CN115445888B - Magnesium alloy-based layered composite material and preparation method thereof - Google Patents
Magnesium alloy-based layered composite material and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
Abstract
The invention provides a magnesium alloy-based layered composite material and a preparation method thereof, comprising the following steps: dispersing carboxylated graphene in a solvent to obtain graphene dispersion liquid; dispersing carbon nanotubes in a solvent to obtain a carbon nanotube dispersion; sequentially spraying and depositing the carbon nanotube dispersion liquid, the graphene dispersion liquid and the carbon nanotube dispersion liquid on the surface of the magnesium foil to obtain a magnesium-based composite sheet layer containing a spraying layer; crushing the magnesium-based composite sheet into layered elements, and placing the layered elements into a die to sequentially perform vacuum hot-press sintering and hot extrusion to obtain the magnesium alloy-based layered composite material. The magnesium alloy-based layered composite material provided by the invention realizes the cooperative enhancement of mechanical property and electromagnetic shielding effect, and widens the application of magnesium alloy in the field of electromagnetic shielding.
Description
Technical Field
The invention relates to the technical field of metal composite materials, in particular to a magnesium alloy-based layered composite material and a preparation method thereof.
Background
The magnesium-based composite material not only has the advantages of high specific strength, high specific rigidity, good wear resistance and the like, but also has good electromagnetic shielding performance, so that the magnesium-based composite material is widely applied to the fields of riding, aerospace, electronic products and the like. However, the magnesium alloy has good shielding effect on low-frequency electromagnetic waves (less than or equal to 300MHz, namely, the radio wave category), and has unsatisfactory shielding effect on high-frequency and ultrahigh-frequency electromagnetic waves, so that the magnesium alloy is difficult to resist attack of weapons of high-frequency and ultrahigh-frequency electronic stations, and the electromagnetic shielding capability of electronic warfare equipment determines the battlefield viability and even affects the success or failure of warfare. Therefore, the defect of narrow shielding frequency band of the existing magnesium alloy seriously hinders the application in the field of national defense electromagnetic shielding.
Disclosure of Invention
The embodiment of the invention provides a magnesium alloy-based layered composite material and a preparation method thereof, wherein the magnesium alloy-based layered composite material has excellent mechanical property and electromagnetic shielding effect, and widens the application of magnesium alloy in the field of electromagnetic shielding.
In a first aspect, the present invention provides a method for preparing a magnesium alloy-based layered composite material, the method comprising:
dispersing carboxylated graphene in a solvent to obtain graphene dispersion liquid; dispersing carbon nanotubes in the solvent to obtain a carbon nanotube dispersion;
sequentially spraying and depositing the carbon nanotube dispersion liquid, the graphene dispersion liquid and the carbon nanotube dispersion liquid on the surface of the magnesium foil to obtain a magnesium-based composite sheet layer comprising a spraying layer;
and crushing the magnesium-based composite sheet into layered elements, and placing the layered elements into a die to sequentially perform vacuum hot-press sintering and hot extrusion to obtain the magnesium alloy-based layered composite material.
Preferably, the carboxylated graphene is obtained by pickling graphene nano sheets.
Preferably, the graphene nanoplatelets have a size of 0.5-5 μm.
More preferably, the thickness of the graphene nanoplatelets is 0.8-1.2 nm.
Preferably, the diameter of the carbon nanotube is 30-80 nm.
Preferably, the carbon nanotubes have a length of less than 10 μm.
Preferably, the preparation method of the carboxylated graphene comprises the following steps: and placing the graphene nano-sheets in an acid solution, and stirring for 4-6 hours at the temperature of 60-80 ℃.
More preferably, the preparation method of carboxylated graphene comprises the following steps: and placing the graphene nano-sheets in an acid solution, performing ultrasonic treatment for 20-40 min, and stirring for 4-6 h at 60-80 ℃.
Preferably, the carbon nanotubes are obtained by the acid washing; the acid washing comprises the steps of placing the carbon nano tube in the acid solution and stirring the carbon nano tube for 4 to 6 hours at the temperature of between 60 and 80 ℃.
More preferably, the carbon nanotubes are obtained by acid washing; the acid washing comprises the steps of placing the carbon nano tube in the acid solution for ultrasonic treatment for 20-40 min, and stirring for 4-6 h at 60-80 ℃.
Preferably, the acid solution is a mixed solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1.
Preferably, the mass concentration of the carboxylated graphene in the graphene dispersion liquid is 0.5-0.7 g/L.
More preferably, the mass concentration of the carboxylated graphene in the graphene dispersion is 0.6g/L.
Preferably, the mass concentration of the carbon nanotubes in the carbon nanotube dispersion liquid is 0.2-0.4 g/L.
More preferably, the mass concentration of the carbon nanotubes in the carbon nanotube dispersion is 0.3g/L.
Preferably, the solvent is absolute ethanol.
Preferably, before the spray deposition, the method further comprises:
and polishing the magnesium foil, and heating the magnesium foil to 80-100 ℃.
Preferably, the spray pressure of the spray deposition is 0.2-0.4 MPa.
More preferably, the spray deposition has a spray pressure of 0.3MPa.
