CN114523104B - Surface nickel-phosphorus-plated graphene reinforced titanium-based composite material and preparation method thereof - Google Patents
Surface nickel-phosphorus-plated graphene reinforced titanium-based composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 181
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 72
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- 238000001291 vacuum drying Methods 0.000 claims description 16
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- 239000000956 alloy Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
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- 239000010439 graphite Substances 0.000 claims description 6
- 238000002490 spark plasma sintering Methods 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 229910052759 nickel Inorganic materials 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
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- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1666—Ultrasonics
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1889—Multistep pretreatment with use of metal first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a surface nickel-phosphorus-plated graphene reinforced titanium-based composite material, wherein the surface of graphene in the composite material is coated with a nickel-phosphorus layer, and the surface nickel-phosphorus-plated graphene is dispersed on the surface of a titanium sphere; wherein the graphene is distributed at the grain boundary of the titanium matrix, and the composite material only has diffraction peaks corresponding to alpha phase and beta phase of titanium. The invention also discloses a preparation method of the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material. The composite material solves the problem that the graphene is easy to generate TiC with titanium, and meanwhile, the graphene has better dispersibility, and the graphene is not easy to damage in the ball milling and sintering processes, so that the performance of the composite material is improved to the greatest extent.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a surface nickel-phosphorus-plated graphene reinforced titanium-based composite material and a preparation method thereof.
Background
The development demands of the new generation of aerospace craft on light weight and high performance make the titanium alloy need to improve the comprehensive performance when being applied to the field. In addition, the heat conduction performance is poor in the titanium alloy processing process, so that the processed heat cannot be conducted out quickly, thermal stress is easy to generate, and the titanium alloy part is damaged.
Graphene (GNFs) is a monoatomic layer material composed of sp2 hybridized carbon atoms, and because of its excellent properties such as excellent mechanical properties, high electrical conductivity and excellent thermal conductivity (5 times diamond, 10 times copper), and GNFs have higher strength, elongation and larger specific surface area, a good match between strength and ductility can be achieved in the fabricated composite, and GNFs will therefore be an advantageous candidate for reinforcing metal-based composites. However, strengthening metal-based composites by GNFs may result in chemical reactions of GNFs with metals, thereby adversely affecting the performance of the composite.
The Chinese patent document published as CN110512109A discloses a preparation method of a graphene reinforced composite material, which comprises the following steps: 1. ultrasonic cleaning spherical titanium powder and drying; 2. pickling the dried spherical titanium powder, and then cleaning and drying; 3. adding the dried spherical titanium powder into a nickel plating solution, heating, preserving heat and drying to obtain nickel plating spherical titanium powder; 4. adding graphene oxide into deionized water for dispersion to obtain graphene oxide dispersion liquid, adding nickel-plated spherical titanium powder into the graphene oxide dispersion liquid, carrying out heat preservation, stirring uniformly, and drying to obtain mixed powder; and fifthly, performing spark plasma hot-pressing sintering on the mixed powder to obtain the graphene reinforced titanium-based composite material. According to the method, nickel is plated on the surface of the spherical titanium powder, so that the contact between graphene and titanium powder is effectively isolated, the adverse effect of the composite material caused by chemical reaction of the graphene and titanium and the generation of interface products is avoided, the structural characteristic integrity of the graphene is ensured, and the mechanical property of the graphene reinforced titanium-based composite material is improved. However, in the ball milling process of the composite material, the structure of graphene is seriously damaged due to ball milling, and the dispersion effect of graphene on the surface of titanium powder is poor due to large density difference of graphene and titanium powder, so that the performance of the composite material is not facilitated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material, which solves the problem that the graphene is easy to generate TiC with titanium, and meanwhile, the dispersibility of the graphene is better, and the graphene is not easy to damage in the ball milling and sintering processes, so that the performance of the composite material is improved to the greatest extent.
