CN117887991A - Graphene aluminum-based alloy material and preparation method thereof - Google Patents
Graphene aluminum-based alloy material and preparation method thereof Download PDFInfo
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- CN117887991A CN117887991A CN202311762006.8A CN202311762006A CN117887991A CN 117887991 A CN117887991 A CN 117887991A CN 202311762006 A CN202311762006 A CN 202311762006A CN 117887991 A CN117887991 A CN 117887991A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 48
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 44
- 239000000956 alloy Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 21
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims description 70
- 229910000838 Al alloy Inorganic materials 0.000 claims description 22
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- 238000002156 mixing Methods 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 16
- 238000001694 spray drying Methods 0.000 claims description 16
- 238000009423 ventilation Methods 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001192 hot extrusion Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 11
- 230000006872 improvement Effects 0.000 description 9
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- 238000005299 abrasion Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- 229910018566 Al—Si—Mg Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 229910000431 copper oxide Inorganic materials 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
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Abstract
The invention provides a graphene-aluminum-based alloy material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, preparing W/Cu oxide modified graphene oxide; s2, preparing W/Cu oxide modified graphene; s3, preparing W/Cu modified graphene; s4, preparing the graphene-aluminum-based alloy material. The graphene-based alloy material prepared by the method has the advantages of light weight, high strength, electric conduction, heat conduction, wear resistance, vibration reduction and the like, and remarkably reduces the thermal expansion coefficient of the composite material, improves the heat conductivity, and remarkably reduces the friction and wear coefficient.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a graphene-aluminum-based alloy material and a preparation method thereof.
Background
Graphene is a novel two-dimensional planar nanomaterial formed by sp2 hybridized carbon atom close packing discovered in recent years, and has huge specific surface area (up to 2630m 2 Per gram), ultra-high carrier mobilityRate of shift (15000-25000 cm) 2 Vs), thermal conductivity (4840-5300W/mK), young's modulus (1000 GPa), and breaking strength (130 GPa), and a forbidden band width equal to about 0, exhibit excellent electrical, thermal, and mechanical properties, making it one of the most desirable reinforcements for metal-based nanocomposites.
The aluminum alloy has low density, high strength and good ductility, and is widely applied in the fields of aerospace and the like. As a structural material, improving strength has been the main direction of aluminum alloy research. At present, the traditional casting metallurgical method such as adjusting the components of the aluminum alloy, optimizing the thermomechanical deformation processing and heat treatment and the like encounters a bottleneck in improving the performance of the aluminum alloy. The preparation of high-performance aluminum-based composite materials by using graphene as a reinforcement is an important direction in the current research of high-performance aluminum alloys.
Patent document CN111101172a discloses a graphene-aluminum composite material and a preparation method thereof, firstly preparing a graphene aerosol cathode, adopting graphene aerogel as a cathode, adopting metal aluminum as an anode, placing the anode and the cathode in molten electrolyte (the electrolyte consists of sodium chloride, potassium chloride and aluminum chloride with different proportions), and carrying out electrolysis under the electrolysis current of 250mA-350mA to obtain the graphene-aluminum composite material.
Patent document CN105112699a discloses a preparation method of graphene/aluminum alloy composite material, which comprises mechanical powder mixing, low-temperature liquid nitrogen ball milling, vacuum packaging, hot isostatic pressing sintering for preparing blanks and hot extrusion molding of the blanks.
Patent document CN109112367B discloses a graphene reinforced Al-Si-Mg cast aluminum alloy and a preparation method thereof, the method adopts vacuum melting, the distribution adopts layered distribution, and a graphene layer is placed at the middle position.
Patent documents CN105081310A, CN104630528A and CN102329976A both propose a method for preparing graphene-metal composite powder by modifying the surface of metal powder with graphene oxide solution, and the problem of uniform dispersion and distribution of graphene in a metal matrix is well solved.