Preferably, the spray layer comprises a carbon nanotube layer, a carboxylated graphene layer and a carbon nanotube layer which are sequentially connected.
Preferably, the mass of the sprayed layer is 0.45-0.55 wt% of the mass of the magnesium foil.
More preferably, the mass ratio of the carbon nanotube layer, the carboxylated graphene layer and the carbon nanotube layer in the spray layer is 1:1:1.
Preferably, the layered element has a size of 1.5 to 2.5mm and a thickness of 45 to 55 μm.
Preferably, the temperature of the vacuum hot-pressing sintering is 625-635 ℃, the pressure is 45-55 MPa, the time is 5.5-6.5 h, and the vacuum degree is 4 multiplied by 10 -3 ～6×10 -3 Pa。
More preferably, the temperature of the vacuum hot press sintering is 630 ℃, the pressure is 50MPa, and the time is 6h.
Preferably, the temperature of the hot extrusion is 380-420 ℃, the pressure ratio is (25-30): 1, and the extrusion speed is 0.1-0.3 mm/s.
More preferably, the temperature of the hot extrusion is 400 ℃, the pressure ratio is 29:1, and the extrusion speed is 0.1mm/s.
In a second aspect, the invention provides a magnesium alloy-based layered composite material prepared by the preparation method in the first aspect.
Preferably, the magnesium alloy-based layered composite material is obtained by vacuum hot-pressing sintering and hot extrusion of layered elements; the layered primitive is a magnesium-based composite sheet layer with a spraying layer on the surface, and the spraying layer comprises a carbon nano tube layer, a carboxylated graphene layer and a carbon nano tube which are sequentially connected.
Compared with the prior art, the invention has at least the following beneficial effects:
firstly, preparing a magnesium-based composite sheet layer containing a nano carbon layer, wherein the nano carbon layer with carbon nano tubes at the bottom and the top and carboxylated graphene in the middle is formed on the surface of the magnesium-based composite sheet layer through the mechanical properties of carboxylated graphene and carbon nano Guan Zengjiang magnesium foil; then crushing the magnesium-based composite sheet layer to obtain a layered primitive, and carrying out vacuum hot-pressing sintering and hot extrusion on the layered primitive to obtain the magnesium alloy-based layered composite material, wherein the existence of the nano carbon layer enables the mechanical property and the electromagnetic wave shielding property of the composite material to be obviously improved, thereby realizing the integration of light-mechanical-shielding function.
According to the invention, the carboxylated graphene and the carbon nanotubes in the nano carbon layer form a three-dimensional network communication structure, so that the transmission path of electromagnetic waves in the nano carbon layer is more complex and roundabout, and the loss of the electromagnetic waves in the transmission process is enhanced. The magnesium alloy-based layered composite material is prepared from layered elements, electromagnetic waves are reflected between the layered composite materials for multiple times, and the enhancement of electromagnetic wave absorption loss is further enhanced, so that the electromagnetic shielding efficiency is remarkably improved, and the application of the magnesium alloy in the field of electromagnetic shielding is widened.
Drawings
FIG. 1 is a flow chart of a method for preparing a magnesium alloy-based layered composite material according to an embodiment of the present invention;
FIG. 2 is an SEM image of the sprayed layer provided in example 1 of the present invention distributed on the surface of magnesium foil;
FIG. 3 is an SEM image of the sprayed layer distribution on the surface of magnesium foil provided in comparative example 2 of the present invention;
FIG. 4 is an SEM image of the sprayed layer distribution on the surface of magnesium foil provided in comparative example 3 of the present invention;
FIG. 5 is an optical microscope photograph of an extruded pure magnesium substrate provided in comparative example 1 of the present invention;
FIG. 6 is an optical microscope photograph of a magnesium alloy-based layered composite material provided in example 1 of the present invention;
FIG. 7 is an SEM image of a layered composite material based on magnesium alloy provided in example 1 of the present invention;
FIG. 8 is a TEM electron microscope image of the magnesium alloy-based layered composite material provided in example 1 of the present invention;
FIG. 9 is a stress-strain plot of the materials provided in inventive example 1, comparative examples 1-3;
FIG. 10 is a graph showing the total shielding effectiveness of the materials provided in example 1, comparative examples 1 to 3 of the present invention in the X-band;
FIG. 11 is a graph showing the absorption loss in the X-band of the materials provided in example 1, comparative examples 1 to 3 of the present invention;
fig. 12 is a graph showing reflection loss in the X-band of the materials provided in example 1, comparative examples 1 to 3 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments of the present invention are all within the scope of protection of the present invention.
The embodiment of the invention provides a preparation method of a magnesium alloy-based layered composite material, as shown in fig. 1, comprising the following steps:
step 1: dispersing carboxylated graphene in a solvent to obtain graphene dispersion liquid; dispersing carbon nanotubes in a solvent to obtain a carbon nanotube dispersion;
step 2: sequentially spraying and depositing the carbon nanotube dispersion liquid, the graphene dispersion liquid and the carbon nanotube dispersion liquid on the surface of the magnesium foil to obtain a magnesium-based composite sheet layer containing a spraying layer;
step 3: crushing the magnesium-based composite sheet into layered elements, and placing the layered elements into a die to sequentially perform vacuum hot-press sintering and hot extrusion to obtain the magnesium alloy-based layered composite material.
