CN110257799B - Preparation method of oil-water separation diamond coating metal net, metal net deposition coating device, diamond coating metal net and application thereof - Google Patents
Preparation method of oil-water separation diamond coating metal net, metal net deposition coating device, diamond coating metal net and application thereof Download PDFInfo
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- CN110257799B CN110257799B CN201810202142.4A CN201810202142A CN110257799B CN 110257799 B CN110257799 B CN 110257799B CN 201810202142 A CN201810202142 A CN 201810202142A CN 110257799 B CN110257799 B CN 110257799B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 285
- 239000002184 metal Substances 0.000 title claims abstract description 285
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 135
- 239000010432 diamond Substances 0.000 title claims abstract description 135
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000000576 coating method Methods 0.000 title claims abstract description 76
- 238000000926 separation method Methods 0.000 title claims abstract description 76
- 239000011248 coating agent Substances 0.000 title claims abstract description 75
- 230000008021 deposition Effects 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002113 nanodiamond Substances 0.000 claims abstract description 76
- 238000000151 deposition Methods 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 62
- 238000004050 hot filament vapor deposition Methods 0.000 claims abstract description 45
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- 239000001257 hydrogen Substances 0.000 claims description 26
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 13
- 230000007246 mechanism Effects 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000005137 deposition process Methods 0.000 abstract description 13
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Water Supply & Treatment (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention discloses a preparation method of an oil-water separation diamond coating metal net, a metal net deposition coating device, a diamond coating metal net and application thereof, and relates to the technical field of oil-water separation metal nets. The preparation method of the diamond coated metal net comprises the following steps: and depositing a diamond coating on the surface of the metal net by adopting a hot wire chemical vapor deposition method. The invention also provides a metal mesh deposition coating device for the hot wire chemical vapor deposition. The invention relieves the problems of high cost, short service life, limited oil-water separation types and easy failure of functions of the existing metal net applied to oil-water separation. According to the invention, the nano diamond is grown by the hot wire chemical vapor deposition method and the metal mesh deposition coating device, so that the deformation of the metal mesh in the deposition process is effectively avoided. The method has the advantages of high film forming rate, simple preparation process, stable process, low cost, suitability for industrial production and large-scale industrial use, high oil-water separation efficiency of the obtained metal net and long service life.
Description
Technical Field
The invention relates to the technical field of oil-water separation metal nets, in particular to a preparation method of an oil-water separation diamond coating metal net, a metal net deposition coating device, a diamond coating metal net and application thereof.
Background
Since the new century, oil-water separation technology has been widely used in various fields such as petrochemical industry, sewage treatment, food engineering, etc. The existing oily wastewater is mainly subjected to secondary treatment by adopting methods such as gravity sedimentation, coarse granulation, centrifugal separation and the like, and the methods can treat the oily wastewater, but have the defects of low separation efficiency, high cost, low recovery rate and the like. Oil-water separation is an important industrial process for treating oily wastewater and aqueous oil. Oil-water separation is to separate oil from water by utilizing the different wettability of the same material to oil and water, for example, the material has super-hydrophobic super-oleophilic property or super-hydrophilic super-oleophobic property. Subsequently, development of super-hydrophobic and super-lipophilic filter materials, which are oleophilic and hydrophobic, is gradually advanced. The general method is to modify the porous structure of the material to be super-hydrophobic, and among various porous structures, a wire mesh is an ideal material due to its low cost, high mechanical strength and porous structure.
The conventional metal mesh can be modified on the surface of the metal mesh structure in a surface modification mode, an acid-base corrosion method or a surface modifier is used for modification treatment, the surface structure is typically changed through corrosion to induce super-hydrophobic super-oleophylic properties, for example, a metal copper mesh is corroded in nitric acid solution, the roughness of the surface of a copper wire is increased, and hexadecanethiol is modified to enable the copper mesh to have the super-hydrophobic super-oleophylic properties, and the method can obtain an oil-water separation effect.
The difficulty of oil-water separation becomes larger and larger due to different factors such as the oil-water mixing state, the oil-water content, the types of organic matters contained in the oil-water mixture, the object of oil-water separation and the like. Meanwhile, the metal mesh is subjected to surface modification to ensure that the metal mesh has hydrophobic and oleophilic characteristics, and various limitations are met in practical application: firstly, the metal net has limited corrosion resistance, is easy to be corroded by the environment, and has short service life; secondly, the specificity of the modified metal mesh surface applied to oil-water separation is strong, the specific oil type is less, and the specific oil-water separation needs to be treated by corresponding specific corrosion and modifier; and when oil-water separation is carried out by acid-base corrosion or a surface modifier modification method, the time is not long, and the hydrophobic functional groups added on the metal surface by the acid-base corrosion and surface modifier addition method are only on the surface and are easy to fail.
In the prior art, some materials for oil-water separation appear, for example, patent CN106987876 a discloses a preparation method of a super-hydrophobic/oleophilic water separation Ni-Cu composite plating layer net film, which comprises the steps of firstly carrying out Ni-Cu composite plating on the surface of metal to enhance the corrosion resistance of the metal, and then carrying out surface modification on the plating layer by using a low-energy surface modifier to obtain the hydrophilic/oleophobic function. The method has complex process, needs two process treatments, has short service life, and is easy to lose effectiveness of the low-energy active agent adsorbed on the metal surface, thereby causing the loss of the hydrophilic/oleophobic function. Patent CN106362439a discloses a method for preparing an oil-water separation metal net with hydrophilic/underwater super oleophobic property. The patent uses a laser processing method to process micro-nano structure micro-protrusions on the metal surface, so that the micro-nano structure micro-protrusions have the functions of hydrophilicity and oleophobicity, but the laser processing cost is extremely high, and the basically original phase structure is easily damaged.
The prior metal net mainly has the technical problems of high cost, short service life, limited oil-water separation types, easy functional failure and the like when being applied to oil-water separation.
Diamond, on the other hand, is the hardest material in the world, possessing extremely stable physicochemical properties and a high modulus of elasticity. In the prior art patent CN 103741116A, a method for growing a CVD diamond coating on a metal mesh substrate to make the surface of the diamond mesh have superhydrophobicity and hydrophilicity has been proposed, but the process of the method is complex, the used deposition equipment is expensive and has high cost, only a diamond film can be grown on a small-sized workpiece, and the method is not suitable for a metal mesh for actual oil-water separation, and is not beneficial to industrial production and industrial use.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of an oil-water separation diamond coating metal net, which adopts a hot wire chemical vapor deposition mode to deposit a diamond coating on the surface of the metal net, wherein the temperature used by the hot wire chemical vapor deposition mode is generally lower than that of other modes, and the deformation of the metal net in the deposition process is effectively avoided by a low-temperature nano diamond growth method. The method has the advantages of high film forming rate, simple preparation process, stable process and low cost, and is suitable for industrial production and large-scale industrial use.