However, there are one or more of the following problems in the foregoing documents: the preparation cost of the graphene aerosol is high, the energy consumption is high, and meanwhile, pollution chlorine and the like can be generated by electrolysis of NaCl and the like; the graphene is unevenly distributed; the raw materials must be aluminum particles; the density difference between the aluminum alloy melt and the graphene is large, and the graphene floats on the surface of the aluminum alloy melt in the aluminum alloy smelting process, so that the loss and the uneven distribution of the graphene in the aluminum alloy preparation process are caused; and/or the graphene sheets blocking diffusion migration of aluminum atoms and the low reactivity of the carbon material also worsen the sintering performance of the aluminum alloy powder and reduce densification thereof.
Disclosure of Invention
The invention aims to provide a graphene aluminum-based alloy material and a preparation method thereof, which have the characteristics of light weight, high strength, electric conduction, heat conduction, wear resistance, vibration reduction and the like, and remarkably reduce the thermal expansion coefficient of a composite material, improve the heat conductivity and remarkably reduce the friction and wear coefficient.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a graphene-aluminum-based alloy material, which comprises the following steps:
s1, preparing W/Cu oxide modified graphene oxide: adding sodium tungstate, copper salt and alkali into the graphene oxide aqueous dispersion, stirring and mixing uniformly, spray-drying, washing, drying again, calcining, and ball-milling to obtain W/Cu oxide modified graphene oxide;
s2, preparing W/Cu oxide modified graphene: reducing the W/Cu oxide modified graphene oxide prepared in the step S1 in hydrazine hydrate steam to prepare W/Cu oxide modified graphene;
s3, preparing W/Cu modified graphene: reducing the W/Cu oxide modified graphene prepared in the step S2 by low-temperature hydrogen to prepare W/Cu modified graphene;
s4, preparing a graphene aluminum-based alloy material: and (3) mixing the matrix raw material and the W/Cu modified graphene prepared in the step (S3), and performing molding treatment to prepare the graphene-aluminum-based alloy material.
As a further improvement of the present invention, the copper salt in step S1 is selected from at least one of copper chloride, copper sulfate, copper nitrate; the alkali is at least one selected from NaOH and KOH.
As a further improvement of the invention, the mass ratio of the graphene oxide aqueous dispersion liquid, sodium tungstate, copper salt and alkali in the step S1 is 100:0.2-0.3:0.1-0.2:0.5-1, and the concentration of the graphene oxide aqueous dispersion liquid is 0.5-1g/L.
As a further improvement of the invention, the spray drying condition in the step S1 is that the air inlet temperature is 80-100 ℃, the air outlet temperature is 30-80 ℃, and the evaporation water amount is 1500-2000mL/h.
As a further improvement of the invention, the calcination temperature in the step S1 is 400-500 ℃, the time is 2-4h, and the ball milling is 1-3h.
As a further improvement of the invention, the time of the reduction in the step S2 is 10-12h, and the concentration of the hydrazine hydrate steam is 20-30g/L.
As a further improvement of the invention, the low-temperature hydrogen reduction in the step S3 adopts a strong drainage ventilation type tubular furnace to introduce hydrogen at 650-750 ℃ for reduction for 2-4h, and the ventilation amount of the hydrogen is 17-22L/min.
As a further improvement of the invention, in the step S4, the base material comprises 99 to 99.6 percent of aluminum, 0.001 to 0.4 percent of iron, 0.0001 to 0.05 percent of manganese, 0.0001 to 0.03 percent of titanium, 0.0001 to 0.05 percent of copper, 0.0001 to 0.05 percent of tin, 0.0001 to 0.05 percent of antimony, 0.01 to 0.02 percent of silicon and 0.01 to 0.1 percent of other impurities in the aluminum alloy.
As a further improvement of the invention, the mixing in the step S4 is to heat to 600-700 ℃ for uniform mixing, the forming treatment is hot extrusion treatment, the extrusion temperature is 400-500 ℃, and the extrusion ratio is 8-12.