The invention further aims to provide a preparation method of the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material comprises a nickel-phosphorus layer coated on the surface of graphene, wherein the surface nickel-phosphorus-plated graphene is dispersed on the surface of a titanium sphere; wherein the graphene is distributed at the grain boundary of the titanium matrix, and the composite material only has diffraction peaks corresponding to alpha phase and beta phase of titanium.
Further, the mass ratio of the graphene to the nickel-phosphorus layer on the surface of the graphene is 1:1-2.
Further, the peak ratio of the D peak to the G peak of the graphene is 0.174.
The preparation method of the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material comprises the following steps:
s1: sensitization of graphene
Placing graphene in deionized water, performing ultrasonic dispersion to obtain graphene suspension, adding a tin chloride solution with the same volume as the graphene suspension, continuing ultrasonic treatment, and then filtering, and washing with deionized water until the pH value of the material is neutral to obtain sensitized graphene;
s2: activation of graphene
Placing the sensitized graphene obtained in the step S1 into deionized water, performing ultrasonic dispersion to obtain sensitized graphene suspension, adding palladium chloride solution with the same volume, performing ultrasonic treatment, filtering, and washing with deionized water until the pH value of the material is neutral to obtain activated graphene;
s3: nickel-phosphorus plating layer on surface of graphene
Placing the activated graphene obtained in the step S2 into deionized water, performing ultrasonic dispersion to obtain an activated graphene suspension, adding an equal volume of chemical nickel-phosphorus plating solution, heating to 40-50 ℃ in a water bath, adjusting the pH to 7-10 by using ammonia water, stirring at constant temperature, filtering, washing by using deionized water until the pH value of the material is neutral, and finally placing the material into a vacuum drying oven for drying to obtain the surface nickel-phosphorus plating graphene;
s4: preparation of composite powder
Placing the surface nickel-phosphorus-plated graphene obtained in the step S3 and Ti-6Al-4V alloy powder into an agate tank, adding absolute ethyl alcohol until the materials are submerged, performing ball milling until the materials are uniformly mixed, transferring the ball-milled materials out, placing the materials into a water bath kettle, stirring and drying the materials until the materials are in slurry state, and placing the materials into a vacuum drying box for drying to obtain composite material powder;
s5: preparation of surface nickel-phosphorus-plated graphene reinforced titanium-based composite material
And (3) placing the composite material powder obtained in the step (S4) into a graphite mold, and performing spark plasma sintering to finally obtain the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material.
Further, in the step S3, the concentration of the activated graphene suspension is 1-3g/L, the concentration of nickel sulfate in the chemical nickel-phosphorus plating solution is 20-30g/L, the concentration of sodium citrate is 40-50g/L, and the concentration of sodium hypophosphite is 13-19g/L.
Further, in the step S3, the water bath drying time is 1-3 hours, the vacuum drying temperature is 40-50 ℃, and the drying time is 8-12 hours.
Further, in the step S4, the mass fraction of the surface nickel-phosphorus-plated graphene in the composite material powder is 0.5-1.5 wt%, the ball milling speed is 250-350rpm, the ball milling time is 2-3h, and the vacuum drying temperature is 40-50 ℃.
Further, in step S5, the sintering parameters are: sintering pressure is 45-55MPa, sintering temperature is 800-1000 ℃, sintering heat preservation and pressure maintaining time is 5-10min, and heating rate is 50-100 ℃/min.
Further, in the step S1, the concentration of the graphene suspension is 1-3g/L, the concentration of stannic chloride in the stannic chloride solution is 10g/L, the concentration of hydrochloric acid is 45mL/L, and the ultrasonic time is 30-60min.
Further, in the step S2, the concentration of the sensitized graphene suspension is 1-3g/L, the concentration of palladium chloride in the palladium chloride solution is 10g/L, the concentration of hydrochloric acid is 25mL/L, and the ultrasonic time is 30-60min.
Further, the ultrasonic power in steps S1, S2 and S3 is 100-150W.
