material is preferably 30-98%, and more preferably 70-80%; the diameter of the filament is preferably 1 to 500 μm, more preferably 5 to 100 μm. The source of the metal porous material substrate is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used.
The corrosion-resistant metal porous material provided by the invention comprises a corrosion-resistant deposition layer which is metallurgically bonded on the surface of a porous framework of a metal porous material substrate through chemical vapor deposition, wherein the corrosion-resistant deposition layer is made of a metal Ta layer, a metal Mo layer or an alternate composite layer of the metal Ta layer and the metal Mo layer. In the invention, the thickness of the corrosion-resistant deposition layer is preferably 0.5-20 μm, and more preferably 1-10 μm; when the corrosion-resistant deposition layer is an alternating composite layer of a metal Ta layer and a metal Mo layer, the invention has no special requirement on the proportion of the metal Ta layer and the metal Mo layer in the alternating composite layer.
The cross-sectional view of the corrosion-resistant metal porous material provided by the invention is shown in fig. 1, wherein 1 in fig. 1 represents metal fibers in a metal porous material substrate, and 2 represents a corrosion-resistant deposition layer.
According to the invention, the metal porous material has a metal porous skeleton composed of metal fibers, the metal porous skeleton has structural strength and rigidity, and the Ta and Mo have good corrosion resistance.
The corrosion-resistant metal porous material provided by the invention has good corrosion resistance in sulfuric acid, hydrofluoric acid, hydrochloric acid, nitric acid and mixed acid of the acids; preferably, when the corrosion-resistant deposition layer is a metal Ta layer, the corrosion-resistant metal porous material has good corrosion resistance in sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and sulfuric acid-nitric acid mixed acid; when the corrosion-resistant deposition layer is a metal Mo layer, the corrosion-resistant metal porous material has good corrosion resistance in hydrofluoric acid, sulfuric acid and hydrofluoric acid-sulfuric acid mixed acid.
The invention provides a preparation method of the corrosion-resistant metal porous material in the technical scheme, which comprises the following steps:
heating the metal porous material substrate, introducing precursor gas of Ta and/or Mo in a direction vertical to the surface direction of the metal porous material substrate to perform chemical vapor deposition, and forming a metal Ta layer, a metal Mo layer or an alternate composite layer of the metal Ta layer and the metal Mo layer on the surface of a porous framework of the metal porous material substrate to obtain the corrosion-resistant metal porous material;
the precursor gas is halide or an organic complex; and when the precursor gas is halide, introducing a reducing gas.
The invention heats the metal porous material substrate. Before heating, the invention preferably carries out pretreatment on the metal porous material substrate; the pretreatment preferably comprises alkali washing, acid washing, water washing and drying of the metal porous material substrate in sequence. In the invention, the detergent for alkali washing is preferably a dilute sodium hydroxide solution with the mass concentration of 5-15%, and the oil stain on the surface of the metal porous material is removed by alkali washing. In the invention, the detergent for acid washing is preferably diluted hydrochloric acid with the mass concentration of 5-15%, and the oxide film on the surface of the metal porous material is removed by acid washing. In the invention, the water for washing is preferably deionized water, and the invention has no special requirement on the frequency of washing and can wash the water to be neutral; the invention has no special requirements on the drying temperature and time, and can fully remove the moisture on the surface of the metal porous material after washing. After the pretreatment, the metal porous material substrate is preferably placed in a chemical vapor deposition chamber for chemical vapor deposition; the invention preferably heats the metal porous material substrate arranged in the deposition chamber through a heating device outside the deposition chamber, wherein the heating temperature of the metal porous material substrate is the deposition temperature.