In the step 1, the solvent is a volatile solvent, so that the carboxylated graphene and the carbon nanotubes can be conveniently dispersed, and the carboxylated graphene and the carbon nanotubes can be easily removed during spray deposition. In step 2, the same spray deposition operation is required for both surfaces of the magnesium foil.
Firstly, preparing a magnesium-based composite sheet layer containing a nano carbon layer, wherein the nano carbon layer with carbon nano tubes at the bottom and the top and carboxylated graphene in the middle is formed on the surface of the magnesium-based composite sheet layer through the mechanical properties of carboxylated graphene and carbon nano Guan Zengjiang magnesium foil; then crushing the magnesium-based composite sheet layer to obtain a layered primitive, and carrying out vacuum hot-pressing sintering and hot extrusion on the layered primitive to obtain the magnesium alloy-based layered composite material, wherein the existence of the nano carbon layer enables the mechanical property and the electromagnetic wave shielding property of the composite material to be obviously improved, thereby realizing the integration of light-mechanical-shielding function.
According to some preferred embodiments, the carboxylated graphene is obtained from graphene nanoplatelets by acid washing.
According to some preferred embodiments, the method of preparing carboxylated graphene comprises: placing the graphene nano-sheets in an acid solution, and stirring for 4-6 hours at 60-80 ℃; the acid solution is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1.
Specifically, the graphene nanoplatelets are placed in an acid solution for pickling and ultrasonic treatment for 20-40 min (for example, 20min, 25min, 30min, 35min or 40 min), then heated to 60-80 ℃ (for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃) in a water bath, stirred for 4-6 h (for example, 4h, 4.5h, 5h, 5.5h or 6 h), and then washed and filtered to pH 7 by distilled water to obtain carboxylated graphene.
According to the invention, through adding oxygen-containing functional groups on the surfaces of the graphene nano sheets, van der Waals force between the graphene nano sheets is reduced, and agglomeration between the graphene nano sheets is reduced, so that the graphene nano sheets can be uniformly dispersed on the magnesium foil during subsequent spray deposition, and the agglomeration is reduced.
According to some preferred embodiments, the graphene nanoplatelets have a size of 0.5 to 5 μm (e.g., may be 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, or 5 μm).
According to some preferred embodiments, the graphene nanoplatelets have a thickness of 0.8 to 1.2nm (e.g., may be 0.8nm, 0.85nm, 0.9nm, 0.95nm, 1nm, 1.05nm, 1.1nm, 1.15nm, or 1.2 nm).
The carboxylated graphene has the same size as the graphene nanoplatelets. The size of the graphene nanoplatelets herein refers specifically to their sheet diameter.
According to some preferred embodiments, the carbon nanotubes have a diameter of 30 to 80nm (e.g., may be 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, or 80 nm).
According to some preferred embodiments, the carbon nanotubes are less than 10 μm in length (e.g., may be 9.9 μm, 9.5 μm, 9 μm, 8.5 μm, 8 μm, 7.5 μm, 7 μm, 6.5 μm, 6 μm, 5.5 μm, 5 μm, etc.).
According to some preferred embodiments, the carbon nanotubes are obtained by acid washing; the acid washing comprises the steps of placing the carbon nano tube in an acid solution and stirring the carbon nano tube for 4 to 6 hours at the temperature of between 60 and 80 ℃.
Specifically, the carbon nanotubes are placed in an acid solution and subjected to acid washing and ultrasonic treatment for 20-40 min (for example, 20min, 25min, 30min, 35min or 40 min), then heated in a water bath to 60-80 ℃ (for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃) and stirred for 4-6 h (for example, 4h, 4.5h, 5h, 5.5h or 6 h), and then the washed carbon nanotubes are washed and filtered by distilled water until the pH value of the washed carbon nanotubes is 7, so that the carbon nanotubes are obtained.
In the invention, impurities and amorphous carbon in the carbon nanotubes are removed by acid washing, and oxygen-containing functional groups are introduced to the surfaces of the carbon nanotubes, so that van der Waals force between the carbon nanotubes is reduced, and agglomeration between the carbon nanotubes is reduced.
In the invention, the sizes of the graphene nano-sheets and the carbon nano-tubes are limited in the range, so that agglomeration can be avoided when the sizes of the graphene nano-sheets and the carbon nano-tubes are undersized, and the graphene nano-sheets and the carbon nano-tubes are not easy to disperse; meanwhile, the mechanical property and electromagnetic shielding effect of the finally prepared magnesium alloy-based layered composite material can be avoided due to the fact that the subsequent adjacent layered elements are difficult to thermally press and combine due to accumulation when the size is too large.
According to some preferred embodiments, the mass concentration of carboxylated graphene in the graphene dispersion is 0.5-0.7 g/L (e.g., may be 0.5g/L, 0.52g/L, 0.55g/L, 0.58g/L, 0.6g/L, 0.62g/L, 0.65g/L, 0.68g/L, or 0.7 g/L).
According to some more preferred embodiments, the mass concentration of carboxylated graphene in the graphene dispersion is 0.6g/L.
