CN115491659A - Method for improving mechanical property of metal-based composite material by modifying graphene on surface of titanium dioxide - Google Patents
Method for improving mechanical property of metal-based composite material by modifying graphene on surface of titanium dioxide Download PDFInfo
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Abstract
The invention provides a method for improving the mechanical property of a metal-based composite material by modifying graphene on the surface of titanium dioxide, wherein a titanium dioxide film is grown on the surface of graphene by an atomic layer deposition method, the growth thickness of the film on the surface of graphene is regulated and controlled by regulating and controlling deposition conditions and cycle times, and deposited TiO 2 Thin film modified graphene powder TiO 2 The @ Gr is mixed with metal powder in a low-energy ball milling mode to prepare composite powder, the composite powder is heated and pressurized to sinter to prepare the formed metal-based composite material, the mechanical strength of the formed composite material is obviously improved, and TiO can be realized by regulating and controlling the ratio of raw materials and the cycle number 2 Thickness of the film layerThe degree is accurate and controllable, and the precision can reach the nanometer level; the preparation process hardly introduces redundant impurities, and near-net TiO is realized 2 The film grows, the graphene is easy to disperse after film coating, the sample preparation period can be shortened, the whole process control can be realized, the safety and the simple operation are realized, and the batch production can be realized.
Description
Technical Field
The invention belongs to the technical field of metal-based composite materials, and particularly relates to a method for improving mechanical properties of a metal-based composite material by modifying graphene on the surface of titanium dioxide.
Background
The metal matrix composite is a multi-component material which improves the strength of matrix alloy through the bearing effect and the strengthening effect of the reinforcement, so the performance of the reinforcement determines the upper limit of the performance of the metal matrix composite. The fracture strength of the graphene is ultrahigh and reaches 130 GPa; ultra-high Young's modulus, up to 1 TPa and lower density, as low as 1.2 g/cm 3 And the super-large specific surface area, and the like, and is considered to be one of the most ideal reinforcements of the composite material. The graphene is compounded with the metal matrix, so that the strength of the metal matrix can be greatly improved, and the weight of the composite material is reduced.
However, due to the large physical and chemical difference between the graphene and the metal matrix, the wettability between the graphene and the metal matrix is poor, so that the interface bonding is poor, and the interface is easy to lose efficacy in the bearing process; this will cause the load-bearing effect of graphene in the composite material to be difficult to achieve, and the strengthening effect thereof is greatly reduced, even the mechanical properties of the graphene/metal matrix composite material are deteriorated.
Chinese patent publication No. CN104451227A discloses a method for preparing a copper-plated graphene reinforced metal matrix composite, the method utilizes a chemical plating method to prepare a nano copper coating on the surface of graphene oxide through sensitization, activation and reduction, the method can improve the interface structure between graphene and a metal matrix, but a sensitized tin layer and an activated silver layer are introduced in the preparation process, and redundant low-melting-point elements can cause a large amount of low-melting-point brittle phases to be generated in an alloy matrix, so that the alloy performance of the matrix is reduced.
The Chinese patent publication No. CN114752800A discloses a preparation method of a rare earth modified graphene reinforced metal-based composite bar, the method utilizes a chemical reduction method to prepare rare earth element modified reduced graphene oxide by reduction on the surface of graphene oxide, and prepares a reinforced metal-based composite material by sintering, but the method has complicated and complicated steps, is easy to introduce a large amount of chemical impurity residues, and the used strong reducing agent hydrazine hydrate is highly toxic and inflammable and explosive, is listed in the easily explosive hazardous chemical record, and is difficult to apply to actual industrial production. And the production efficiency is low, and large-scale structural components cannot be produced in batches.
Chinese patent publication No. CN106881466A discloses a graphene metal-based composite material and a preparation method thereof, the method utilizes an electrochemical method to reduce low-melting-point nano metal particles on the surface of graphene to prepare composite powder, but the method is easy to introduce a large amount of chemical impurity residues, has low production efficiency, is only suitable for miniature electronic components and cannot produce and prepare large-scale structural members in batches.