According to the invention, precursor gas of Ta and/or Mo is introduced in a direction vertical to the surface direction of the metal porous material substrate to carry out chemical vapor deposition, and a metal Ta layer, a metal Mo layer or an alternate composite layer of the metal Ta layer and the metal Mo layer is formed on the surface of a porous framework of the metal porous material substrate, so that the corrosion-resistant metal porous material is obtained. In the present invention, the precursor gas is a halide or an organic complex, preferably TaF5、TaCl5、TaBr5、MoF6Or Mo (CO)6(ii) a The precursor gas is preferably obtained by heating a corresponding precursor solid material to a temperature above the thermal evaporation temperature, in particular, the TaF5、TaCl5、TaBr5、MoF6And Mo (CO)6The thermal evaporation temperatures of the corresponding precursor solid materials were 95 ℃, 145 ℃, 205 ℃, 33.6 ℃ and 55 ℃, respectively. In the invention, the flow rate of the precursor gas is preferably 0.01-50L/min, and more preferably 0.05-10L/min.
In the invention, when the precursor gas is halide, reducing gas is also introduced; the reducing gas is preferably H2The molar ratio of the halide to the reducing gas is preferably 1 (2-6); the flow rate of the reducing gas is preferably 0.01 to 50L/min, and more preferably 0.01 to 50L/min1～15L/min。
In the present invention, when chemical vapor deposition forms a metallic Ta layer, the chemical vapor deposition is preferably thermally activated Chemical Vapor Deposition (CVD) or plasma enhanced chemical vapor deposition (PECVD-Ta). In the present invention, when the chemical vapor deposition is a thermally activated chemical vapor deposition, the precursor gas for forming the metallic Ta layer is preferably TaF5Or TaCl5The molar ratio of the precursor gas to the reducing gas is more preferably 1 (2.5 to 4). When the chemical vapor deposition is thermal activation chemical vapor deposition, the invention also preferably introduces carrier gas, and the carrier gas is preferably Ar, He or N2(ii) a The flow rate of the carrier gas is preferably 0.01-50L/min, and more preferably 1-15L/min. In the invention, the deposition temperature of the thermal activation chemical vapor deposition is preferably 800-1300 ℃, and when the precursor gas is TaCl5When the deposition temperature is more preferably 1000-1300 ℃, and when the precursor gas is TaF5When the temperature is higher than the deposition temperature, the deposition temperature is more preferably 800-1000 ℃; the deposition pressure of the thermal activation chemical vapor deposition is preferably 10-105Pa, more preferably 600 to 1000 Pa.
In the present invention, when the chemical vapor deposition is a plasma enhanced chemical vapor deposition, the precursor gas for forming the metal Ta layer is preferably TaF5、TaCl5Or TaBr5The molar ratio of the precursor gas to the reducing gas is preferably 1 (2.5-4); the deposition temperature is preferably 300-500 ℃, more preferably 400-500 ℃, and the deposition pressure is preferably 10-10%5Pa, more preferably 10 to 600 Pa.
In the invention, the thermal activation chemical vapor deposition promotes the chemical reaction of the precursor gas and the reducing gas by means of heating, and the deposition temperature is relatively high. Plasma enhanced chemical vapor deposition is a process in which a chemical reaction is carried out by generating plasma from a gas discharge, and the deposition temperature can be lowered. In the present invention, the chemical reaction that occurs when the chemical vapor deposition forms the Ta layer is such that the precursor gas is TaF5For example, as shown in formula 1:
2TaF5+5H2-2Ta +10HF of formula1。
In the present invention, when the chemical vapor deposition forms the metal Mo layer, the chemical vapor deposition is preferably a thermally activated chemical vapor deposition, and the precursor gas for forming the metal Mo layer is preferably MoF6Or Mo (CO)6. In the present invention, when the precursor gas for forming the metal Mo layer is MoF6In the case, the molar ratio of the precursor gas to the reducing gas is more preferably 1 (3-4); the deposition temperature of the chemical vapor deposition is preferably 600-850 ℃, more preferably 700-800 ℃, and the deposition pressure is preferably 10-10%5Pa, more preferably 1000 to 2000 Pa.
In the invention, when the precursor gas for forming the metal Mo layer is Mo (CO)6When the temperature is high, the deposition temperature of the chemical vapor deposition is preferably 350-700 ℃, and more preferably 500-600 ℃; the deposition pressure is preferably 10-105Pa, more preferably 10 to 1000 Pa; the Mo (CO)6Thermal decomposition occurs, so when the precursor gas is Mo (CO)6In this case, it is not necessary to introduce a reducing gas.