In the invention, because the graphene nano sheet is of a two-dimensional lamellar structure, when the concentration of the graphene dispersion liquid is too low, carboxylated graphene deposited on the surface of the magnesium foil is scattered too sparsely; when the concentration of the graphene dispersion liquid is too high, the spray nozzle of the spray gun can be easily blocked, and the carboxylated graphene is easily agglomerated.
According to some preferred embodiments, the mass concentration of carbon nanotubes in the carbon nanotube dispersion is 0.2 to 0.4g/L (e.g., may be 0.2g/L, 0.22g/L, 0.25g/L, 0.28g/L, 0.3g/L, 0.32g/L, 0.35g/L, 0.38g/L, or 0.4 g/L).
According to some more preferred embodiments, the mass concentration of carbon nanotubes in the carbon nanotube dispersion is 0.3g/L.
In the invention, experiments prove that when the concentration of the carbon nano tube dispersion liquid is too low, the carbon nano tube deposited on the surface of the magnesium foil can be scattered too sparsely; when the concentration of the carbon nanotube dispersion is too high, the spray gun nozzle is easily blocked, and carbon nanotubes are easily agglomerated.
In order to uniformly disperse the carboxylated graphene and the carbon nanotubes in the solvent, the method further comprises the step of performing ultrasonic treatment on the graphene dispersion liquid and the carbon nanotube dispersion liquid for 10-13 hours (for example, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours or 13 hours), wherein the ultrasonic power is 200w and the ultrasonic frequency is 40kHz.
According to some preferred embodiments, in step 1, the solvent is absolute ethanol.
According to some preferred embodiments, before performing the spray deposition, further comprising:
the magnesium foil is subjected to polishing treatment and heated to 80 to 100 c (for example, 80 c, 85 c, 90 c, 95 c or 100 c).
The magnesium foil is polished to remove an oxide film on the surface thereof, for example, by using 350# sand paper. The magnesium foil is heated in order to evaporate the solvent in the carbon nanotube dispersion or graphene dispersion sprayed and deposited on the surface of the magnesium foil rapidly, so as to further prevent carboxylated graphene or carbon nanotube agglomeration.
According to some preferred embodiments, in step 2, the spray deposition is performed at a spray pressure of 0.2 to 0.4MPa (for example, may be 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa or 0.4 MPa).
Specifically, the nozzle used in the spray deposition of the present invention is a slit-type linear nozzle, and the spray distance is 30 to 50cm (for example, 30cm, 35cm, 40cm, 45cm, or 50cm may be used).
According to some more preferred embodiments, in step 2, the spray deposition is performed at a spray pressure of 0.3MPa.
In the invention, experiments prove that if the spraying pressure is lower during spraying and depositing, the atomization of graphene dispersion liquid or carbon nano tube dispersion liquid is not facilitated, and the initial liquid drop deposited on the surface of the magnesium foil is larger, so that the rapid volatilization of a solvent is not facilitated, and the agglomeration of graphene or carbon nano tube is caused; if the spray pressure is high during spray deposition, the graphene dispersion liquid or the carbon nanotube dispersion liquid is excessively atomized, so that the solvent which is not deposited on the surface of the magnesium foil is volatilized in the air, and the graphene or the carbon nanotube cannot be effectively deposited on the surface of the magnesium foil.
According to some preferred embodiments, the ejection layer comprises a carbon nanotube layer, a carboxylated graphene layer and a carbon nanotube layer connected in sequence.
According to some preferred embodiments, the mass of the sprayed layer is 0.45-0.55 wt% (e.g. may be 0.45wt%, 0.46wt%, 0.48wt%, 0.5wt%, 0.52wt%, 0.54wt% or 0.55 wt%) of the mass of the magnesium foil.
According to some more preferred embodiments, the mass of the sprayed layer is 0.5wt% of the mass of the magnesium foil.
According to some more preferred embodiments, the mass ratio of the carbon nanotube layer, the carboxylated graphene layer and the carbon nanotube layer in the ejection layer is 1:1:1.
In particular, in the present invention,in the first spray deposition, only the dispersion liquid of carbon nano tubes is sprayed and deposited on the surface of the magnesium foil to obtain a carbon nano tube layer, and the mass of the carbon nano tubes deposited on the layer is recorded as m 1 The method comprises the steps of carrying out a first treatment on the surface of the In the second spray deposition, spraying and depositing graphene dispersion liquid on the deposited carbon nano tube layer to obtain a carboxylated graphene layer, wherein the mass of the carboxylated graphene deposited on the layer is recorded as m 2 The method comprises the steps of carrying out a first treatment on the surface of the In the third spray deposition, spraying and depositing carbon nanotube dispersion liquid on the well-deposited carboxylated graphene layer to obtain a carbon nanotube layer, wherein the mass of the carbon nanotube deposited on the layer is recorded as m 3 . And finally, forming a spray layer on the surface of the magnesium foil, namely, forming a nano carbon film with a sandwich mixed structure, wherein the middle layer is carboxylated graphene, and the bottom and the top of the nano carbon film are carbon nano tubes. Preferably, the mass ratio of each deposition is m 1 :m 2 :m 3 =1:1:1 (i.e. the mass ratio of carbon nanotube layer, carboxylated graphene layer and carbon nanotube layer in the ejection layer is 1:1:1).