Chinese patent publication No. CN201510521976.6 discloses a chemical plating graphene, a preparation method thereof, and a metal matrix composite, in which an electrochemical method is used to modify and incorporate a low-melting-point sensitizing layer and an activating layer on the surface of graphene, so as to reduce nickel atoms on the surface layer and form a modification layer, but the method is easy to introduce a large amount of chemical impurity residues, and the low-melting-point sensitizing layer and the activating layer are easy to introduce a large amount of impurity elements into the matrix, which causes unstable texture and phase composition of the matrix alloy, and leads to unstable product quality, and thus, standardized production cannot be realized.
Based on the method, the method for improving the mechanical property of the metal matrix composite material by modifying the graphene on the surface of the titanium dioxide is provided.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for improving the mechanical property of a metal-based composite material by modifying graphene on the surface of titanium dioxide, so as to solve the problems in the background art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for improving mechanical properties of a metal matrix composite material by modifying graphene on the surface of titanium dioxide comprises the following steps:
s1, pouring a graphene raw material into an acid solution for acid washing, carrying out ultrasonic cleaning for 30 min, filtering and drying;
s2, weighing a certain mass of graphene processed in the step S1, placing the graphene on a deposition plate, diluting the graphene with alcohol, uniformly spreading the graphene, and standing and drying the graphene;
s3, placing the deposition plate of the graphene in the S2 into a chamber of the atomic layer deposition equipment, and setting deposition parameters and deposition cycle times according to the deposition thickness;
s4, depositing and growing TiO in the S3 2 Collecting @ Gr, and carrying out low-energy ball milling on the collected @ Gr and metal powder to prepare composite powder;
and S5, heating and pressurizing the composite powder uniformly mixed in the step S4, sintering and forming to finish the preparation.
Further, in S1, the graphene is specifically a graphene nanosheet, graphene oxide, redox graphene, multi-layer graphene or few-layer graphene; the acid solution is at least one of nitric acid, sulfuric acid and hydrochloric acid, and the acid concentration of the acid solution is 10 to 20 percent; when the pickling concentration is lower than 10%, the cleaning effect of impurities on the surface of the graphene is poor; when the pickling concentration is higher than 20%, the pickling effect is not obviously influenced.
Furthermore, the deposition plate material is a thin plate with smooth surface, and the surface stacking mass of the graphene is less than 0.2 mg/cm 2 When the accumulation amount of the graphene on the surface of the deposited plate exceeds 0.2 mg/cm 2 In the process, aggregation is easily generated between the graphenes, so that the coating layer is not uniform.
Further, in S3, the deposition raw materials of the chamber of the atomic layer deposition equipment are titanium-containing titanium titanate tetra-isopropanol and deionized water, and TiO is settled through medium-high temperature oxidation hydrolysis reaction of organic compounds 2 ；
Wherein, the titanium tetraisopropoxide cavity is heated to 60-100 ℃ according to the thickness of the deposition layer, the titanium tetraisopropoxide is beneficial to volatilization, the air flow pumped in the cavity is 50 mL/min, the cavity is in a vacuum drying state, and otherwise, flash explosion can occur.
Further, in S3, the deposition generation process is a constant temperature process, and the holding temperature is 100 to 180 ℃; the theoretical deposition thickness is specifically as follows; the unit is nm:
where N is the number of deposition cycles.
The cycle of the single deposition process is specifically as follows:
vacuumizing a sample bin of atomic layer deposition equipment to 10-100 Pa, and keeping the sample bin for 20-50 s to remove excessive water vapor, wherein the water vapor is insufficiently removed when the holding time is less than 20s, and the tetraisopropanol titanate is easy to decompose in advance, so that a deposited layer cannot be attached to the surface of graphene; the holding time is more than 50s, and the water vapor removal effect is not obvious;
pumping in vaporized tetra-isopropanol titanate by pulse, and keeping the load for 4 to 20 seconds to ensure that the tetra-isopropanol titanate is fully attached to the surface of the graphene; the load holding time is less than 1 s, and no attachment effect exists; when the duration is 1 to 4 s, tiO 2 Granular deposition, which cannot be layered; the time length is more than 20s, the deposition layer grows irregularly, and the titanium tetraisopropyl alcohol is easy to attach to the wall of the container in a large amount, so that the pollution of the inner wall is caused, and the waste of raw materials and the uneven deposition are caused;
and then vacuumizing and keeping the vacuum for 15 to 60 seconds to remove the redundant titanium tetraisopropyl alcohol, wherein the vacuum keeping time is shorter than 15 s, residual titanium tetraisopropyl alcohol exists in the cavity, the cavity is polluted, and the quality of a deposition layer is influenced. When the holding time is more than 60s, the promotion effect on the reactants is weaker. Wherein the ratio of the holding time to the graphene mass is more than 0.8 s/mg; when the ratio is less than 0.8 s/mg, the deposition layer grows in a point shape;
then pumping deionized water vapor in a pulse manner, and keeping the load for 1 to 20 seconds to ensure that the titanium-containing organic matter is fully oxidized and hydrolyzed to generate H 4 TiO 4 With a hold load below 1 s, the reaction is insufficient and the deposited layer is unstable. When the holding time is longer than 20s, no promotion is caused to the reactionThe action is carried out.