In the process of the thermal activation chemical vapor deposition of Mo, a carrier gas is preferably introduced, and the condition of the carrier gas is the same as that in the above scheme, and is not described herein again.
In the present invention, MoF is used6The chemical reaction for chemical vapor deposition of Mo layer in precursor gas is shown in formula 2, and Mo (CO)6The chemical reaction for chemical vapor deposition of a Mo layer in a precursor gas is shown in formula 3:
MoF6+3H2-Mo +6HF, formula 2,
Mo(CO)6-Mo +6CO formula 3.
In the invention, when chemical vapor deposition is carried out to form an alternating composite layer of a metal Ta layer and a metal Mo layer, the precursor gas of Ta and the precursor gas of Mo alternately pass through the metal porous material, so that the deposition of the metal Ta layer and the metal Mo layer is alternately carried out. In the present invention, when chemical vapor deposition forms an alternating composite layer of metallic Ta and metallic Mo layers, the precursor gas for Ta is preferably TaF5The precursor gas of Mo is preferably MoF6(ii) a Said TaThe conditions for layer deposition and Mo layer deposition are the same as in the above scheme and will not be described further herein.
According to the invention, Ta and/or Mo precursor gas is introduced in a direction vertical to the surface direction of the metal porous material substrate, namely the flow direction of the reaction gas is vertical to the surface direction of the metal porous material, so that the reaction gas can be ensured to flow through the inner pores of the metal porous material substrate, and a corrosion-resistant deposition layer completely wrapping the metal porous framework is deposited; moreover, the flowing reaction gas can supplement the reaction gas consumed by the reaction in time and discharge the generated tail gas, thereby promoting the continuous proceeding of the deposition reaction.
In the present invention, the off-gas includes an excess of precursor gas, an excess of reducing gas, a carrier gas, and a reaction-generated gas. The invention also preferably carries out post-treatment on the tail gas, and the post-treatment method preferably carries out separation in a cooling device according to different melting points and boiling points of different gases; the separated precursor gas, reducing gas and carrier gas are preferably recycled, and the separated gas generated by the reaction is preferably absorbed by an alkaline substance.
In the invention, a device for preparing the corrosion-resistant metal porous material is shown in fig. 2, wherein 1 in fig. 2 represents a precursor gas generating device, and a precursor solid material is heated to a temperature higher than a thermal evaporation temperature to prepare a precursor gas; 2 denotes a reducing gas storage means for supplying a reducing gas; 3 a carrier gas storage device for supplying a carrier gas; 4 a gas control device for controlling the flow rates of the precursor gas, the reducing gas and the carrier gas; 5, a chemical vapor deposition chamber for depositing a corrosion-resistant layer on the surface of the porous skeleton of the metal porous material substrate; 6 denotes a heating device for heating the metal porous material outside the deposition chamber; 7 represents a metal porous material substrate; and 8, a tail gas treatment device for post-treating the tail gas generated by the chemical vapor deposition.
The present invention does not require any particular structure for each of the devices illustrated in fig. 2, and the corresponding devices known to those skilled in the art may be employed.
The invention provides the application of the corrosion-resistant metal porous material prepared by the technical scheme or the corrosion-resistant metal porous material prepared by the preparation method in fuel cells, chemical reactors, filter materials and bionic implants.
In the present invention, when applied to a fuel cell, the corrosion-resistant metallic porous material is preferably used as a fuel cell bipolar plate or a metal gas diffusion layer; the metal porous material base material in the corrosion-resistant metal porous material is preferably a metal fiber sintered body, the porosity is preferably more than 50%, the material of the corrosion-resistant deposition layer in the corrosion-resistant metal porous material is preferably metal Ta, metal Mo or Ta-Mo composite metal, and the thickness is preferably 0.5-5 μm.
In the invention, the chemical reactor is preferably a reforming hydrogen production micro-reactor or a micro-channel reactor, and the application is preferably that the corrosion-resistant metal porous material is used as a reforming hydrogen production micro-reactor or a micro-channel reactor chip.