In the present invention, the total mass of carboxylated graphene and carbon nanotubes added after the above three depositions is 0.45-0.55 wt% of the mass of the magnesium foil. Experiments prove that if the mass fraction is lower, the introduced interlayer nano carbon material is less, and the enhancement effect of carboxylated graphene or carbon nano tubes cannot be effectively exerted; in contrast, if the mass fraction is higher, the agglomeration of the interlayer nano carbon material is easy to cause, the interface combination between adjacent lamellar elements is not facilitated, and the mechanical property of the prepared magnesium alloy-based lamellar composite material can be seriously influenced.
According to some preferred embodiments, the layered element has a size of 1.5-2.5 mm (e.g., may be 1.5mm, 1.6mm, 1.8mm, 2mm, 2.1mm, 2.2mm, 2.4mm, or 2.5 mm) and a thickness of 45-55 μm (e.g., may be 45 μm, 46 μm, 48 μm, 50 μm, 52 μm, 54 μm, or 55 μm).
According to some preferred embodiments, in step 3, the vacuum hot press sintering is performed at a temperature of 625-635 ℃ (e.g., may be 625 ℃, 626 ℃, 628 ℃, 630 ℃, 632 ℃, or 635 ℃), at a pressure of 45-55 MPa (e.g., may be 45MPa, 46MPa, 48MPa, 50MPa, 51MPa, 52MPa, 54MPa, or 55 MPa), for a time of 5.5-6.5 h (e.g., may be5h, 5.2h, 5.5h, 5.8h, 6h, 6.2h or 6.5 h) and a vacuum of 4X 10 -3 ～6×10 -3 Pa(4×10 -3 Pa、4.5×10 -3 Pa、5×10 -3 Pa、5.5×10 -3 Pa or 6X 10 -3 Pa)。
According to some more preferred embodiments, in step 3, the temperature of the vacuum hot press sintering is 630 ℃, the pressure is 50MPa, and the time is 6 hours.
According to some preferred embodiments, in step 3, the temperature of the hot extrusion is 380-420 ℃ (e.g., can be 380 ℃, 385 ℃, 390 ℃, 395 ℃, 400 ℃, 405 ℃, 410 ℃, 415 ℃, or 420 ℃), the backlog ratio is (25-30): 1 (e.g., can be 25:1, 25.5:1, 26:1, 26.5:1, 27:1, 27.5:1, 28:1, 28.5:1, 29:1, 29.5:1, or 30:1), and the extrusion speed is 0.1-0.3 mm/s (e.g., can be 0.1mm/s, 0.15mm/s, 0.2mm/s, 0.25mm/s, or 0.3 mm/s).
According to some more preferred embodiments, in step 3, the hot extrusion temperature is 400 ℃, the pressure ratio is 29:1, and the extrusion speed is 0.1mm/s.
In the invention, the layered element with the carbon nano tube layer-carboxylated graphene layer-carbon nano tube layer is placed in a die, and the magnesium alloy-based layered composite material is obtained by vacuum hot-pressing sintering and hot extrusion in sequence, so that the prepared composite material has a layered structure of the layered element, and the existence of the nano carbon layer remarkably improves the mechanical property and electromagnetic wave shielding property of the composite material, thereby realizing the integration of light-mechanical-shielding function.
According to the invention, the carboxylated graphene and the carbon nanotubes in the nano carbon layer form a three-dimensional network communication structure, so that the transmission path of electromagnetic waves in the nano carbon layer is more complex and roundabout, and the loss of the electromagnetic waves in the transmission process is enhanced. The magnesium alloy-based layered composite material is prepared from layered elements, electromagnetic waves are reflected between the layered composite materials for multiple times, and the enhancement of electromagnetic wave absorption loss is further enhanced, so that the electromagnetic shielding efficiency is remarkably improved, and the application of the magnesium alloy in the field of electromagnetic shielding is widened.
The invention also provides the magnesium alloy-based layered composite material prepared by the preparation method.
In order to more clearly illustrate the technical scheme and advantages of the invention, a magnesium alloy-based layered composite material and a preparation method thereof are described in detail below through several embodiments.
In the following examples and comparative examples, the magnesium foil used had a thickness of 50. Mu.m.