The invention further protects the graphene-aluminum-based alloy material prepared by the preparation method.
The invention has the following beneficial effects:
graphene is directly added into aluminum alloy, so that agglomeration phenomenon is easy to occur due to poor dispersibility of the graphene, and the performance of the composite material is reduced; meanwhile, the interface reaction of the graphene-aluminum-based composite material is difficult to control, and Al is easy to form 4 C 3 Damage by destruction ofProperties of the composite material; the wettability of the graphite material with aluminum and its alloys is generally poor, and strong interface bonding is not easy to form.
According to the invention, the W/Cu modified graphene is prepared, copper and tungsten oxide are doped in the graphene oxide stage, so that the wettability between the graphene and an aluminum metal melt is improved, and meanwhile, the tungsten on the surface layer of the W/Cu modified graphene prepared after reduction can improve the combination of a composite interface and inhibit Al 4 C 3 And the phase is generated, and moreover, the W/Cu oxide modified graphene oxide prepared by spray drying has a wrinkled structure, so that the stacking of graphene in an aluminum alloy matrix is effectively reduced, the aggregation caused by an ordered structure between graphene sheets is avoided, uniform dispersion is realized, and the excellent performance of the graphene is fully exerted.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
Fig. 1 is an electron micrograph of W/Cu modified graphene obtained in step S3 of example 1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a graphene-aluminum-based alloy material, which comprises the following steps:
s1, preparing W/Cu oxide modified graphene oxide: adding 0.2 part by weight of sodium tungstate, 0.1 part by weight of copper chloride and 0.5 part by weight of NaOH into 100 parts by weight of 0.5g/L graphene oxide aqueous dispersion, stirring and mixing uniformly, spray drying, washing, drying again, calcining at 400 ℃ for 2 hours, and ball milling for 1 hour to obtain W/Cu oxide modified graphene oxide;
the spray drying condition is that the air inlet temperature is 80 ℃, the air outlet temperature is 30 ℃ and the evaporation water quantity is 1500mL/h;
s2, preparing W/Cu oxide modified graphene: reducing the W/Cu oxide modified graphene oxide prepared in the step S1 in hydrazine hydrate steam for 10 hours, wherein the concentration of the hydrazine hydrate steam is 20g/L, and preparing the W/Cu oxide modified graphene;
s3, preparing W/Cu modified graphene: reducing the W/Cu oxide modified graphene prepared in the step S2 by introducing hydrogen at 650 ℃ for 2 hours by adopting a strong drainage ventilation type tubular furnace, wherein the ventilation amount of the hydrogen is 17L/min, and preparing the W/Cu modified graphene;
s4, preparing a graphene aluminum-based alloy material: and (3) heating the aluminum alloy 1050 and the W/Cu modified graphene prepared in the step (S3) to 600 ℃ for uniform mixing, and performing hot extrusion treatment at the extrusion temperature of 400 ℃ and the extrusion ratio of 8 to prepare the graphene-aluminum-based alloy material.
Example 2
The embodiment provides a preparation method of a graphene-aluminum-based alloy material, which comprises the following steps:
s1, preparing W/Cu oxide modified graphene oxide: adding 0.3 part by weight of sodium tungstate, 0.2 part by weight of copper sulfate and 1 part by weight of KOH into 100 parts by weight of 1g/L graphene oxide aqueous dispersion, stirring and mixing uniformly, spray-drying, washing, drying, calcining at 500 ℃ for 4 hours, and ball-milling for 3 hours to obtain W/Cu oxide modified graphene oxide;
the spray drying condition is that the air inlet temperature is 100 ℃, the air outlet temperature is 80 ℃ and the evaporation water quantity is 2000mL/h;
s2, preparing W/Cu oxide modified graphene: reducing the W/Cu oxide modified graphene oxide prepared in the step S1 in hydrazine hydrate steam for 12h, wherein the concentration of the hydrazine hydrate steam is 30g/L, and preparing the W/Cu oxide modified graphene;
s3, preparing W/Cu modified graphene: reducing the W/Cu oxide modified graphene prepared in the step S2 by introducing hydrogen at 750 ℃ for 4 hours by adopting a strong drainage ventilation type tubular furnace, wherein the ventilation amount of the hydrogen is 22L/min, and preparing the W/Cu modified graphene;
s4, preparing a graphene aluminum-based alloy material: and (3) heating the aluminum alloy 1050 and the W/Cu modified graphene prepared in the step (S3) to 700 ℃ for uniform mixing, and performing hot extrusion treatment at 500 ℃ with an extrusion ratio of 12 to prepare the graphene-aluminum-based alloy material.