In the invention, when the corrosion-resistant metal porous material is applied to a filter material, the metal porous material substrate in the corrosion-resistant metal porous material is preferably a metal fiber sintered felt or a metal fiber needled felt, and the material is preferably stainless steel, iron-chromium-aluminum alloy, nickel or nickel alloy; the material of the corrosion-resistant deposition layer in the corrosion-resistant metal porous material is preferably metal Ta, metal Mo or Ta-Mo composite metal; the corrosion-resistant metal porous material can filter liquid or gaseous corrosive media.
In the invention, when the corrosion-resistant metal porous material is applied to a bionic implant, the material of the metal porous material base material in the corrosion-resistant metal porous material is preferably stainless steel or titanium alloy, the Young modulus of the corrosion-resistant metal porous material is equivalent to that of a substituted human tissue organ, and the porosity of the metal porous material base material is preferably 40-90%; the material of the corrosion-resistant deposition layer in the corrosion-resistant metal porous material is preferably metal Ta, the Ta layer is not corroded with the human environment and has biocompatibility, and the thickness of the corrosion-resistant deposition layer is preferably 5-20 mu m.
The corrosion-resistant metal porous material provided by the present invention, the preparation method and the application thereof are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Selecting a titanium fiber sintered plate with the porosity of 80% and the average wire diameter of 65 mu m as a base material, carrying out thermal activation Chemical Vapor Deposition (CVD) Ta on the surface of the titanium fiber sintered plate to prepare a corrosion-resistant full-through-hole metal fiber sintered body which can be used as a fuel cell bipolar plate, and comprising the following steps of:
sequentially carrying out alkali washing, acid washing, deionized water cleaning and drying on the titanium fiber sintered plate, and then placing the titanium fiber sintered plate in a chemical vapor deposition reaction chamber; TaF is added5The solid material is heated to above boiling point (229.2 ℃) by a constant temperature heater under normal pressure to prepare TaF5Gas, with H2Mixing and introducing the mixture into a deposition reaction chamber, wherein the flow direction is vertical to the surface direction of the titanium fiber sintered plate, and the molar ratio of the two gases is TaF5：H2＝1:2.5，TaF5Flow rate of 1g/min, H2The flow rate is 1L/min, the carrier gas is Ar, the flow rate is 1L/min, and the pressure of the reaction chamber filled with the carrier gas is 1000 Pa; the titanium fiber sintering plate is heated in a mode of heating outside a deposition chamber, and the deposition temperature is 950 ℃. At this time, the deposition rate was 0.17 μm/min, the deposition time was 18min, the thickness of the deposited layer was 3 μm, and the porosity was 76%, to obtain a corrosion-resistant metal fiber sintered body.
The tail gas comprises unreacted TaF5、H2Ar, reaction product HF, freezing tail gas at-20 deg.C, H2And Ar are in a gaseous state and can be separated out; HF is liquefied to a liquid, TaF5Crystallizing to obtain solid, performing primary solid-liquid separation, heating the separated solid above HF boiling point, and performing secondary gas-solid separation to obtain pure TaF5Solid and HF gas, and tail gas (residual HF gas) which cannot be recovered are introduced into an alkaline substance for absorption.