The second object of the present invention is to provide a metal mesh deposition coating device for hot filament chemical vapor deposition in the preparation method of the oil-water separation diamond coating metal mesh, wherein the deposition device is simple, the metal mesh can be fixed, the metal mesh can not deform in the deposition process, and the metal mesh deposition coating device is very suitable for preparing chemical vapor deposition coatings in three dimensions.
The invention further aims to provide the diamond coating metal net prepared by the preparation method of the oil-water separation diamond coating metal net or the diamond coating metal net obtained by using the metal net deposition coating device through a hot wire chemical vapor deposition mode, and the metal net has the advantages of high oil-water separation efficiency and long service life.
The invention aims at providing an application of the diamond coated metal net in oil-water separation.
The invention aims at providing an oil-water separation device comprising the diamond coating metal net.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
In a first aspect, a method for preparing an oil-water separation diamond coated metal mesh is provided, comprising the following steps:
depositing a diamond coating on the surface of the metal net by adopting a hot filament chemical vapor deposition mode to obtain a diamond coating metal net;
preferably, the metal mesh is a copper mesh, a titanium mesh or a stainless steel mesh.
Preferably, on the basis of the technical scheme of the invention, when hot wire chemical vapor deposition is carried out, the gas source comprises hydrogen and methane gas, and the temperature of a reaction zone is 500-800 ℃, preferably 500-700 ℃, and further preferably 500-600 ℃;
Preferably, the reaction zone temperature is raised from room temperature to 500-800 ℃ at a heating rate of 15-25 ℃/min and maintained for 10-20min.
Preferably, on the basis of the technical scheme of the invention, the gas source also comprises inert gas; the total flow rate of hydrogen, methane gas and inert gas in the reaction process is 400-600mL/min, preferably 400-500mL/min, wherein the methane gas flow rate is 1-5% of the total flow rate, the hydrogen gas flow rate is 25-45% of the total flow rate, and the inert gas flow rate is 50-70% of the total flow rate;
and/or the deposition pressure is 1500-2000Pa, preferably 1500-1800Pa, further preferably 1500-1600Pa;
and/or the vertical distance between the upper heat extraction wire and the metal net is 20-25mm, and the vertical distance between the lower heat extraction wire and the metal net is 15-20mm;
and/or the deposition time is 1.5 to 3 hours, preferably 1.5 to 2.5 hours, further preferably 2 to 2.5 hours.
Preferably, on the basis of the technical scheme of the invention, the metal net is the metal net after the nano diamond crystal planting treatment;
Preferably, the crystal planting treatment comprises the steps of putting a metal net into a crystal planting solution, taking out and drying after ultrasonic treatment for 20-60min, and preferably drying by using inert gas;
Preferably, the seeding solution is a nano-diamond suspension; the nano diamond suspension preferably comprises nano diamond powder, dimethyl carbonate and water, wherein the mass of the nano diamond powder accounts for 0.005-0.01% of the mass of the nano diamond suspension, and the concentration of the dimethyl carbonate in the nano diamond suspension is 1X 10 -6-10×10-6 mol/L; preferably the pH of the nanodiamond suspension is 2-4.
Preferably, on the basis of the technical scheme of the invention, the preparation method of the oil-water separation diamond coating metal net comprises the following steps:
(a) Cleaning the surface of the metal net;
(b) Carrying out corrosion treatment on the cleaned metal net;
(c) Cleaning the metal net again;
(d) Carrying out nano diamond crystal planting treatment on the metal net;
(e) After the crystal planting treatment, depositing a diamond coating on the surface of the metal net by adopting a hot wire chemical vapor deposition mode to obtain a diamond coating metal net;
Preferably, step (a) and step (c) each independently comprise ultrasonically cleaning with water for 2-3 times, each time for 5-10min, and then ultrasonically cleaning with alcohol for 1-2 times, each time for 5-10min;
Preferably, step (b) comprises sonicating in an alkaline solution for 5-10min, followed by sonicating in an acid solution for 30-60s; preferably, the alkali solution is a NaOH solution with the concentration of 0.5-1 mol/L; preferably the acid solution is 0.5-1mol/L HCl solution;
preferably, the step (d) comprises putting the metal mesh into the seeding solution, taking out and drying after ultrasonic treatment for 20-60min, and preferably drying by drying with nitrogen; preferably, the crystal planting solution is nano diamond suspension; the nano diamond suspension preferably comprises nano diamond powder, dimethyl carbonate and water, wherein the mass of the nano diamond powder accounts for 0.005-0.01% of the mass of the nano diamond suspension, and the concentration of the dimethyl carbonate in the nano diamond suspension is 1X 10 -6-10×10-6 mol/L; preferably the pH of the nanodiamond suspension is 2-4.
In a second aspect, a metal mesh deposition coating device for hot filament chemical vapor deposition in the preparation method of the oil-water separation diamond coating metal mesh is provided, wherein the metal mesh deposition coating device comprises a clamp body positioned between an upper heat extraction wire and a lower heat extraction wire;
The clamp body comprises a first body and a second body which are arranged in parallel, hollows are formed in the first body and the second body independently, a metal net is arranged between the first body and the second body, the edge size of the metal net is larger than the hollows of the first body and the second body, and the first body and the second body are fixed through a detachable clamping mechanism perpendicular to the first body so as to clamp the metal net between the first body and the second body;
preferably, the first body and the second body are both molybdenum discs;
Preferably, the detachable clamping mechanism comprises a bolt and a nut.
Preferably, on the basis of the technical scheme of the invention, the clamp body further comprises a first spring piece and/or a second spring piece;
the first spring piece is positioned on the inner side of the first body;
the second spring piece is positioned on the inner side of the second body.
In a third aspect, the diamond coated metal mesh prepared by the preparation method of the oil-water separation diamond coated metal mesh or the diamond coated metal mesh prepared by using the metal mesh deposition coating device through a hot wire chemical vapor deposition mode is provided.
In a fourth aspect, there is provided an application of the diamond coated metal mesh in oil-water separation.