Example 3
The embodiment provides a preparation method of a graphene-aluminum-based alloy material, which comprises the following steps:
s1, preparing W/Cu oxide modified graphene oxide: adding 0.25 part by weight of sodium tungstate, 0.2 part by weight of copper nitrate and 0.7 part by weight of NaOH into 100 parts by weight of 0.7g/L graphene oxide aqueous dispersion, stirring and mixing uniformly, spray drying, washing, drying, calcining at 450 ℃ for 3 hours, and ball milling for 2 hours to obtain W/Cu oxide modified graphene oxide;
the spray drying condition is that the air inlet temperature is 90 ℃, the air outlet temperature is 50 ℃ and the evaporation water quantity is 1700mL/h;
s2, preparing W/Cu oxide modified graphene: reducing the W/Cu oxide modified graphene oxide prepared in the step S1 in hydrazine hydrate steam for 11h, wherein the concentration of the hydrazine hydrate steam is 25g/L, and preparing the W/Cu oxide modified graphene;
s3, preparing W/Cu modified graphene: reducing the W/Cu oxide modified graphene prepared in the step S2 by introducing hydrogen at 700 ℃ for 3 hours by adopting a strong drainage ventilation type tubular furnace, wherein the ventilation amount of the hydrogen is 20L/min, and preparing the W/Cu modified graphene;
s4, preparing a graphene aluminum-based alloy material: and (3) heating the aluminum alloy 1050 and the W/Cu modified graphene prepared in the step (S3) to 650 ℃ for uniform mixing, and performing hot extrusion treatment at the extrusion temperature of 450 ℃ and the extrusion ratio of 10 to prepare the graphene-aluminum-based alloy material.
Comparative example 1
In comparison with example 3, the difference is that sodium tungstate is not added in step S1.
The method comprises the following steps:
s1, preparing Cu oxide modified graphene oxide: adding 0.4 part by weight of copper nitrate and 0.7 part by weight of NaOH into 100 parts by weight of 0.7g/L graphene oxide aqueous dispersion, stirring and mixing uniformly, spray drying, washing, drying, calcining at 450 ℃ for 3 hours, and ball milling for 2 hours to obtain Cu oxide modified graphene oxide;
the spray drying condition is that the air inlet temperature is 90 ℃, the air outlet temperature is 50 ℃ and the evaporation water quantity is 1700mL/h;
s2, preparing Cu oxide modified graphene: reducing the Cu oxide modified graphene oxide obtained in the step S1 in hydrazine hydrate steam for 11 hours, wherein the concentration of the hydrazine hydrate steam is 25g/L, and obtaining Cu oxide modified graphene;
s3, preparing Cu modified graphene: reducing the Cu oxide modified graphene prepared in the step S2 by introducing hydrogen at 700 ℃ for 3 hours by adopting a strong drainage ventilation type tubular furnace, wherein the ventilation amount of the hydrogen is 20L/min, and preparing the Cu modified graphene;
s4, preparing a graphene aluminum-based alloy material: and (3) heating the aluminum alloy 1050 and the Cu-modified graphene prepared in the step (S3) to 650 ℃ for uniform mixing, and performing hot extrusion treatment at the extrusion temperature of 450 ℃ and the extrusion ratio of 10 to prepare the graphene-aluminum-based alloy material.