Example 1
(1) Placing graphene nano sheets with the sheet diameter of 0.5-5 mu m and the thickness of 0.8-1.2 nm into mixed liquid with the volume fraction ratio of concentrated sulfuric acid to concentrated nitric acid of 3:1, carrying out ultrasonic treatment for 30min, then heating to 70 ℃ in a water bath, stirring for 5h, and finally washing and filtering the pickled graphene nano sheets by distilled water until the pH value is 7 to obtain carboxylated graphene; dispersing the carboxylated graphene in absolute ethyl alcohol, and carrying out ultrasonic treatment for 12 hours to obtain graphene dispersion liquid with the mass concentration of 0.6g/L of carboxylated graphene;
putting a carbon nano tube with the diameter of 30-80 nm and the length of less than 10 mu m into a mixed solution with the volume fraction ratio of concentrated sulfuric acid to concentrated nitric acid of 3:1, carrying out ultrasonic treatment for 30min, then heating to 70 ℃ in a water bath, stirring for 5h, and finally flushing and filtering the pickled graphene nano sheet by distilled water until the pH value is 7 to obtain the pickled carbon nano tube; dispersing the carbon nano tube in absolute ethyl alcohol, and carrying out ultrasonic treatment for 12 hours to obtain carbon nano tube dispersion liquid with the mass concentration of 0.3g/L of the carbon nano tube;
wherein, the ultrasonic power of the ultrasonic treatment is 200w, and the frequency is 40kHz;
(2) And (3) polishing the magnesium foil by using 350# sand paper to remove the oxide film on the surface of the magnesium foil. Heating the polished magnesium foil to 90 ℃ on a heating table, and then sequentially spraying and depositing the carbon nano tube dispersion liquid, the graphene dispersion liquid and the carbon nano tube dispersion liquid prepared in the step (1) on the surface of the magnesium foil for three times to obtain a magnesium-based composite sheet layer comprising a spraying layer; wherein the injection pressure is 0.3MPa;
first spray deposition: spraying and depositing only carbon nanotube dispersion liquid on the surface of the magnesium foil to obtain a first carbon nanotube layer, wherein the mass of the deposited carbon nanotubes is recordedIs m 11 ；
Second spray deposition: spraying and depositing graphene dispersion liquid on the deposited first carbon nano tube layer to obtain a carboxylated graphene layer, wherein the mass of the carboxylated graphene deposited on the layer is recorded as m 21 ；
Third spray deposition: spraying and depositing carbon nano tube dispersion liquid on the deposited carboxylated graphene layer to obtain a second carbon nano tube layer, wherein the mass of the deposited carbon nano tube layer is recorded as m 31 ；
The spray layer has a structure of a first carbon nano tube layer-a carboxylated graphene layer-a second carbon nano tube layer; and m is 11 :m 21 :m 31 The mass of the sprayed layer was 0.5wt% of the mass of the magnesium foil =1:1:1;
(3) Crushing the magnesium-based composite sheet into layered elements with the size of (1.5-2.5) mm x (1.5-2.5) mm and the thickness of 45-55 mu m, and placing the layered elements into an isostatic graphite die at 630 ℃, 50MPa and 5 x 10 -3 Vacuum hot-pressing sintering for 6h under Pa to obtain
Is a cylindrical block of (a); and carrying out hot extrusion deformation on the cylindrical block, wherein the hot extrusion temperature is 400 ℃, the extrusion ratio is 29:1, and the extrusion speed is 0.1mm/s, so as to obtain the magnesium alloy basal layer composite material.
Example 2
Example 2 is substantially the same as example 1 except that:
in the step (1), preparing graphene dispersion liquid with the mass concentration of carboxylated graphene of 0.5 g/L; preparing a carbon nanotube dispersion liquid with the mass concentration of the carbon nanotubes of 0.4g/L.
Example 3
Example 3 is substantially the same as example 1 except that:
in the step (1), preparing graphene dispersion liquid with the mass concentration of carboxylated graphene of 0.7 g/L; preparing a carbon nanotube dispersion liquid with the mass concentration of the carbon nanotubes of 0.2 g/L.
Example 4
Example 4 is substantially the same as example 1 except that:
in step (2), the injection pressure was 0.2MPa.
Example 5
Example 5 is substantially the same as example 1 except that:
in step (2), the injection pressure was 0.4MPa.
Example 6
Example 6 is substantially the same as example 1 except that:
in step (2), the mass of the sprayed layer was 0.45wt% of the mass of the magnesium foil.
Example 7
Example 7 is substantially the same as example 1 except that:
in step (2), the mass of the sprayed layer was 0.55wt% of the mass of the magnesium foil.
Comparative example 1
Will directly take
The cylindrical block of pure magnesium is placed in an isostatic pressing graphite mould at 630 ℃, 50MPa and 5 multiplied by 10 -3 Vacuum hot-pressing sintering for 6h under Pa; and carrying out hot extrusion deformation on the cylindrical block, wherein the hot extrusion temperature is 400 ℃, the extrusion ratio is 29:1, and the extrusion speed is 0.1mm/s, so as to obtain the extruded pure magnesium matrix.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that: in the step (2), spraying and depositing the graphene dispersion liquid prepared in the step (1) on the surface of the magnesium foil by adopting the spraying pressure of 0.3MPa to obtain a magnesium-based composite sheet layer comprising a spraying layer; wherein the structure of the ejection layer only carboxylates the graphene layer; and the mass of the sprayed layer was 0.5wt% of the mass of the magnesium foil.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that: in the step (2), spraying and depositing the carbon nano tube dispersion liquid prepared in the step (1) on the surface of the magnesium foil by adopting the spraying pressure of 0.3MPa to obtain a magnesium-based composite sheet layer comprising a spraying layer; wherein, the structure of the spray layer is only a carbon nano tube layer; and the mass of the sprayed layer was 0.5wt% of the mass of the magnesium foil.
The magnesium alloy-based layered composite material prepared in example 1, the extruded pure magnesium matrix prepared in comparative example 1, and the magnesium alloy-based layered composite materials prepared in comparative examples 2 and 3 were subjected to material characterization and performance test, wherein the mechanical property test results are shown in table 1.