Carrying out electrochemical test on the obtained corrosion-resistant metal fiber sintered body in a simulated battery environment, wherein the corrosion medium is 0.5mol/LH2SO4+2ppmF-The solution of (1) has an etching rate of 0.8. mu.A/cm2Can be used as a bipolar plate of a fuel cell; while the titanium fiber sintered plate without Ta deposition has an etching rate of 201 muA/cm in the same etching medium2。
Example 2
A Ta corrosion-resistant layer is deposited on a 3D printing TC4 porous material with the porosity of 70% by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, and the corrosion-resistant 3D printing TC4 porous material is prepared and can be used as a metal porous implant, and the process is as follows:
and sequentially carrying out alkali washing, acid washing, deionized water cleaning and drying on the 3D printed TC4 porous material, and then placing the porous material in a chemical vapor deposition reaction chamber. Adding TaCl5Heating the solid material to a temperature above 150 ℃ in a sealed evaporator to produce TaCl5The vapor pressure of the gas is 800Pa, and under the action of the self pressure, TaCl5The precursor gas directly enters the deposition reaction chamber without the auxiliary transmission of carrier gas, and TaCl5The flow rate of the precursor gas is 3g/min, H2The flow rate is 3L/min, and the molar ratio of the two gases is TaCl5：H2The flow direction of the reaction gas is perpendicular to the plane direction of the porous material of the 3D printed TC4, and the reaction chamber pressure is 600 Pa. The 3D printing TC4 porous material is heated by adopting a mode of heating outside a deposition chamber, the deposition temperature is 500 ℃, the deposition thickness is 2 mu m, and TC is used at the moment4The reduction in porosity of the porous material was 66%.
The Young modulus of the prepared corrosion-resistant 3D printing TC4 porous material is close to that of human bone tissue and is 0.55GPa, because the deposition temperature at 500 ℃ is lower than that of TC4Phase transition point (995 +/-15 ℃), and no beta transformation and TC can be generated in the preparation process4The porous implant does not become brittle. Meanwhile, the Ta deposition layer can prevent V and Al in the titanium alloy from dissolving out, so that cytotoxicity caused by V and anemia and nervous disorder caused by Al are avoided, and the titanium alloy is not corroded after being continuously used for 1000 hours in a human body environment.
Example 3
Selecting a stainless steel fiber sintered felt with the porosity of 85% and the wire diameter of 12 mu m as a base material, and carrying out thermal activation Chemical Vapor Deposition (CVD) Mo on the surface of the base material to prepare the corrosion-resistant stainless steel fiber sintered felt which can be used as a filter material, wherein the process comprises the following steps:
and sequentially carrying out alkali washing, acid washing, deionized water cleaning and drying on the stainless steel fiber sintered felt, and then placing the stainless steel fiber sintered felt in a chemical vapor deposition reaction chamber. Mixing MoF6Is heated by a constant temperature heater under normal pressureHeating to boiling point (33.6 deg.C) to obtain MoF6Precursor gas and H2Introducing into a deposition reaction chamber, wherein the flow direction is vertical to the surface direction of the stainless steel fiber sintered felt, and the molar ratio of the two gases is MoF6：H2＝1:4，MoF6Flow rate of 2g/min, H2The flow rate is 1L/min, the carrier gas is Ar, the flow rate is 1L/min, and the pressure of the reaction chamber filled with the carrier gas is 1000 Pa. And heating the stainless steel fiber sintered felt by adopting a deposition outdoor heating mode, wherein the deposition temperature is 700 ℃, the deposition rate is 0.8 mu m/min, the deposition time is 2min, the deposition thickness is 1.6 mu m, and the porosity is 70%, so that the corrosion-resistant stainless steel fiber sintered felt is obtained.
The tail gas comprises unreacted MoF6、H2Ar, reaction product HF, freezing the tail gas at 0 deg.C, H2And Ar are in a gaseous state and can be separated out; HF is liquefied to liquid, MoF6Crystallizing to obtain solid, performing solid-liquid separation, heating the separated solid to 25 deg.C above HF boiling point, and performing gas-solid separation to obtain pure MoF6Solid and HF gas, and tail gas which cannot be recovered are introduced into an alkaline substance for absorption.
Preparing the obtained corrosion-resistant stainless steel fiber sintered felt into a filter bag sample, and mixing 0.5mol/LH2SO4The aerosol is blown through a filter bag sample, and the corrosion rate is 0.01mg/h when the test is carried out for 72h at the use temperature of 250 ℃; and the corrosion rate of the stainless steel fiber sintered felt without Mo deposition under the same conditions is 2.3 mg/h.