Comparative example 2
The difference from example 3 is that copper nitrate is not added in step S1.
The method comprises the following steps:
s1, preparation of W oxide modified graphene oxide: adding 0.4 part by weight of sodium tungstate and 0.7 part by weight of NaOH into 100 parts by weight of 0.7g/L graphene oxide aqueous dispersion, stirring and mixing uniformly, spray drying, washing, drying, calcining at 450 ℃ for 3 hours, and ball milling for 2 hours to obtain W oxide modified graphene oxide;
the spray drying condition is that the air inlet temperature is 90 ℃, the air outlet temperature is 50 ℃ and the evaporation water quantity is 1700mL/h;
preparation of S2.W oxide modified graphene: reducing the W oxide modified graphene oxide prepared in the step S1 in hydrazine hydrate steam for 11 hours, wherein the concentration of the hydrazine hydrate steam is 25g/L, and preparing the W oxide modified graphene oxide;
s3, preparing W modified graphene: introducing hydrogen into the W oxide modified graphene prepared in the step S2 at 700 ℃ for reduction for 3 hours by adopting a strong drainage ventilation type tubular furnace, wherein the ventilation amount of the hydrogen is 20L/min, and preparing the W/Cu modified graphene;
s4, preparing a graphene aluminum-based alloy material: and (3) heating the aluminum alloy 1050 and the W-modified graphene prepared in the step S3 to 650 ℃ for uniform mixing, and performing hot extrusion treatment at the extrusion temperature of 450 ℃ and the extrusion ratio of 10 to prepare the graphene aluminum-based alloy material.
Comparative example 3
In comparison with example 3, the difference is that in step S1, spray drying is not performed and direct drying is employed.
The method comprises the following steps:
s1, preparing W/Cu oxide modified graphene oxide: adding 0.25 part by weight of sodium tungstate, 0.15 part by weight of copper nitrate and 0.7 part by weight of NaOH into 100 parts by weight of 0.7g/L graphene oxide aqueous dispersion liquid, stirring and mixing uniformly, drying at 105 ℃ for 2 hours, washing, drying, calcining at 450 ℃ for 3 hours, and ball-milling for 2 hours to obtain W/Cu oxide modified graphene oxide;
s2, preparing W/Cu oxide modified graphene: reducing the W/Cu oxide modified graphene oxide prepared in the step S1 in hydrazine hydrate steam for 11h, wherein the concentration of the hydrazine hydrate steam is 25g/L, and preparing the W/Cu oxide modified graphene;
s3, preparing W/Cu modified graphene: reducing the W/Cu oxide modified graphene prepared in the step S2 by introducing hydrogen at 700 ℃ for 3 hours by adopting a strong drainage ventilation type tubular furnace, wherein the ventilation amount of the hydrogen is 20L/min, and preparing the W/Cu modified graphene;
s4, preparing a graphene aluminum-based alloy material: and (3) heating the aluminum alloy 1050 with the aluminum content not lower than 70% and the W/Cu modified graphene prepared in the step (S3) to 650 ℃ for uniform mixing, performing hot extrusion treatment at the extrusion temperature of 450 ℃ and the extrusion ratio of 10, and preparing the graphene aluminum-based alloy material.
Test example 1
The graphene-aluminum-based alloy materials prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance test, and the results are shown in Table 1.
The Vickers hardness test uses a loading weight of 300g and a dwell time of 10 s;
the graphene-aluminum-based alloy material is processed into a cylinder with the size phi of 4 multiplied by 10mm, and constant strain compression test is carried out, wherein the compression rate is 0.3mm/s.
Impact test: the graphene-aluminum-based alloy material is processed into the dimensions of 55mm×25mm×5mm. The test equipment is a JK-KC impact tester, the test temperature is room temperature, and the impact absorption power of the sample is recorded.