The invention has the beneficial effects that:
1. according to the invention, the nickel-phosphorus layer is plated on the surface of the graphene, and then the graphene with the nickel-phosphorus layer on the surface is subjected to ball milling dispersion with titanium powder, so that the nickel-phosphorus layer has good hardness and wear resistance in the ball milling process, and can resist the impact and wear of the graphene from a grinding body in the ball milling process, so that the structural damage of the graphene caused by ball milling is avoided under the protection of the nickel-phosphorus layer on the surface of the graphene, the modification effect of the graphene on the composite material is ensured, and the density of the graphene modified by the nickel-phosphorus layer is higher than that of the original graphene, so that the self-agglomeration of the graphene is effectively avoided, the modified graphene can be dispersed on the surface of the titanium powder, and the performance of the composite material is further ensured; after the graphene plated with nickel and phosphorus is uniformly dispersed on the surface of titanium powder through ball milling, a compact composite material with complete graphene structure is rapidly obtained through short-time sintering of discharge plasma, and in the process, the nickel and phosphorus layer effectively isolates the contact between titanium and the graphene, so that the situation that the graphene is easy to form hard and brittle phases TiC with the titanium is avoided, and the plasticity of the material is not affected.
2. According to the composite material disclosed by the invention, the graphene has a complete structure, the graphene is uniformly distributed on the surface of the titanium powder, and TiC is not easily generated by the graphene due to the protection of the nickel-phosphorus layer, so that the graphene can be completely brought into a matrix material, the performance of the graphene serving as a reinforcing phase is completely fused into the composite material, the performance of the composite material is maximally improved, and compared with TC4 which is only wrapped with the graphene, the compressive yield strength of the nickel-plated graphene/TC 4 composite material disclosed by the invention is improved by 15.43%.
Drawings
Fig. 1 is an SEM image of pristine graphene.
Fig. 2 is an SEM image of the nickel-phosphorus modified graphene in example 2.
Fig. 3 is an EDS face scan of pristine graphene.
FIGS. 4a,4b,4c are EDS scans of carbon, nickel, and phosphorus, respectively, for the different regions of FIG. 2.
FIG. 5 is an SEM image of a 0.5% GNTs+TC4 powder mixture obtained in step S4 of example 2.
FIG. 6 is a high-magnification SEM image of the 0.5% GNTs+TC4 powder mixture obtained in step S4 of example 2.
FIGS. 7a,7b,7c are EDS scans of carbon, nickel, and phosphorus, respectively, for the different regions of FIG. 6.
FIG. 8 is an SEM image of a 0.5% GNTs+TC4 composite material obtained at step S5 of example 2.
FIGS. 9a,9b,9c are EDS scans of carbon, nickel, and phosphorus, respectively, for the different regions of FIG. 8.
Fig. 10 is an XRD pattern of the TC4 and 0.5% gnfs+tc4 composite material after sintering in example 2.
FIG. 11 is a Raman spectrum of the TC4 and 0.5% GNFs+TC4 composite after sintering in example 2.
FIG. 12 is a graph showing the compression performance of the composite material, TC4 alloy and graphene-coated TC4 alloy obtained in examples 1 to 3.
Detailed Description
For a better understanding of the technical content of the present invention, specific examples are set forth below, along with the accompanying drawings.
Unless otherwise indicated, the starting materials in the examples below were all purchased commercially.
Example 1
The ultrasonic power in this embodiment is 100W, including the following steps:
s1: sensitization of graphene
0.25g of graphene is placed in 250mL of deionized water and subjected to ultrasonic dispersion for 30min to obtain graphene suspension, and 250mL of tin chloride solution (SnCl) is added 2 10g/L and HCl 40 ml/L) is continuously treated by ultrasonic for 40min, and then is filtered, and deionized water is used for flushing until the pH value of the material is neutral, so that sensitized graphene is obtained.
S2: activation of graphene
Placing the sensitized graphene obtained in the step S1 into 250mL of deionized water, performing ultrasonic dispersion for 30min to obtain sensitized graphene suspension, and adding 250mL of palladium chloride solution (PdCl 2 10g/L, 25ml/L of HCl) and ultrasonic treatment for 40min, and then filtering, and flushing with deionized water until the pH value of the material is neutral, thus obtaining the activated graphene.