Preferably, on the basis of the technical scheme of the invention, the diamond coated metal net is placed in an oil-water mixture, oil can pass through the diamond coated metal net, and water cannot pass through the diamond coated metal net, so that the purpose of oil-water separation is achieved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention has strong practicability, and adopts the hot wire chemical vapor deposition technology to deposit the low-temperature nano diamond on the metal net. The method is suitable for the deposition of any metal mesh diamond coating, and effectively avoids the deformation of the metal mesh in the deposition process. The method has the advantages of simple diamond deposition equipment, high film forming speed, convenient operation and stable process. The diamond film prepared on the metal net is suitable for industrialized mass production, has low cost, and can deposit diamond coating with good binding force on each surface of the metal net in three dimensions. The method can grow the diamond film on a large-size workpiece, and is suitable for large-scale industrialized application.
(2) The invention adopts the action of hot filament chemical vapor deposition to grow the diamond coating on the metal net in three dimensions, so that the metal net with the diamond coating can be obtained, oil-water separation can be carried out, and the diamond has extremely high physical and chemical stability, so that the diamond can resist corrosion of strong acid, strong alkali and the like, and the high hardness and the elastic modulus of the diamond can greatly improve the service life of the diamond. Compared with other methods, the diamond coating metal net prepared by the method has high oil-water separation efficiency and long service life.
(3) The invention designs the fixture for metal mesh deposition and the device suitable for three-dimensionally depositing the nano diamond coating on the surface of the metal mesh, the designed hot filament chemical vapor deposition device has simple structure, can fix the metal mesh, can not deform the metal mesh in the deposition process, has more uniform metal mesh deposition temperature, has more uniform diamond film growth on the metal mesh, and is very suitable for preparing the chemical vapor deposition coating in the three-dimensional direction.
Drawings
FIG. 1 is a top view of a wire mesh deposition coating apparatus according to one embodiment of the present invention;
FIG. 2 is a front view of a metal mesh deposition coating apparatus according to one embodiment of the present invention;
FIG. 3 is a surface topography of a metal mesh according to example 1 of the present invention;
fig. 4 is a surface topography of a diamond film grown on a metal mesh according to example 1 of the present invention.
Icon: 100-a clamp body; 110-a first body; 120-a second body; 130-a detachable clamping mechanism; 131-bolts; 132-nut; 141-a first spring piece; 142-a second spring piece; 200-metal mesh; 300-upper and lower heat discharging wires.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
According to a first aspect of the present invention, there is provided a method for preparing an oil-water separation diamond coated metal mesh, comprising the steps of:
and depositing a diamond coating on the surface of the metal net by adopting a hot filament chemical vapor deposition mode to obtain the diamond coated metal net.
Hot filament chemical vapor deposition (hot filament CVD) is one of the chemical vapor deposition methods, and this method mainly thermally decomposes hydrocarbon gases to produce carbon atom groups having the SP 3 hybridization orbitals necessary for diamond synthesis.
The hot wire chemical vapor deposition mode is not limited, and can be performed by adopting a conventional hot wire chemical vapor deposition device and/or process, and can be a common hot wire method, an electronic auxiliary hot wire method and other improved hot wire methods.
Typical but non-limiting metal mesh is, for example, copper mesh, titanium mesh or stainless steel mesh.
Diamond is the hardest material in the world, possessing extremely stable physicochemical properties and a high modulus of elasticity. A three-dimensional nano diamond coating is deposited on the surface of a metal wire mesh by adopting a hot wire chemical vapor deposition method, a carbon source and a hydrogen source are introduced in the deposition process, wherein the carbon source provides diamond growth, and the hydrogen source generates active hydrogen groups-H to etch SP 2 bonds of a non-diamond phase, so that a large number of-H group terminals exist in the whole deposition process, the whole deposition process is doped in the diamond coating, and the-H terminals can cause a super-hydrophobic special structure but cannot be oleophobic. And directly depositing a nano diamond coating with hydrophobicity and oleophylic property on the surface of the metal net by adopting a hot wire assisted chemical vapor deposition technology.
The temperature of the hot wire chemical vapor deposition method is generally lower than that of other methods (such as a microwave method and a flame combustion method), so that the method is a method for growing nano-diamond at low temperature, and the deformation of a metal net in the deposition process can be effectively avoided. Compared with other methods, the method has the advantages of high film forming rate, simple deposition equipment, suitability for large-area deposition, simple preparation process, stable process and low cost, and is suitable for industrial production and large-scale industrial use. The diamond coating grows on the metal mesh in three dimensions (all directions) by adopting the action of hot filament chemical vapor deposition, and the metal mesh with the diamond coating prepared by the method is hydrophobic and oleophilic, can be applied to oil-water separation, and has high oil-water separation efficiency; because the diamond has extremely high physical and chemical stability, the corrosion of strong acid, strong alkali and the like can be resisted, and the high hardness and the elastic modulus of the diamond can greatly improve the service life of the metal net.
In a preferred embodiment, the gas source comprises hydrogen and methane gas during hot filament chemical vapor deposition, and the reaction zone temperature is 500-800 ℃, preferably 500-700 ℃, and more preferably 500-600 ℃.
CH 4 and H 2 are required to be introduced during the deposition process, wherein CH 4 provides a carbon source for the growth of diamond and H 2 generates active hydrogen groups-H to etch the SP 2 bonds of the non-diamond phase.
The reaction zone temperature is typically, but not limited to, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, for example.
Preferably, the reaction zone temperature is raised from room temperature to 500-800 ℃ at a heating rate of 15-25 ℃/min and maintained for 10-20min.
The rate of heating is typically, but not limited to, for example 15 deg.C/min, 20 deg.C/min or 25 deg.C/min.
Incubation times are typically, but not limited to, for example 10min, 15min or 20min.
The temperature of the reaction area is lower during hot wire chemical vapor deposition, and the defect that the metal mesh is easy to deform in the deposition process and cannot be effectively deposited is overcome.
In a preferred embodiment, the gas source further comprises an inert gas; the total flow rate of hydrogen, methane gas and inert gas in the reaction process is 400-600mL/min, preferably 400-500mL/min, wherein the methane gas flow rate is 1-5% of the total flow rate, the hydrogen gas flow rate is 25-45% of the total flow rate, and the inert gas flow rate is 50-70% of the total flow rate.
A typical but non-limiting inert gas is argon.
The total flow rates of the hydrogen gas, the methane gas and the inert gas are controlled to be 400mL/min, 450mL/min, 500mL/min, 550mL/min or 600mL/min, for example.