Abrasion test: the graphene-aluminum-based alloy material is processed into abrasion parallel test blocks with the dimensions of 20mm multiplied by 20mm, the abrasion parallel test blocks are processed on a TRM500 type friction tester, the working load is 90N, the rotating speed of a grinding wheel is 320r/min, the testing temperature is room temperature, the relative sliding speed is 100mm/min, the abrasion time is 15min, the abrasion test results of 3 groups of parallel test blocks are recorded, and the final test data are arithmetic average values of abrasion volumes.
TABLE 1
From the above table, the comprehensive properties of the graphene-aluminum-based alloy materials prepared in examples 1 to 3 of the invention are obviously improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the graphene-aluminum-based alloy material is characterized by comprising the following steps of:
s1, preparing W/Cu oxide modified graphene oxide: adding sodium tungstate, copper salt and alkali into the graphene oxide aqueous dispersion, stirring and mixing uniformly, spray-drying, washing, drying again, calcining, and ball-milling to obtain W/Cu oxide modified graphene oxide;
s2, preparing W/Cu oxide modified graphene: reducing the W/Cu oxide modified graphene oxide prepared in the step S1 in hydrazine hydrate steam to prepare W/Cu oxide modified graphene;
s3, preparing W/Cu modified graphene: reducing the W/Cu oxide modified graphene prepared in the step S2 by low-temperature hydrogen to prepare W/Cu modified graphene;
s4, preparing a graphene aluminum-based alloy material: and (3) mixing the matrix raw material and the W/Cu modified graphene prepared in the step (S3), and performing molding treatment to prepare the graphene-aluminum-based alloy material.
2. The preparation method according to claim 1, wherein the copper salt in step S1 is at least one selected from the group consisting of copper chloride, copper sulfate and copper nitrate; the alkali is at least one selected from NaOH and KOH.
3. The preparation method according to claim 1, wherein the mass ratio of the graphene oxide aqueous dispersion, sodium tungstate, copper salt and alkali in the step S1 is 100:0.2-0.3:0.1-0.2:0.5-1, and the concentration of the graphene oxide aqueous dispersion is 0.5-1g/L.
4. The method according to claim 1, wherein the spray drying in step S1 is performed under conditions of 80-100 ℃ for inlet air temperature, 30-80 ℃ for outlet air temperature, and 1500-2000mL/h for evaporated water.
5. The method according to claim 1, wherein the calcination in step S1 is performed at a temperature of 400 to 500 ℃ for a time of 2 to 4 hours, and the ball milling is performed for 1 to 3 hours.
6. The preparation method according to claim 1, wherein the time of the reduction in the step S2 is 10-12 hours, and the concentration of the hydrazine hydrate vapor is 20-30g/L.
7. The preparation method according to claim 1, wherein the low-temperature hydrogen reduction in step S3 is performed by introducing hydrogen at 650-750 ℃ for 2-4 hours using a strongly-draining and breathable tubular furnace, and the hydrogen ventilation is 17-22L/min.
8. The preparation method according to claim 1, wherein in the step S4, the base material is aluminum alloy having an aluminum content of 99-99.6%, an iron content of 0.001-0.4%, a manganese content of 0.0001-0.05%, a titanium content of 0.0001-0.03%, a copper content of 0.0001-0.05%, a tin content of 0.0001-0.05%, an antimony content of 0.0001-0.05%, a silicon content of 0.01-0.02%, and other elements of 0.01-0.1%.
9. The preparation method according to claim 1, wherein the mixing in the step S4 is performed by heating to 600-700 ℃ for uniform mixing, and the molding treatment is performed by hot extrusion at 400-500 ℃ with an extrusion ratio of 8-12.
10. A graphene-aluminum-based alloy material prepared by the preparation method according to any one of claims 1 to 9.
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