Example 4
Selecting a stainless steel fiber needled felt with porosity of 78% and average filament diameter of 8 mu m as a base material, carrying out thermal activation Chemical Vapor Deposition (CVD) Mo on the surface of the base material to prepare the corrosion-resistant stainless steel fiber needled felt which can be used as a filter material, and comprising the following steps of:
and sequentially carrying out alkali washing, acid washing, deionized water cleaning and drying on the stainless steel fiber needled felt, and then placing the stainless steel fiber needled felt in a chemical vapor deposition reaction chamber. Mixing Mo (CO)6Heating the solid material in a sealed evaporator to 100 ℃ to form gas, mixing the gas with carrier gas Ar, introducing the gas into a deposition reaction chamber, and allowing the gas to flow in the direction of the surface of the stainless steel fiber needled feltIn the vertical direction, the molar ratio of the two gases is Ar: mo (CO)6＝5：1，Mo(CO)6The flow rate of (3) is 2g/min, the flow rate of Ar is 2L/min, and the pressure of the reaction chamber is 10 Pa. The stainless steel fiber needled felt is heated in a mode of heating outside a deposition chamber to the deposition temperature of 500 ℃, and Mo (CO)6The gas is heated to generate decomposition reaction, and the gas is thermally decomposed into a Mo layer and CO gas on the surface of the fiber. After deposition for 10min, the thickness of the deposition layer is 1 μm, and the porosity of the stainless steel fiber needled felt is reduced to 67% at this time, so as to obtain the corrosion-resistant stainless steel fiber needled felt.
The tail gas comprises unreacted Mo (CO)6Ar, reaction product CO, freezing tail gas at 0 ℃, wherein CO and Ar are in gaseous state and can be separated out; mo (CO)6The crystal is solid and can be recycled; and igniting and treating the CO tail gas which cannot be recovered.
The obtained corrosion-resistant stainless steel fiber needled felt is 0.5mol/LH2SO4The solution is soaked for 48 hours at room temperature, and the corrosion rate of the corrosion-resistant stainless steel fiber needled felt is zero.
Example 5
Selecting foamed nickel with the porosity of 66% as a base material, carrying out thermal activation Chemical Vapor Deposition (CVD) on the surface of the base material to form an alternate composite layer of a metal Ta layer and a metal Mo layer, preparing the corrosion-resistant foamed nickel, and using the foamed nickel as a catalyst carrier of a chemical reactor, wherein the process comprises the following steps:
sequentially carrying out alkali washing, acid washing, deionized water cleaning and drying on the foamed nickel, and then placing the foamed nickel in a chemical vapor deposition reaction chamber; TaF is added5And MoF6Respectively heating the solid materials in a constant temperature heater under normal pressure to above respective boiling points to obtain TaF5Gas and MoF6A gas. Then respectively reacting with H2Mixing, alternately introducing into deposition reaction chamber, wherein the flow direction is perpendicular to the foam nickel surface direction, and TaF5And H2In a molar ratio of 1:4, TaF5Flow rate of 1g/min, H2The flow rate is 1L/min, and the deposition temperature is 900 ℃; MoF6And H2In a molar ratio of 1:4, MoF6Flow rate of 1g/min, H2The flow rate is 1L/min, and the deposition temperature is 750 ℃; the carrier gas used by the two is Ar, the flow rate is 1L/min, and the deposition chamberPressure of 105Pa. The thickness of metal Ta after 20min was 3 μm, followed by a reduction of the deposition temperature to 750 ℃ and a thickness of 10 μm after 10min for the deposition of metal Mo. And (3) depositing a metal Ta layer on the metal Mo layer under the same condition, wherein the porosity is reduced to 45%, and preparing the corrosion-resistant foamed nickel.
The tail gas comprises unreacted TaF5、MoF6、H2Ar, reaction product HF, freezing tail gas at-20 deg.C, H2And Ar are in a gaseous state and can be separated out; HF is liquefied to a liquid, TaF5Crystallized as a solid, MoF6Crystallizing to obtain solid, performing primary solid-liquid separation, heating the separated solid above HF boiling point, and performing secondary gas-solid separation to obtain pure TaF5And MoF6Solid and HF gas, and tail gas (residual HF gas) which cannot be recovered are introduced into an alkaline substance for absorption.