Methane gas flow amounts to 1-5%, e.g., 1%, 2%, 3%, 4% or 5%, and hydrogen gas flow amounts to 25-45% of the total flow. For example 25%, 30%, 35%, 40% or 45%, the inert gas flow being 50-70%, for example 50%, 55%, 60%, 65% or 70%, of the total flow.
The nano diamond film with good quality and strong adhesive force can be grown by controlling the total flow and the flow ratio of hydrogen, methane gas and inert gas. Too little hydrogen gas is detrimental to the generation of active hydrogen radicals-H to etch SP 2 bonds of the non-diamond phase and too little CH 4 gas does not provide a sufficient carbon source for diamond growth.
In a preferred embodiment, the deposition pressure is 1500 to 2000Pa, preferably 1500 to 1800Pa, further preferably 1500 to 1600Pa.
The deposition pressure is typically, but not limited to, for example 1500Pa, 1600Pa, 1700Pa, 1800Pa, 1900Pa, or 2000Pa.
By controlling the deposition pressure, the high-quality film layer is obtained, and the grown diamond film has compact structure.
In a preferred embodiment, the upper heat drain wire is at a vertical distance of 20-25mm from the metal mesh and the lower heat drain wire is at a vertical distance of 15-20mm from the metal mesh.
The distance from the upper hot wire to the sample is, for example, 20mm, 21mm, 22mm, 23mm, 24mm or 25mm; the distance from the lower heat discharging wire to the sample is, for example, 15mm, 16mm, 17mm, 18mm, 19mm or 20mm.
The deposition temperature of the metal net is ensured by controlling the sample separation distance of the upper and lower heat discharging wires, so that the deposition temperature is more suitable and uniform.
In a preferred embodiment, the deposition time is from 1.5 to 3 hours, preferably from 1.5 to 2.5 hours, further preferably from 2 to 2.5 hours.
The deposition time is typically, but not limited to, for example, 1.5h, 2h, 2.5h, or 3h.
The thickness of the diamond film grown by controlling the deposition time is proper, and the adhesive force is good.
In a preferred embodiment, the metal mesh is a metal mesh subjected to nano-diamond seeding treatment; the nano diamond crystal planting treatment is carried out on the metal net before the diamond coating is deposited on the surface of the metal net by adopting a hot filament chemical vapor deposition mode.
The crystal planting treatment is to implant a layer of tiny diamond particles as nucleation points on the surface of the matrix in advance so as to improve the deposition density of the diamond.
A typical but non-limiting manner of seeding is by sonicating the surface of the substrate with a suspension containing a fine powder of diamond.
Preferably, the seeding treatment comprises ultrasonic treatment of the metal mesh in the seeding solution for 20-60min, and then taking out and drying, preferably drying by drying with inert gas, preferably nitrogen.
The ultrasound time is typically, but not limited to, for example 20min, 30min, 40min, 50min or 60min.
Preferably, the seeding solution is a nano-diamond suspension; preferably, the nano diamond suspension comprises nano diamond powder, dimethyl carbonate and water, wherein the mass of the nano diamond powder accounts for 0.005-0.01% of the mass of the nano diamond suspension, and the concentration of the dimethyl carbonate in the nano diamond suspension is 1X 10 -6-10×10-6 mol/L; preferably the pH of the nanodiamond suspension is 2-4.
The nano diamond suspension is prepared by dispersing nano diamond powder in a solvent of dimethyl carbonate and water, wherein the mass fraction of the nano diamond powder is 0.005-0.01%, such as 0.005%, 0.006%, 0.007%, 0.008%, 0.009% or 0.01%. The concentration of dimethyl carbonate (DMC) was 1×10-6mol/L、2×10-6mol/L、3×10-6mol/L、4×10-6mol/L、5×10- 6mol/L、6×10-6mol/L、7×10-6mol/L、8×10-6mol/L、9×10-6mol/L or 10X 10 -6 mol/L. The pH of the nanodiamond suspension is 2-4, for example pH2, pH3 or pH4.
The chip of diamond micro powder remained in the surface defect of the metal mesh after the metal mesh is subjected to crystal planting treatment by adopting the nano diamond suspension (crystal planting solution) can provide a nucleation core for diamond deposition by a hot wire chemical vapor deposition method, so that the nucleation density is improved, and the adhesive force of a diamond film and a substrate is remarkably improved.
In a preferred embodiment, the method for preparing the oil-water separation diamond coated metal mesh comprises the following steps:
(a) Cleaning the surface of the metal net;
(b) Carrying out corrosion treatment on the cleaned metal net;
(c) Cleaning the metal net again;
(d) Carrying out nano diamond crystal planting treatment on the metal net;
(e) After the crystal planting treatment, depositing a diamond coating on the surface of the metal net by adopting a hot wire chemical vapor deposition mode to obtain a diamond coating metal net;
preferably, step (a) comprises ultrasonically cleaning with water for 2-3 times, each time for 5-10min, and then ultrasonically cleaning with alcohol for 1-2 times, each time for 5-10min.
Firstly, cleaning the surface of the metal net, removing impurities on the surface of the metal net, and keeping the surface of the sample clean.
Preferably, step (b) comprises sonicating in an alkaline solution for 5-10min, followed by sonicating in an acid solution for 30-60s; preferably, the alkali solution is a NaOH solution with the concentration of 0.5-1 mol/L; preferably the acid solution is a solution of 0.5-1mol/L HCl.
Ultrasonic treatment is performed in an alkaline solution for 5-10min, such as 5min, 6min, 7min, 8min, 9min or 10min, and then in an acid solution for 30-60s, such as 30s, 40s, 50s or 60s.
The concentration of the alkali solution is, for example, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L; the acid solution concentration is, for example, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L.
And (3) carrying out corrosion treatment on the cleaned metal net, increasing the surface roughness and improving the adsorption density of diamond particles.
Preferably, step (c) comprises ultrasonically cleaning with water for 2-3 times, each time for 5-10min, and then ultrasonically cleaning with alcohol for 1-2 times, each time for 5-10min.
And cleaning the metal net after the corrosion treatment, and cleaning the corrosion solution remained in the metal net.
Preferably, the step (d) comprises putting the metal mesh into the seeding solution, taking out and drying after ultrasonic treatment for 20-60min, and preferably drying by drying with nitrogen; preferably, the crystal planting solution is nano diamond suspension; preferably, the nano diamond suspension comprises nano diamond powder, dimethyl carbonate and water, wherein the mass of the nano diamond powder accounts for 0.005-0.01% of the mass of the nano diamond suspension, and the concentration of the dimethyl carbonate in the nano diamond suspension is 1X 10 -6-10×10-6 mol/L; preferably the pH of the nanodiamond suspension is 2-4.