The hydrolysis equation is as follows:
then pumping out excessive water vapor in a pulse mode, and keeping the load for 20 to 50s to decompose titanic acid at high temperature to generate TiO 2
When the holding time is less than 20s, the pyrolysis reaction is insufficient, and the deposited layer is easy to be unstable; on the other hand, when the length of the catalyst is higher than 50s in the holding state, no reactant promoting effect is exerted on the deposited layer;
further, in S4, the grown TiO is deposited 2 In the preparation of composite powder material by low-energy ball milling of @ Gr and metal powder, tiO 2 The mass fraction of @ Gr is 0 to 10 wt%; the particle size of the metal powder is larger than 10 mu m, the metal powder is iron, aluminum, magnesium, titanium, nickel or alloy powder, the difference between the particle size of the metal powder and the particle size of the graphene sheet is small, a serious grinding effect is easily caused, and the coating is easy to fall off.
Further, in S4, the ball milling is carried out by low-energy ball milling of vibration type powder mixing, wherein the ball-material ratio is controlled to be 0.1 to 2, the diameter of a grinding ball is 5 to 15 mm, the vibration frequency is 40 to 80 Hz, and the powder occupies 20 to 30 percent of the volume of the container.
Further, when the powder is subjected to heating and pressurizing sintering molding in S5, pre-cooling and pressurizing treatment can be performed on the powder according to the type of a die before sintering, and the load-holding pressure is kept at 10 to 20 MPa when the powder is subjected to cold pressing; the vacuum degree is lower than 1 Pa during sintering, and the sintering pressure is 10 to 80 MPa;
when a graphite die is adopted, the sintering pressure is controlled to be 30 to 60 MPa.
Further, in S5, the sintering temperature of the composite powder is T, and the melting point T of the metal material is T 0 Wherein:
T=(0.5~0.9)T 0 ，
the heat preservation time is 5 min to 6 h;
when the titanium-based composite material is prepared, the sintering temperature is controlled to be 900-1200 ℃, and the pressure is controlled to be 30-60 MPa;
when the aluminum matrix composite material is prepared, the sintering temperature is controlled to be 450-600 ℃, and the pressure is controlled to be 45-80 MPa;
when SPS sintering is adopted, the sintering time is controlled within 60 min.
Compared with the prior art, the invention has the following advantages:
1. according to the method, a titanium dioxide film is grown on the surface of graphene by an atomic layer deposition method, the growth thickness of the film on the surface of the graphene is regulated and controlled by regulating and controlling deposition conditions and cycle times, and deposited TiO 2 Thin film modified graphene powder (TiO) 2 @ Gr), prepare composite powder through mixing with metal powder the mode of low energy ball-milling, prepare the metal matrix composite that takes shape through the sintering of heating pressurization to composite powder, the composite mechanical strength who takes shape obviously promotes.
2. The invention can realize TiO through regulating and controlling the raw material proportion and the cycle number 2 The thickness of the thin film layer is accurate and controllable, and the accuracy can reach the nanometer level; the preparation process hardly introduces redundant impurities, and near-net TiO is realized 2 And (5) growing the film.
3. The graphene is easy to disperse after the film is coated, the sample preparation period can be shortened, the whole process control can be realized, the operation is safe and simple, and the batch production can be realized.