Specifically, the distribution of the nanocarbon material on the surface of the magnesium foil and the layered structure of the magnesium alloy-based layered composite material in the ejection layer were observed using a field emission Scanning Electron Microscope (SEM), as shown in fig. 2, 3, 4, and 7. The layered structure of the extruded pure magnesium matrix and magnesium alloy based layered composite material was observed using an Optical Microscope (OM), as shown in fig. 5 and 6. The interface structure of the magnesium alloy-based layered composite material was observed using a transmission microscope (TEM), as shown in fig. 8. The tensile properties of the materials were tested using an electronic universal stretcher, the dimensions of the gauge length of the tensile test specimen were 15X 6X 2mm, and the tensile speed was 0.5mm/min. The electromagnetic shielding effectiveness of the material in the X-wave band (8.2-12.4 GHz) is tested by adopting a waveguide method by adopting a network vector analyzer, and the size of a sample is 22.86 multiplied by 10.16 multiplied by 5mm.
As can be seen from fig. 2 to 4, the nanocarbon material in the spray layer is uniformly dispersed on the surface of the magnesium foil after spray deposition, and no obvious stacking phenomenon is generated; and as shown in fig. 2, the surface of the layered primitive prepared by the invention has a three-dimensional network communication structure composed of carboxylated graphene nano-sheets and carbon nano-tubes.
As can be seen from fig. 5 and 6, in comparison with fig. 5, a micro-nano layered structure composed of a micro-scale magnesium layer and a nano-scale nano carbon material layer stacked one on top of the other was successfully constructed in fig. 6. After hot extrusion, the layered structure converts the equiaxed grains of the pure magnesium matrix into brick-like rectangular grains. The magnesium layer is oriented parallel to the Extrusion Direction (ED), and it is notable that the initial magnesium foil thickness decreases from 50 μm to about 22 μm after hot extrusion deformation, as shown in FIG. 7. No obvious impurities and defects are observed between adjacent magnesium layers, so that the nano carbon material/magnesium interface combination in the magnesium alloy-based layered composite material prepared by the invention is good, as shown in fig. 8.
TABLE 1
As can be seen from Table 1 and FIG. 9, the yield strength of the magnesium alloy-based layered composite material prepared in example 1 of the present invention was increased from 93MPa to 142MPa, the tensile strength was increased from 154MPa to 237MPa, and the elongation was increased from 6.5% to 10.1%, as compared with the extruded pure magnesium matrix prepared in comparative example 1, wherein the increase in yield strength was as high as 53%. Moreover, the yield strength and the tensile strength of the magnesium alloy-based layered composite materials of comparative example 2 and comparative example 3 are both significantly improved over those of the same nanocarbon material content, and the elongation is still high.
As can be seen from FIGS. 10 to 12, the magnesium alloy-based layered composite material prepared in example 1 of the present invention exhibits higher SE than the extruded pure magnesium matrix prepared in comparative example 1 T And SE A Value, however, SE R The value is not changed obviously, so that the micro-nano layered structure designed by the invention mainly increases electromagnetic shielding effectiveness by increasing absorption loss. The magnesium alloy-based layered composite material prepared in example 1 of the present invention was SE compared to the extruded pure magnesium matrix prepared in comparative example 1 T Increasing from 30dB to 70dB, SE A From 20dB to 65dB. Wherein SE is T For characterising the total shielding effectiveness, SE A For characterising absorption losses, SE R For characterizing the reflection loss. Obviously, this is very different from conventional shielding metallic materials, which mainly improve the electromagnetic shielding effectiveness by reflecting electromagnetic waves at the metallic surface. In addition, the absorption loss of the magnesium alloy-based layered composite material prepared by the invention to electromagnetic waves is obviously higher than that of the magnesium alloy-based layered composite materials prepared by comparative examples 2 and 3, which shows that the spray layer with a sandwich structure is beneficial to improving the mechanical property of the composite material and is also beneficial to the absorption of electromagnetic waves. Therefore, the magnesium alloy basal layer-shaped composite material prepared by the invention realizes the integration of mechanical and shielding functions.
In summary, the electromagnetic shielding performance of the magnesium alloy-based layered composite material prepared by the present invention is mainly due to the enhancement of electromagnetic wave absorption loss, which is mainly due to the multiple reflection of electromagnetic waves between the interlayer structures inside the composite material. In the process of multiple reflection of electromagnetic waves in the layered structure, different transmission paths in the micro-nano layer provide different phase offsets for the propagation of the electromagnetic waves, so that the original electromagnetic plane waves lose phase coherence (phase mismatch) and a special electromagnetic wave absorption mechanism is formed. In addition, since carboxylated graphene nanoplatelets and carbon nanotubes possess an ultra-high dielectric constant, electromagnetic waves can be effectively reflected and incident, and thus are recognized as a potential electromagnetic shielding material. The propagation path of the incident electromagnetic wave is further increased due to the presence of the graphene nanoplatelets and the carbon nanotubes in the composite material. In addition, the interface between the two conductive materials having a large impedance difference, the nanocarbon material and the magnesium-based substrate, can further enhance the back and forth reflection of electromagnetic waves at the interface. All of these factors as described above enhance the dissipation of electromagnetic wave energy in the nanocarbon/magnesium layered composite material. In addition, due to the spray layer of the sandwich structure, the carboxylated graphene nano sheet and the carbon nano tube form a communicated three-dimensional network structure, so that the transmission path of electromagnetic waves in the nano carbon layer is more complex and roundabout, and the loss of the electromagnetic waves in the transmission process is enhanced, and therefore, the electromagnetic shielding effectiveness is higher than that of a composite material with only the carboxylated graphene nano sheet or only the carbon nano tube.