And carrying out diamond crystal planting treatment on the metal net. The typical seeding solution is detonation nano-diamond suspension, the composition is diamond powder with the mass fraction of 0.005%, DMC concentration of 5× -6 M, the rest is deionized water, and pH is 3. The crystal planting mode is to put the sample into crystal planting solution for ultrasonic treatment for 30 minutes, take out and blow-dry with nitrogen.
Step (e) uses a hot wire chemical vapor deposition process to deposit a diamond coating on the surface of the wire mesh in the same manner as described above.
The preparation method of the typical diamond coating metal net increases the nucleation density and the secondary nucleation rate of growth by a surface pretreatment method of corrosion treatment and crystal planting treatment before hot filament chemical vapor deposition, and obtains the film with the nano-size grain size, and the prepared diamond coating metal net has high oil-water separation efficiency and long service life.
According to a second aspect of the present invention, there is provided a wire mesh deposition coating apparatus for hot filament chemical vapor deposition in the above-mentioned method for preparing an oil-water separation diamond coated wire mesh, as shown in fig. 1 and 2, the wire mesh deposition coating apparatus comprising a jig body 100 positioned between upper and lower heat discharging wires 300; the fixture body 100 includes a first body 110 and a second body 120 arranged in parallel, the interiors of the first body 110 and the second body 120 are respectively provided with a cavity, the metal mesh 200 is arranged between the first body 110 and the second body 120, the edge size of the metal mesh 200 is larger than the cavity size of the first body 110 and the second body 120, and the first body 110 and the second body 120 are fixed by a detachable clamping mechanism 130 perpendicular to the first body 110 so as to clamp the metal mesh 200 between the first body 110 and the second body 120.
In use, the metal mesh 200 is placed between the first body 110 and the second body 120, the first body 110 and the second body 120 are clamped by the detachable clamping mechanism 130, so that the metal mesh 200 between the clamping is clamped, and since the middle of the first body 110 and the second body 120 is empty, the edge size of the metal mesh 200 is larger than the cavity size of the first body 110 and the second body 120, and the metal mesh 200 can be supported between the first body 110 and the second body 120. The shape of the hollow is not limited as long as the edge of the metal mesh 200 is supported between the first body 110 and the second body 120 without being moved out, forming a clamp. The device is placed in position on the deposition substrate while depositing the coating.
The hot wire chemical vapor deposition device designed by the invention has a simple structure, can fix the metal mesh, can not deform the metal mesh in the deposition process, is very suitable for preparing the chemical vapor deposition coating in the three-dimensional direction, ensures that the deposition temperature of the metal mesh is more uniform, ensures that the deposited diamond film of the low-temperature nano diamond coating grows uniformly by using the designed device, and has better oil-water separation effect of the obtained diamond coating metal mesh.
Preferably, the first body and the second body are both molybdenum discs.
The molybdenum has high melting point, can keep high strength at high temperature, has high elastic modulus and low weight, and is an ideal carrier material for the clamp body.
Preferably, the removable clamping mechanism 130 includes a bolt 131 and a nut 132.
The detachable clamping mechanism comprises a plurality of bolts and nuts, the bolts penetrate through the first body and the second body which are parallel, the distance between the first body and the second body is adjusted through the nuts, the first body and the second body are screwed down, the middle metal net is clamped, the metal net is fixed, and the metal net is prevented from deforming at high temperature.
In a preferred embodiment, the clip body 100 further includes a first spring piece 141 and/or a second spring piece 142; the first spring piece 141 is located inside the first body 110; the second spring piece 142 is located inside the second body 120.
The inner side here means the side of the metal mesh in contact with the body.
Through setting up first spring leaf and/or second spring leaf, can avoid the metal mesh to appear the gap when fixed with bolt and nut, make the metal mesh press from both sides tightly fixed more firm, further prevent the metal mesh deformation.
According to a third aspect of the present invention, there is provided a diamond coated metal mesh prepared by the above-mentioned preparation method of an oil-water separation diamond coated metal mesh or a diamond coated metal mesh obtained by a hot wire chemical vapor deposition method using the above-mentioned metal mesh deposition coating apparatus.
The diamond coated metal net prepared by the method or the diamond coated metal net prepared by using the device to carry out hot wire chemical vapor deposition has good oil-water separation effect, high oil-water separation efficiency and long service life.
According to a fourth aspect of the present invention there is provided the use of a diamond coated metal mesh as described above in oil-water separation.
The obtained diamond coating metal net has hydrophobic and oleophilic properties, can be applied to oil-water separation, has good separation effect, high efficiency and long service life, and has wide application prospect.
Preferably, the method can be used for separating oily sewage containing common organic solvents, animal and vegetable oils, petroleum, gasoline, diesel oil, crude oil and the like.
Preferably, the diamond coated metal mesh is placed in an oil-water mixture, and oil can pass through the diamond coated metal mesh while water cannot pass through the diamond coated metal mesh, so as to achieve the purpose of oil-water separation.
When oil-water separation is carried out, the metal net can be manufactured into various shapes according to actual conditions, for example, an oil-water mixture is poured on the metal net, oil drops (filters) through the metal net, and water still stays on the surface of the metal net. For example, the metal net can be enclosed into a fence (a circle is enclosed), the fence is placed in an oil-water mixture, oil enters the fence enclosed by the metal net and is collected, and water cannot enter the metal net, so that marine petroleum pollution can be treated by the method.
According to a fifth aspect of the present invention there is provided an oil-water separator comprising the diamond coated metal mesh described above.
The oil-water separation device has the same advantages as the diamond coated metal mesh.
The invention is further illustrated by the following specific examples and comparative examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any way. The raw materials involved in the invention are all available commercially.
The metal mesh of the examples and comparative examples was copper mesh.
The detonation nanodiamond suspension used in the examples and comparative examples had a composition of 0.005% diamond powder mass fraction, DMC concentration of 5×10 -6 M, balance deionized water, pH 3.