S3: nickel-phosphorus plating layer on surface of graphene
Placing the activated graphene obtained in the step S2 into 250mL of deionized water, performing ultrasonic dispersion for 60min to obtain an activated graphene suspension, adding 250mL of chemical nickel-phosphorus plating solution (nickel sulfate 20g/L, sodium citrate 50g/L and sodium hypophosphite 13 g/L), heating to 40-50 ℃ in a water bath, regulating the pH to 7-10 by using ammonia water, stirring at constant temperature for 1-3h, filtering, washing with deionized water until the pH value of the material is neutral, and finally drying at 45 ℃ in a vacuum drying oven for 8h to obtain the surface nickel-phosphorus plating graphene; wherein the mass ratio of the graphene to the nickel-phosphorus layer is 1:1.
S4: preparation of composite powder
And (3) placing the surface nickel-phosphorus-plated graphene obtained in the step (S3) and Ti-6Al-4V alloy powder into an agate tank, wherein the graphene accounts for 1.5wt.% of the mixed powder, adding absolute ethyl alcohol until the materials are submerged, performing omnibearing ball milling with parameters of 350rpm and 3h until the materials are uniformly mixed, transferring the ball-milled materials into a beaker, placing the beaker into a water bath kettle at 40-60 ℃ for stirring and drying, placing the materials into a vacuum drying box at 40 ℃ for 6h after the materials are in slurry state, and obtaining composite material powder.
S5: preparation of surface nickel-phosphorus-plated graphene reinforced titanium-based composite material
Putting the composite material powder obtained in the step S4 into a graphite mold, performing spark plasma sintering, and finally obtaining the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material; wherein, sintering parameters are as follows: sintering pressure is 45MPa, sintering temperature is 800 ℃, sintering heat preservation and pressure maintaining time is 5min, and heating rate is 50 ℃/min.
Example 2
The ultrasonic power in this embodiment is 100W, including the following steps:
s1: sensitization of graphene
0.5g of graphene is placed in 250mL of deionized water and subjected to ultrasonic dispersion for 60min to obtain graphene suspension, and 250mL of tin chloride solution (SnCl) is added 2 10g/L and 40ml/L of HCl) for 30min, and then filtering, and flushing with deionized water until the pH value of the material is neutral, thus obtaining the sensitized graphene.
S2: activation of graphene
The sensitization obtained in the step S1Placing the graphene in 250mL of deionized water, performing ultrasonic dispersion for 60min to obtain sensitized graphene suspension, and adding 250mL of palladium chloride solution (PdCl 2 10g/L, 25ml/L of HCl) and ultrasonic treatment for 30min, and then filtering, and flushing with deionized water until the pH value of the material is neutral, thus obtaining the activated graphene.
S3: nickel-phosphorus plating layer on surface of graphene
Placing the activated graphene obtained in the step S2 into 250mL of deionized water, performing ultrasonic dispersion for 60min to obtain an activated graphene suspension, adding 250mL of chemical nickel-phosphorus plating solution (nickel sulfate 25g/L, sodium citrate 45g/L and sodium hypophosphite 15 g/L), heating to 40-50 ℃ in a water bath, regulating the pH to 7-10 by using ammonia water, stirring at constant temperature for 1-3h, filtering, washing with deionized water until the pH value of the material is neutral, and finally drying for 10h at 45 ℃ in a vacuum drying oven to obtain the surface nickel-phosphorus plating graphene; wherein the mass ratio of the graphene to the nickel-phosphorus layer is 1:1.5.
S4: preparation of composite powder
And (3) placing the surface nickel-phosphorus-plated graphene obtained in the step (S3) and Ti-6Al-4V alloy powder into an agate tank, wherein the graphene accounts for 0.5wt.% of the mixed powder, adding absolute ethyl alcohol until the materials are submerged, performing omnibearing ball milling with parameters of 300rpm and 3h until the materials are uniformly mixed, transferring the ball-milled materials into a beaker, placing the beaker into a water bath kettle at 40-60 ℃ for stirring and drying, placing the slurry-like materials into a vacuum drying oven for drying at 45 ℃ for 10 hours, and obtaining composite material powder.