Placing the prepared corrosion-resistant foamed nickel in 0.5mol/L H2SO4When the sample is soaked for 24 hours, the mass of the sample is not reduced, which indicates that the material is not corroded.
It can be seen from the above examples that the invention realizes the combination of the metal porous layer material and Ta and Mo by chemical vapor deposition under the condition of being far lower than the melting points of Ta and Mo, and the obtained corrosion-resistant metal porous material has good corrosion resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The corrosion-resistant metal porous material is characterized by comprising a metal porous material substrate and a corrosion-resistant deposition layer metallurgically bonded on the surface of a porous framework of the metal porous material substrate through chemical vapor deposition, wherein the corrosion-resistant deposition layer is a metal Ta layer, a metal Mo layer or an alternate composite layer of the metal Ta layer and the metal Mo layer.
2. The corrosion-resistant metallic porous material of claim 1, wherein said metallic porous material substrate comprises a metal fiber sintered felt, a metal fiber sintered body, a metal fiber needle felt, a metal foam sheet, a metal powder sintered porous material, or a 3D printed metallic porous material;
the material of the metal porous material base material comprises one or more of stainless steel, titanium alloy, nickel alloy, copper alloy and iron-chromium-aluminum alloy.
3. The corrosion-resistant metallic porous material according to claim 1, wherein the thickness of the corrosion-resistant deposition layer is 0.5 to 20 μm.
4. The method for preparing the corrosion-resistant porous metal material according to any one of claims 1 to 3, comprising the steps of:
heating the metal porous material substrate, introducing precursor gas of Ta and/or Mo in a direction vertical to the surface direction of the metal porous material substrate to perform chemical vapor deposition, and forming a metal Ta layer, a metal Mo layer or an alternate composite layer of the metal Ta layer and the metal Mo layer on the surface of a porous framework of the metal porous material substrate to obtain the corrosion-resistant metal porous material;
the precursor gas is halide or an organic complex; and when the precursor gas is halide, introducing a reducing gas.
5. The method according to claim 4, wherein the flow rate of the precursor gas is 0.1 to 50 g/min.
6. The production method according to claim 4, wherein the reducing gas is H2The molar ratio of the halide to the reducing gas is 1 (2-6); the flow rate of the reducing gas is 0.01-50L/min.
7. The method according to claim 4, wherein when chemical vapor deposition forms the metallic Ta layer, the chemical vapor deposition is thermally activated chemical vapor deposition or plasma enhanced chemical vapor deposition;
when the chemical vapor deposition is the thermal activation chemical vapor deposition, the precursor gas for forming the metal Ta layer is TaF5Or TaCl5The deposition temperature is 800-1300 ℃, and the deposition pressure is 10-10 DEG C5Pa；
When the chemical vapor deposition is plasma enhanced chemical vapor deposition, the precursor gas for forming the metal Ta layer is TaF5、TaCl5Or TaBr5The deposition temperature is 300-500 ℃, and the deposition pressure is 10-105Pa。
8. The method according to claim 4, wherein the chemical vapor deposition is a thermally activated chemical vapor deposition and the precursor gas for forming the metal Mo layer is MoF when the chemical vapor deposition forms the metal Mo layer6Or Mo (CO)6；
When the precursor gas for forming the metal Mo layer is MoF6The deposition temperature of the chemical vapor deposition is 600-850 ℃, and the deposition pressure is 10-10 DEG C5Pa; when the precursor gas for forming the metal Mo layer is Mo (CO)6The deposition temperature of the chemical vapor deposition is 350-700 ℃, and the deposition pressure is 10-10 DEG C5Pa。
9. The production method according to claim 7 or 8, wherein when the chemical vapor deposition is a thermally activated chemical vapor deposition, a carrier gas is further introduced; the carrier gas is Ar, He or N2(ii) a The flow rate of the carrier gas is 0.01-50L/min.
10. Use of the corrosion-resistant metal porous material according to any one of claims 1 to 3 or the corrosion-resistant metal porous material prepared by the preparation method according to any one of claims 4 to 9 in fuel cells, chemical reactors, filter materials and biomimetic implants.
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