Example 1
The preparation method of the diamond coated metal net comprises the following steps:
(1) Cleaning the surface of the metal mesh, firstly ultrasonically cleaning the metal mesh with deionized water for 2 times, each time for 5 minutes, and finally ultrasonically cleaning the metal mesh with alcohol for 5 minutes, and drying the metal mesh with nitrogen;
(2) And (3) carrying out corrosion treatment on the cleaned metal net, increasing the surface roughness and improving the adsorption density of the diamond nano particles. The etching treatment was ultrasonic cleaning in an alkali solution for 5 minutes, followed by cleaning in an acid solution for 30 seconds. Wherein the alkali solution is 1M NaOH, and the acid solution is 1M HCl;
(3) And cleaning the metal net, and cleaning the corrosive solution remained in the metal net. Ultrasonically cleaning with deionized water for 2 times, 5 minutes each time, and finally ultrasonically cleaning with alcohol for 5 minutes, and drying with nitrogen;
(4) Carrying out crystal planting treatment on the nano diamond on the metal net, wherein the crystal planting solution is detonation nano diamond suspension, and the crystal planting mode is that a sample is placed into the crystal planting solution for ultrasonic treatment for 30 minutes, taken out and dried by nitrogen;
(5) Preparing a three-dimensional nano diamond film on the metal net after the crystal planting by using hot filament CVD, heating from room temperature to 600 ℃ at a heating rate of 20 ℃/min, and preserving heat for 15min; in the reaction process, the total flow of gas is controlled to be 500mL/min, the total flow of methane, argon and hydrogen is controlled to be 500mL/min, wherein the total flow of methane, argon and hydrogen is 10mL/min, argon is 282mL/min, and hydrogen is 208mL/min. The pressure was 1500Pa. The distance between the upper heat extraction filament and the sample is 25mm, the distance between the lower heat extraction filament and the sample is 15mm, and the deposition time is 2 hours.
FIG. 3 is a surface topography of the metal mesh of example 1; fig. 4 is a surface topography of a diamond film grown on a wire mesh of example 1.
Example 2
The preparation method of the diamond coated metal net comprises the following steps:
(1) And cleaning the surface of the metal mesh, firstly ultrasonically cleaning the metal mesh with deionized water for 3 times, each time for 5 minutes, and finally ultrasonically cleaning the metal mesh with alcohol for 5 minutes, and drying the metal mesh with nitrogen.
(2) And (3) carrying out corrosion treatment on the cleaned metal net, increasing the surface roughness and improving the adsorption density of the diamond nano particles. The etching treatment was ultrasonic cleaning in an alkali solution for 10 minutes, followed by cleaning in an acid solution for 60 seconds. Wherein the alkali solution is as follows: 0.5M NaOH and 0.5M HCl as acid solution.
(3) And cleaning the metal net, and cleaning the corrosive solution remained in the metal net. Ultrasonic cleaning with deionized water for 3 times each for 5 minutes, ultrasonic cleaning with alcohol for 5 minutes, and blow-drying with nitrogen.
(4) And (3) carrying out nano-diamond crystal planting treatment on the metal net, wherein the crystal planting solution is detonation nano-diamond suspension. The crystal planting mode is to put the sample into crystal planting solution for ultrasonic treatment for 30 minutes, take out and blow-dry with nitrogen.
(5) Preparing a three-dimensional nano diamond film on the metal net after the crystal planting by using hot filament CVD, heating from room temperature to 600 ℃ at a heating rate of 20 ℃/min, and preserving heat for 15min; in the reaction process, the total flow of gas is controlled to be 400mL/min, the total flow of methane, argon and hydrogen is controlled to be 400mL/min, wherein the total flow of methane is 5mL/min, the total flow of argon is 255mL/min, and the total flow of hydrogen is 140mL/min. The pressure was 1500Pa. The distance between the upper heat extraction filament and the sample is 25mm, the distance between the lower heat extraction filament and the sample is 15mm, and the deposition time is 3 hours.
Example 3
The preparation method of the diamond coated metal net comprises the following steps:
(1) And cleaning the surface of the metal mesh, firstly ultrasonically cleaning the metal mesh with deionized water for 2 times, each time for 10 minutes, and finally ultrasonically cleaning the metal mesh with alcohol for 5 minutes, and drying the metal mesh with nitrogen.
(2) And (3) carrying out corrosion treatment on the cleaned metal net, increasing the surface roughness and improving the adsorption density of the diamond nano particles. The etching treatment was ultrasonic cleaning in an alkali solution for 8 minutes, followed by cleaning in an acid solution for 40 seconds. Wherein the alkali solution is as follows: 0.6M NaOH and 0.6M HCl as acid solution.
(3) And cleaning the metal net, and cleaning the corrosive solution remained in the metal net. Ultrasonic cleaning with deionized water for 2 times each for 10 minutes, ultrasonic cleaning with alcohol for 5 minutes, and blow-drying with nitrogen.
(4) And (3) carrying out nano-diamond crystal planting treatment on the metal net, wherein the crystal planting solution is detonation nano-diamond suspension. The crystal planting mode is to put the sample into crystal planting solution for ultrasonic treatment for 30 minutes, take out and blow-dry with nitrogen.
(5) Preparing a three-dimensional nano diamond film on the metal net after the crystal planting by using hot filament CVD, heating from room temperature to 600 ℃ at a heating rate of 20 ℃/min, and preserving heat for 15min; in the reaction process, the total flow of gas is controlled to be 420mL/min, the total flow of methane, argon and hydrogen is controlled to be 420mL/min, wherein the total flow of methane is 15mL/min, the total flow of argon is 255mL/min, and the total flow of hydrogen is 150mL/min. The pressure was 1500Pa. The distance between the upper heat extraction filament and the sample is 25mm, the distance between the lower heat extraction filament and the sample is 15mm, and the deposition time is 1.5 hours.
Example 4
The preparation method of the diamond coated metal net comprises the following steps:
(1) And cleaning the surface of the metal mesh, firstly ultrasonically cleaning the metal mesh with deionized water for 2 times, each time for 5 minutes, and finally ultrasonically cleaning the metal mesh with alcohol for 10 minutes, and drying the metal mesh with nitrogen.
(2) And (3) carrying out corrosion treatment on the cleaned metal net, increasing the surface roughness and improving the adsorption density of the diamond nano particles. The etching treatment was ultrasonic cleaning in an alkali solution for 5 minutes, followed by cleaning in an acid solution for 30 seconds. Wherein the alkali solution is as follows: 1M NaOH and 1M HCl as acid solution.
(3) And cleaning the metal net, and cleaning the corrosive solution remained in the metal net. Ultrasonic cleaning with deionized water for 2 times each for 5 minutes, ultrasonic cleaning with alcohol for 10 minutes, and blow-drying with nitrogen.