S5: preparation of surface nickel-phosphorus-plated graphene reinforced titanium-based composite material
Putting the composite material powder obtained in the step S4 into a graphite mold, performing spark plasma sintering, and finally obtaining the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material; wherein, sintering parameters are as follows: sintering pressure is 50MPa, sintering temperature is 900 ℃, sintering heat preservation and pressure maintaining time is 5min, and heating rate is 100 ℃/min.
Example 3
The ultrasonic power in this embodiment is 100W, including the following steps:
s1: sensitization of graphene
0.75g of graphene is placed in 250mL of deionized water and subjected to ultrasonic dispersion for 60min to obtain graphene suspension, and 250mL of tin chloride solution (SnCl) is added 2 10g/L and 40ml/L of HCl) for 30min, and then filtering, and flushing with deionized water until the pH value of the material is neutral, thus obtaining the sensitized graphene.
S2: activation of graphene
Placing the sensitized graphene obtained in the step S1 into 250mL of deionized water, performing ultrasonic dispersion for 60min to obtain sensitized graphene suspension, and adding 250mL of palladium chloride solution (PdCl 2 10g/L, 25ml/L of HCl) and ultrasonic treatment for 30min, and then filtering, and flushing with deionized water until the pH value of the material is neutral, thus obtaining the activated graphene.
S3: nickel-phosphorus plating layer on surface of graphene
Placing the activated graphene obtained in the step S2 into 250mL of deionized water, performing ultrasonic dispersion for 60min to obtain an activated graphene suspension, adding 250mL of chemical nickel-phosphorus plating solution (30 g/L of nickel sulfate, 40g/L of sodium citrate and 19g/L of sodium hypophosphite), heating to 40-50 ℃ in a water bath, adjusting the pH to 7-10 by using ammonia water, stirring at constant temperature for 1-3h, filtering, washing with deionized water until the pH value of the material is neutral, and finally drying at 45 ℃ for 12h in a vacuum drying oven to obtain the surface nickel-phosphorus plating graphene; wherein the mass ratio of the graphene to the nickel-phosphorus layer is 1:2.
S4: preparation of composite powder
And (3) placing the surface nickel-phosphorus-plated graphene obtained in the step (S3) and Ti-6Al-4V alloy powder into an agate tank, wherein the graphene accounts for 1wt.% of the mixed powder, adding absolute ethyl alcohol until the materials are submerged, performing omnibearing ball milling with parameters of 300rpm and 3h until the materials are uniformly mixed, transferring the ball-milled materials into a beaker, placing the beaker into a water bath kettle at 40-60 ℃ for stirring and drying, placing the slurry-like materials into a vacuum drying box for drying at 45 ℃ for 12h, and obtaining composite material powder.
S5: preparation of surface nickel-phosphorus-plated graphene reinforced titanium-based composite material
Putting the composite material powder obtained in the step S4 into a graphite mold, performing spark plasma sintering, and finally obtaining the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material; wherein, sintering parameters are as follows: sintering pressure is 55MPa, sintering temperature is 1000 ℃, sintering heat preservation and pressure maintaining time is 5min, and heating rate is 100 ℃/min.
Comparative example
S1: sensitization of graphene
0.5g of graphene is placed in 250mL of deionized water and subjected to ultrasonic dispersion for 60min to obtain graphene suspension, and 250mL of tin chloride solution (SnCl) is added 2 10g/L and 40ml/L of HCl) for 30min, and then filtering, and flushing with deionized water until the pH value of the material is neutral, thus obtaining the sensitized graphene.
S2: activation of graphene
Placing the sensitized graphene obtained in the step S1 into 250mL of deionized water, performing ultrasonic dispersion for 60min to obtain sensitized graphene suspension, and adding 250mL of palladium chloride solution (PdCl 2 10g/L, 25ml/L of HCl) and ultrasonic treatment for 30min, and then filtering, and flushing with deionized water until the pH value of the material is neutral, thus obtaining the activated graphene.