In fig. 5 to 8, the directions of the magnesium layers in fig. 6 to 8 are all parallel to the Extrusion Direction (ED), and the directions are the same as those shown in fig. 5. In fig. 9 to 12, bulk Mg was used to characterize the extruded pure magnesium matrix prepared in comparative example 1, CNTs/Mg was used to characterize the magnesium alloy-based layered composite prepared in comparative example 3, GNs/Mg was used to characterize the magnesium alloy-based layered composite prepared in comparative example 2, and Hybrid/Mg was used to characterize the magnesium alloy-based layered composite prepared in example 1.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention. The invention is not described in detail in a manner known to those skilled in the art.
Claims (19)
1. A method for preparing a magnesium alloy-based layered composite material, which is characterized by comprising the following steps:
dispersing carboxylated graphene in a solvent to obtain graphene dispersion liquid; dispersing carbon nanotubes in the solvent to obtain a carbon nanotube dispersion; the mass concentration of the carbon nano tube in the carbon nano tube dispersion liquid is 0.2-0.4 g/L;
sequentially spraying and depositing the carbon nanotube dispersion liquid, the graphene dispersion liquid and the carbon nanotube dispersion liquid on the surface of the magnesium foil to obtain a magnesium-based composite sheet layer comprising a spraying layer; the mass of the spraying layer is 0.45-0.55wt% of the mass of the magnesium foil;
crushing the magnesium-based composite sheet into layered elements, and placing the layered elements in a die to sequentially perform vacuum hot-press sintering and hot extrusion to obtain the magnesium alloy-based layered composite material; the temperature of the vacuum hot-pressing sintering is 625-635 ℃, the pressure is 45-55 MPa, and the time is 5.5-6.5 h; the hot extrusion temperature is 380-420 ℃, the lamination ratio is (25-30): 1, and the extrusion speed is 0.1-0.3 mm/s.
2. The method of manufacturing according to claim 1, characterized in that:
the carboxylated graphene is obtained by pickling graphene nano sheets.
3. The method of manufacturing according to claim 1, characterized in that:
the diameter of the carbon nano tube is 30-80 nm, and the length of the carbon nano tube is less than 10 mu m.
4. The preparation method according to claim 2, characterized in that:
the graphene nano sheet has a size of 0.5-5 mu m and a thickness of 0.8-1.2 nm.
5. The preparation method according to claim 2, characterized in that:
the preparation method of the carboxylated graphene comprises the following steps: and placing the graphene nano sheet in an acid solution, and stirring for 4-6 hours at the temperature of 60-80 ℃.
6. A method of preparation according to claim 3, characterized in that:
the carbon nano tube is obtained by acid washing; the acid washing comprises the steps of placing the carbon nano tube in an acid solution and stirring for 4-6 hours at the temperature of 60-80 ℃.
7. The method of manufacturing according to claim 5 or 6, characterized in that:
the acid solution is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1.
8. The method of manufacturing according to claim 1, wherein:
the mass concentration of the carboxylated graphene in the graphene dispersion liquid is 0.5-0.7 g/L.
9. The method of manufacturing according to claim 1, wherein:
the mass concentration of the carbon nano tube in the carbon nano tube dispersion liquid is 0.3g/L.
10. The method of manufacturing according to claim 1, wherein:
the mass concentration of the carboxylated graphene in the graphene dispersion liquid is 0.6g/L.
11. The method of manufacturing according to claim 1, wherein:
the solvent is absolute ethyl alcohol.
12. The method of manufacturing according to claim 1, wherein:
before the spray deposition, further comprising:
and polishing the magnesium foil, and heating the magnesium foil to 80-100 ℃.
13. The method of manufacturing according to claim 1, wherein:
the jet pressure of the jet deposition is 0.2-0.4 MPa.
14. The method of manufacturing according to claim 1, wherein:
the spray deposition spray pressure is 0.3MPa.
15. The method of manufacturing according to claim 1, wherein:
the spray layer comprises a carbon nano tube layer, a carboxylated graphene layer and a carbon nano tube layer which are sequentially connected.
16. The method of manufacturing as claimed in claim 15, wherein:
the mass ratio of the carbon nano tube layer, the carboxylated graphene layer and the carbon nano tube layer in the spray layer is 1:1:1.
17. The method of manufacturing according to claim 1, characterized in that:
the size of the layered element is 1.5-2.5 mm, and the thickness is 45-55 mu m.
18. The method of manufacturing according to claim 1, characterized in that:
the vacuum degree of the vacuum hot-pressed sintering is 4 multiplied by 10 -3 ~6×10 -3 Pa。
19. A magnesium alloy-based layered composite material prepared by the preparation method of any one of claims 1 to 18.
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