(4) And (3) carrying out nano-diamond crystal planting treatment on the metal net, wherein the crystal planting solution is detonation nano-diamond suspension. The crystal planting mode is to put the sample into crystal planting solution for ultrasonic treatment for 20 minutes, take out and blow-dry with nitrogen.
(5) Preparing a three-dimensional nano diamond film on the metal net after the crystal planting by using hot filament CVD, heating from room temperature to 500 ℃ at a heating rate of 15 ℃/min, and preserving heat for 20min; in the reaction process, the total flow of gas is controlled to be 500mL/min, the total flow of methane, argon and hydrogen is controlled to be 500mL/min, wherein the total flow of methane is 5mL/min, the argon is 255mL/min, and the hydrogen is 140mL/min. The pressure was 2000Pa. The distance between the upper heat extraction filament and the sample is 25mm, the distance between the lower heat extraction filament and the sample is 15mm, and the deposition time is 4 hours.
Example 5
The preparation method of the diamond coated metal net comprises the following steps:
(1) And cleaning the surface of the metal mesh, firstly ultrasonically cleaning the metal mesh with deionized water for 2 times, each time for 5 minutes, and finally ultrasonically cleaning the metal mesh with alcohol for 5 minutes, and drying the metal mesh with nitrogen.
(2) And (3) carrying out corrosion treatment on the cleaned metal net, increasing the surface roughness and improving the adsorption density of the diamond nano particles. The etching treatment was ultrasonic cleaning in an alkali solution for 5 minutes, followed by cleaning in an acid solution for 30 seconds. Wherein the alkali solution is as follows: 1M NaOH and 1M HCl as acid solution.
(3) And cleaning the metal net, and cleaning the corrosive solution remained in the metal net. Ultrasonic cleaning with deionized water for 2 times each for 5 minutes, ultrasonic cleaning with alcohol for 5 minutes, and blow-drying with nitrogen.
(4) And (3) carrying out nano-diamond crystal planting treatment on the metal net, wherein the crystal planting solution is detonation nano-diamond suspension. The crystal planting mode is to put the sample into crystal planting solution for ultrasonic treatment for 60 minutes, take out and blow-dry with nitrogen.
(5) Preparing a three-dimensional nano diamond film on the metal net after the crystal planting by using hot filament CVD, heating from room temperature to 800 ℃ at a heating rate of 25 ℃/min, and preserving heat for 10min; in the reaction process, the total flow of gas is controlled to be 500mL/min, the total flow of methane, argon and hydrogen is controlled to be 500mL/min, wherein the total flow of methane is 5mL/min, the argon is 255mL/min, and the hydrogen is 140mL/min. The pressure was 1500Pa. The distance between the upper heat extraction filament and the sample is 20mm, the distance between the lower heat extraction filament and the sample is 18mm, and the deposition time is 2 hours.
Example 6
Unlike example 1, the temperature of step (5) was raised from room temperature to 1000 ℃ at a heating rate of 20 ℃/min, and the temperature was maintained for 15min.
Example 7
Unlike example 1, the total flow of the gases in step (5) was controlled to be 500mL/min, the total flow of methane+argon+hydrogen was controlled to be 500mL/min, wherein methane was 50mL/min, argon was 282mL/min, and hydrogen was 168mL/min.
Example 8
Unlike example 1, step (5) uses a wire mesh deposition coating apparatus to prepare a three-dimensional nano-diamond film on the wire mesh after the crystal planting.
The metal mesh deposition coating device comprises a clamp body positioned between the upper heat extraction wire and the lower heat extraction wire; the fixture body comprises an upper molybdenum disc and a lower molybdenum disc which are arranged in parallel, spring pieces are arranged on the inner sides of the upper molybdenum disc and the lower molybdenum disc, the metal net is arranged between the spring pieces of the molybdenum discs, bolts vertically penetrate the fixture body and penetrate the upper molybdenum disc and the lower molybdenum disc, and nuts are used for tightening the upper molybdenum disc and the lower molybdenum disc, so that the metal net is clamped.
Comparative example 1
Unlike example 2, the preparation method of the diamond coated metal mesh is that in step (5), the metal mesh after the crystal planting is subjected to three-dimensional nano diamond film preparation by using a microwave plasma CVD method, and experimental conditions are as follows: the total flow rate of the reaction gas was 300sccm, and the ratio was H 2：CH4 =292: 8 (sccm), a pressure of 130Torr, a microwave power of 1.7kw, a deposition substrate temperature of about 800℃and a deposition time of 7 hours, and a diamond film thickness of about 2 μm.
Comparative example 2
The preparation method of the diamond coated metal mesh is different from the preparation method in the embodiment 2, wherein in the step (5), the metal mesh after the crystal planting is subjected to three-dimensional nano diamond film preparation by using a flame combustion method, and experimental conditions are as follows: the total flow of reaction gas was 500sccm, the ratio H 2：C2H2：O2 =5: 245:250 (sccm), a pressure of 1000Pa, a deposition substrate temperature of about 1000 ℃, and a deposition time of 5 hours, to obtain a diamond film thickness of about 2. Mu.m.
Test examples
The diamond coated metal mesh obtained in example 1 was measured with a contact angle measuring instrument, and the contact angle of the diamond coated metal mesh surface to 3 microliters of n-hexane in an air environment was less than 15 degrees, and the diamond coated metal mesh was a super-hydrophobic material; and immersing the diamond coated metal mesh in n-hexane, and measuring the contact angle of the metal mesh surface to 3 microliters of water to be more than 135 degrees, wherein the diamond coated metal mesh is an oleophilic material.
In order to examine the oil-water separation performance of the diamond coated metal mesh obtained in examples and comparative examples, oil-water separation efficiency and service life were carried out, and the test method was as follows:
(1) Oil-water separation efficiency: the obtained metal net is placed in the middle of a vertically placed filter and fixed by a clamp, n-hexane and water are mixed under the magnetic stirring condition according to the proportion of 1:2 to obtain an oil-water mixture, the mixture is poured into an inlet at the upper part and poured into the filter, the n-hexane in the mixture rapidly passes through the metal net, the water is blocked above the metal net and cannot pass through the metal net, oil-water separation is realized, and the separation efficiency is obtained by calculating the ratio of the weight of the water reserved above the metal net to the weight of the water originally poured into the oil-water mixture.
(2) Service life is as follows: and repeatedly using the obtained metal net according to the oil-water separation test, cleaning with water after each use, and calculating the separation efficiency after 50 times of use.
The test results are shown in Table 1.