S3: graphene blank sample
And (3) placing the activated graphene obtained in the step (S2) in 250mL of deionized water, performing ultrasonic dispersion for 60min to obtain an activated graphene suspension, adding 250mL of deionized water, heating to 40-50 ℃ in a water bath, adjusting the pH to 7-10 by using ammonia water, stirring at constant temperature for 1-3h, filtering, washing by using deionized water until the pH value of the material is neutral, and finally drying at 45 ℃ in a vacuum drying oven for 10h to obtain a graphene blank sample.
S4: preparation of composite powder
And (3) placing the graphene blank sample obtained in the step (S3) and Ti-6Al-4V alloy powder into an agate tank, wherein the graphene accounts for 0.5wt.% of the mixed powder, adding absolute ethyl alcohol until the materials are submerged, performing omnibearing ball milling with parameters of 300rpm and 3h until the materials are uniformly mixed, transferring the ball milled materials into a beaker, placing the beaker into a water bath kettle at 40-60 ℃ for stirring and drying, placing the materials into a vacuum drying box at 45 ℃ for drying for 10 hours when the materials are in slurry state, and obtaining composite material powder.
S5: preparation of graphene reinforced titanium-based composite material
Putting the composite material powder obtained in the step S4 into a graphite mold, and performing spark plasma sintering to finally obtain the graphene reinforced titanium-based composite material; wherein, sintering parameters are as follows: sintering pressure is 50MPa, sintering temperature is 900 ℃, sintering heat preservation and pressure maintaining time is 5min, and heating rate is 100 ℃/min.
[ PREPARATION METHOD ]
The surface nickel-phosphorus-plated graphene-reinforced titanium-based composite material obtained in example 2 and intermediates in the process thereof were characterized as follows:
1. SEM image and EDS face scan
Fig. 1 is an SEM image of original graphene, and fig. 2 is an SEM image of nickel-phosphorus modified graphene, where, compared with fig. 1, after the electroless nickel-phosphorus treatment in fig. 2, a number of granular nickel-phosphorus layers (as marked in circles) have been attached to the surface of the graphene.
Fig. 3 is an EDS sweep of original graphene, and fig. 4a,4b, and 4c are EDS sweep analysis of carbon, nickel, and phosphorus performed on different areas of fig. 2, respectively, compared with fig. 3, it can be seen in fig. 4 that nickel phosphorus is well distributed on the surface of graphene, and under the effect of the coverage of nickel phosphorus, carbon element is hard to characterize treatment, which also demonstrates the good nickel phosphorus coating effect of the process from the side.
Fig. 5 is an SEM image of the 0.5% gnts+tc4 mixed powder obtained in step S4, and it can be seen from the image that, through the high-energy short-time ball milling process, the nickel-phosphorus modified graphene is dispersed on the surface of the titanium ball (as shown by the arrow). In order to further determine the nickel-phosphorus modified graphene on the surface of the titanium ball, high-power SEM (FIG. 6) and EDS (electronic scanning system) surface scanning analysis (FIGS. 7a,7b and 7C) are used, and as can be seen from FIGS. 7a-7C, the energy spectrum surface scanning of the C element hardly detects the C element, the nickel and phosphorus elements are quite obvious, and the distribution area corresponds to the position of the nickel-phosphorus modified graphene on the surface of the titanium ball (FIG. 6), which also indicates that the graphene after ball milling is still coated by the nickel-phosphorus layer, so that the structure of the graphene is protected from being damaged.
Fig. 8 is an SEM image of the 0.5% gnts+tc4 composite obtained in step S5, fig. 9 is an EDS facial scan analysis corresponding to fig. 8, and fig. 8 shows that graphene is distributed at the grain boundaries of the titanium matrix, and that no significant new phase is formed between graphene and the titanium matrix, and that in combination with EDS facial scan analysis of the carbon element in this region (fig. 9 a), the carbon element is also demonstrated and diffused in the titanium matrix.