TABLE 1
From the results in table 1, the oil-water separation efficiency of the metal net obtained by the method is high and reaches more than 99%, and after the metal net is reused for 50 times, the separation efficiency is almost unchanged and still reaches more than 98%, which shows that the prepared metal net has excellent recoverability and long service life.
Further analysis shows that the temperature of the hot filament CVD reaction in the example 1 is lower than that in the example 6, and as a result, the oil-water separation efficiency and the service life of the metal mesh obtained in the example 1 are better, and the quality of the obtained diamond film is better because the metal mesh is not deformed due to the lower temperature. Example 1 the ratio of hydrogen gas to methane gas of example 1 was in the preferred range of the present invention compared to example 7, and as a result, it was found that the metal mesh obtained in example 1 was better in oil-water separation performance, and thus it was found that the diamond film obtained with a certain ratio of hydrogen gas to methane gas was better in quality and performance.
Compared with example 1, the deposition device designed by the invention is adopted to carry out hot filament CVD deposition, and the result shows that the metal mesh obtained after deposition has better oil-water separation performance, because the device can prevent the metal mesh from deforming and lead the deposition temperature of the metal mesh to be more uniform, the diamond film can grow more uniformly, the obtained metal mesh has better hydrophobic and oleophilic performance and higher separation efficiency.
The method for depositing the diamond coating in the comparative example 1 adopts a microwave plasma CVD method, and has better oil-water separation effect, but the deposition equipment is expensive and has high cost, and the diamond film can only be grown on small-size workpieces, and the oil-water separated metal net is large-area, so that the method for depositing the diamond film on the surface of the metal net is only suitable for laboratory research, and is not suitable for industrial production and a large number of industrial uses.
Comparative example 2 the deposition of diamond coating was carried out by flame combustion, and the oil-water separation performance of the obtained metal mesh was inferior to that of the present invention.
In conclusion, the nano diamond is grown by the hot wire chemical vapor deposition method and the metal mesh deposition coating device, so that the deformation of the metal mesh in the deposition process is effectively avoided, the method has the advantages of high film forming rate, simple preparation process, stable process and low cost, is suitable for industrial production and large-scale industrial use, and the obtained metal mesh has high oil-water separation efficiency and long service life.
While particular embodiments of the present invention have been illustrated and described, it should be appreciated that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (4)
1. The preparation method of the oil-water separation diamond coating metal net is characterized by comprising the following steps of:
(a) Cleaning the surface of the metal net;
(b) Carrying out corrosion treatment on the cleaned metal net;
(c) Cleaning the metal net again;
(d) Carrying out nano diamond crystal planting treatment on the metal net;
(e) After the crystal planting treatment, depositing a diamond coating on the surface of the metal net by adopting a hot wire chemical vapor deposition mode to obtain a diamond coating metal net;
in hot wire chemical vapor deposition, the gas source comprises hydrogen and methane gas, and the temperature of a reaction zone is 600 ℃;
the temperature of the reaction zone is raised from room temperature to 600 ℃ at a heating rate of 20 ℃/min, and the temperature is kept for 15min;
the gas source also comprises inert gas; the total flow of hydrogen, methane gas and inert gas in the reaction process is 500mL/min, wherein the flow of methane is 10 mL/min, the flow of argon is 282/mL/min, and the flow of hydrogen is 208/mL/min;
the deposition pressure is 1500Pa;
The vertical distance between the upper heat extraction wire and the metal net is 25mm, and the vertical distance between the lower heat extraction wire and the metal net is 15mm;
The deposition time is 2h;
Step (b) comprises ultrasonic treatment in an alkali solution for 5min, and ultrasonic treatment in an acid solution for 30s; the alkali solution is NaOH solution with the concentration of 1 mol/L; the acid solution is HCl solution of 1 mol/L;
the crystal planting treatment comprises the steps of putting a metal net into a crystal planting solution, taking out and drying after ultrasonic treatment for 30min, wherein the drying mode is that nitrogen is used for drying;
the crystal planting solution is nano diamond suspension; the nano diamond suspension comprises nano diamond powder, dimethyl carbonate and water, wherein the mass of the nano diamond powder is 0.005% of the mass of the nano diamond suspension, and the concentration of the dimethyl carbonate in the nano diamond suspension is 5 multiplied by 10 -6 mol/L; the pH of the nanodiamond suspension was 3;
A diamond coating metal net is obtained by a hot wire chemical vapor deposition mode by using a metal net deposition coating device;
The metal mesh deposition coating device comprises a clamp body (100) positioned between an upper heat extraction wire (300) and a lower heat extraction wire;
the clamp body (100) comprises a first body (110) and a second body (120) which are arranged in parallel, the interiors of the first body (110) and the second body (120) are respectively and independently provided with a cavity, a metal net (200) is arranged between the first body (110) and the second body (120), the edge size of the metal net (200) is larger than the cavity size of the first body (110) and the second body (120), and the first body (110) and the second body (120) are fixed through a detachable clamping mechanism (130) perpendicular to the first body (110) so as to clamp the metal net (200) between the first body (110) and the second body (120);
the clamp body (100) further comprises a first spring piece (141) and a second spring piece (142);
The first spring piece (141) is positioned on the inner side of the first body (110);
a second spring piece (142) is located inside the second body (120).
2. The method of preparing a diamond coated metal mesh for oil-water separation according to claim 1, wherein each of the steps (a) and (c) independently comprises ultrasonic cleaning with water for 2 to 3 times, each time for 5 to 10 minutes, and ultrasonic cleaning with alcohol for 1 to 2 times, each time for 5 to 10 minutes.
3. The method for preparing the oil-water separation diamond coated metal mesh according to claim 1, wherein the metal mesh is a copper mesh, a titanium mesh or a stainless steel mesh.
4. A method of producing a metal mesh coated with an oil-water separation diamond according to any one of claims 1 to 3, characterized in that the first body (110) and the second body (120) are both molybdenum discs;
the detachable clamping mechanism (130) comprises a bolt (131) and a nut (132).
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| CN208346252U (en) * | 2018-03-12 | 2019-01-08 | 深圳先进技术研究院 | Metal mesh deposition of diamond coatings device and metal mesh deposition of diamond coatings system |
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| CN101514445A (en) * | 2009-04-08 | 2009-08-26 | 南京航空航天大学 | Device for preparing double-sided diamond coating based on heat wire method |
| CN103741116A (en) * | 2014-01-27 | 2014-04-23 | 吉林大学 | Diamond net and application of diamond net in separating oil-water mixture and transferring liquid drops |
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