Fig. 9b and 9c are EDS scans of the nickel element and EDS scans of the corresponding grain boundary in the region of fig. 8, respectively, and the results show that the nickel element and the phosphorus element can be found to be mainly and intensively distributed at the grain boundary position of titanium, which is the same as the position where the graphene is distributed in fig. 9a, and meanwhile, the nickel in contact with the titanium substrate can be found to be slightly diffused from the spectrum line scan, while the phosphorus element is not diffused in the titanium substrate, which shows that the plating layer is still on the surface of the graphene, and the nickel-phosphorus plating layer is proved to protect the structure of the graphene and prevent the graphene from reacting with the titanium substrate.
2. XRD and Raman spectra
Fig. 10 and fig. 11 are XRD and raman spectra of the TC4 and 0.5% gnfs+tc4 composite materials sintered in step S5, respectively, and XRD results show that only the α phase and the β phase of titanium are detected in the sintered composite materials, and no TiC phase is detected, which indicates that graphene and titanium do not react significantly in the sintered composite materials, and further indicates that the nickel-phosphorus layer effectively protects the structure of graphene, and effectively isolates graphene and titanium matrix.
The raman spectrum analysis of fig. 11 can further effectively detect the integrity of graphene, and it is known from the raman spectrum analysis that, first, the graphene in the sintered composite material can still detect the marked diffraction peaks D, G and 2D of the graphene, which indicates that the structure of the graphene is not transformed in the previous ball milling and sintering process, and the nickel-phosphorus plating layer plays a significant role in protection and isolation; secondly, the peak intensity ratio of the D peak and the G peak in the graphene is effective information for judging the structural integrity of the graphene, and the closer the peak intensity ratio is to the original graphene, the smaller the damage of ball milling and sintering to the graphene is, as can be seen in fig. 11, the peak intensity ratio of the D peak and the G peak of the graphene in the composite material is 0.174, and compared with the 0.074 of the original graphene, the closer the peak intensity ratio is to the peak intensity ratio of the D peak and the G peak of the graphene in the composite material is, and the smaller the structural damage of the graphene in the composite material is further illustrated due to the protection of a nickel-phosphorus layer on the surface of the graphene.
[ Performance test ]
FIG. 12 is a graph comparing compression performance of TC4 alloy and the composites obtained in examples 1-3, wherein the composite obtained in example 1 has a yield strength of 1091.3MPa, and the addition of 1.5% GNFs increases the compressive yield strength of the composite by 24.87% compared with TC4 alloy; the yield strength of the composite material obtained in the embodiment 2 is 1129.47Mpa, compared with a TC4 alloy, the compressive yield strength of the material is improved by 29.23% by adding 0.5% GNFs, and compared with a TC4 alloy which is coated with 0.5% graphene, the compressive yield strength of the material is improved by 15.43% by adding 0.5% GNFs; the yield strength of the composite material obtained in example 3 was 1144.08Mpa, and the addition of 1% gnfs improved the compressive yield strength of the material by 30.90% compared to the TC4 alloy.
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (8)
1. The preparation method of the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material is characterized by comprising the following steps of:
s1: sensitization of graphene
Placing graphene in deionized water, performing ultrasonic dispersion to obtain graphene suspension, adding a tin chloride solution with the same volume as the graphene suspension, continuing ultrasonic treatment, and then filtering, and washing with deionized water until the pH value of the material is neutral to obtain sensitized graphene;
s2: activation of graphene
Placing the sensitized graphene obtained in the step S1 into deionized water, performing ultrasonic dispersion to obtain sensitized graphene suspension, adding palladium chloride solution with the same volume, performing ultrasonic treatment, filtering, and washing with deionized water until the pH value of the material is neutral to obtain activated graphene;
s3: nickel-phosphorus plating layer on surface of graphene
Placing the activated graphene obtained in the step S2 into deionized water, performing ultrasonic dispersion to obtain an activated graphene suspension, adding an equal volume of chemical nickel-phosphorus plating solution, heating to 40-50 ℃ in a water bath, adjusting the pH to 7-10 by using ammonia water, stirring at constant temperature, filtering, washing by using deionized water until the pH value of the material is neutral, and finally placing the material into a vacuum drying oven for drying to obtain the surface nickel-phosphorus plating graphene;
s4: preparation of composite powder
Placing the surface nickel-phosphorus-plated graphene obtained in the step S3 and Ti-6Al-4V alloy powder into an agate tank, adding absolute ethyl alcohol until the materials are submerged, performing ball milling until the materials are uniformly mixed, transferring the ball-milled materials out, placing the materials into a water bath kettle, stirring and drying the materials until the materials are in slurry state, and placing the materials into a vacuum drying box for drying to obtain composite material powder;
s5: preparation of surface nickel-phosphorus-plated graphene reinforced titanium-based composite material
Putting the composite material powder obtained in the step S4 into a graphite mold, performing spark plasma sintering, and finally obtaining the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material; wherein, the sintering parameters are as follows: sintering pressure is 45-55Mpa, sintering temperature is 800-1000 ℃, sintering heat preservation and pressure maintaining time is 5-10min, and heating rate is 50-100 ℃/min;
in the surface nickel-phosphorus-plated graphene reinforced titanium-based composite material, graphene is distributed at the grain boundary of a titanium matrix, the peak ratio of a D peak to a G peak of the graphene is 0.174, and the composite material only has diffraction peaks corresponding to an alpha phase and a beta phase of titanium.
2. The method for preparing the surface nickel-phosphorus-plated graphene-reinforced titanium-based composite material according to claim 1, which is characterized by comprising the following steps: the mass ratio of the graphene to the nickel-phosphorus layer on the surface of the graphene is 1:1-2.
3. The method for preparing the surface nickel-phosphorus-plated graphene-reinforced titanium-based composite material according to claim 1, which is characterized by comprising the following steps: in the step S3, the concentration of the activated graphene suspension is 1-3g/L, the concentration of nickel sulfate in the chemical nickel-phosphorus plating solution is 20-30g/L, the concentration of sodium citrate is 40-50g/L, and the concentration of sodium hypophosphite is 13-19g/L.
4. The method for preparing the surface nickel-phosphorus-plated graphene-reinforced titanium-based composite material according to claim 1, which is characterized by comprising the following steps: in the step S3, the water bath time is 1-3h, the vacuum drying temperature is 40-50 ℃ and the drying time is 8-12h.
5. The method for preparing the surface nickel-phosphorus-plated graphene-reinforced titanium-based composite material according to claim 1, which is characterized by comprising the following steps: in the step S4, the mass fraction of the surface nickel-phosphorus-plated graphene in the composite material powder is 0.5-1.5 wt%, the ball milling speed is 250-350rpm, the ball milling time is 2-3h, and the vacuum drying temperature is 40-50 ℃.
6. The method for preparing the surface nickel-phosphorus-plated graphene-reinforced titanium-based composite material according to claim 1, which is characterized by comprising the following steps: in the step S1, the concentration of the graphene suspension is 1-3g/L, the concentration of stannic chloride in the stannic chloride solution is 10g/L, the concentration of hydrochloric acid is 45mL/L, and the ultrasonic time is 30-60min.
7. The method for preparing the surface nickel-phosphorus-plated graphene-reinforced titanium-based composite material according to claim 1, which is characterized by comprising the following steps: in the step S2, the concentration of the sensitized graphene suspension is 1-3g/L, the concentration of palladium chloride in the palladium chloride solution is 10g/L, the concentration of hydrochloric acid is 25mL/L, and the ultrasonic time is 30-60min.
8. The method for preparing the surface nickel-phosphorus-plated graphene-reinforced titanium-based composite material according to claim 1, which is characterized by comprising the following steps: the ultrasonic power in steps S1, S2 and S3 is 100-150W.
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