Drawings
Fig. 1 is a topographic map (GNS) of Graphene nanoplates used in embodiments 1 and 2 of the present invention;
FIG. 2 is an appearance of graphene uniformly laid on a square deposition plate of 10X 10 cm in example 1 of the present invention;
FIG. 3 shows the surface deposition of 50 nm thickness of TiO on graphene in example 1 of the present invention 2 Scanning the transmission profile map;
FIG. 4 is a secondary electron scan of the composite powder after vibration mixing in example 1 of the present invention;
FIG. 5 shows a sintered TiO compound in example 1 of the present invention 2 The appearance diagram of the @ GNS/TC4 composite material;
FIG. 6 is a graph showing the room temperature tensile properties of the sintered composite material of example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Embodiment 1, as shown in fig. 1 to 6, the present invention provides a technical solution: a method for improving mechanical properties of a metal matrix composite material by modifying graphene on the surface of titanium dioxide adopts tetraisopropyl titanate C as a raw material 12 H 28 O 4 Ti and Graphene nano-sheets Graphene nanosheets, GNSs and TC4 powder, wherein the particle size of the powder is 15-53 mu m.
S1, weighing 0.5 g of GNS powder, pouring the GNS powder into a nitric acid solution with the concentration of 100 ml of 10%, ultrasonically cleaning 25 Hz for 30 min, filtering, and vacuum-drying 1 h at 120 ℃;
s2, weighing 10 mg GNS powder from S1, placing the GNS powder on a square deposition plate of 10 x 10 cm, diluting the GNS powder with alcohol, uniformly coating the GNS powder, standing and airing the GNS powder;
s3, placing the deposition plate in the S2 into an atomic layer deposition chamber, sealing a bin gate, heating to 160 ℃, and preserving heat;
s4, setting whisker parameters on the basis of S3, wherein the pulse time is 1S, the holding time is 8S, the degassing time is 20S, and the cycle number is 200;
s5, preparing TiO in S4 2 Collecting the @ Gr powder, weighing 0.5 g graphene and 99.5 g TC4 powder, mixing in a vibration mode, wherein the vibration frequency is 60 Hz, and the ball-material ratio is 1:1, grinding the material for 1 hour, wherein the diameter of a grinding ball is 10 mm;
s6, weighing 80 g of the composite powder prepared in the S5, placing the powder into a die with the inner diameter of 45 mm, sintering at 1000 ℃ and 60 MPa for 30 min to obtain TiO 2 The yield strength of the modified graphene reinforced titanium-based composite material is obviously improved.
s1, weighing 0.2 g redox graphene powder, pouring 100 ml hydrochloric acid solution with the concentration of 10%, carrying out ultrasonic cleaning on 20 Hz for 30 min, filtering, and carrying out vacuum drying on 1 h at 120 ℃;
s2, weighing 20 mg ORG powder from S1, placing the ORG powder on a square deposition plate of 15 x 15 cm, diluting the ORG powder with alcohol, uniformly coating the ORG powder, standing and airing;
s3, placing the deposition plate in the S2 into an atomic layer deposition chamber, sealing a bin gate, heating to 160 ℃, and preserving heat;
s4, setting whisker parameters on the basis of S3, wherein the pulse time is 0.8S, the load-holding time is 15S, the degassing time is 30S, and the cycle number is 100;
s5, preparing TiO in S4 2 Collecting the @ Gr powder, weighing 0.1 g graphene and 99.9 g Al powder, and mixing in a vibration mode, wherein the vibration frequency is 60 Hz, and the ball-material ratio is 1:1, the diameter of a grinding ball is 10 mm, and the ball milling is carried out for 1 hour;
s6, weighing 60 g in the composite powder prepared in S5, placing the powder into a mold with the inner diameter of 45 mm, sintering at 550 ℃ and 60 MPa for 30 min to obtain TiO 2 Modified graphene reinforced aluminum matrix composite.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for improving mechanical properties of a metal matrix composite material by modifying graphene on the surface of titanium dioxide is characterized by comprising the following steps: the method comprises the following steps:
s1, pouring a graphene raw material into an acid solution for acid washing, carrying out ultrasonic cleaning for 30 min, filtering and drying;
s2, weighing a certain mass of graphene processed in the step S1, placing the graphene on a deposition plate, diluting the graphene with alcohol, uniformly spreading the graphene, and standing and drying the graphene;
s3, placing the deposition plate of the graphene in the S2 into a chamber of the atomic layer deposition equipment, and setting deposition parameters and deposition cycle times according to the deposition thickness;
s4, depositing and growing TiO in the S3 2 Collecting the @ Gr, and carrying out low-energy ball milling on the collected @ Gr and metal powder to prepare composite powder;
and S5, heating and pressurizing the composite powder uniformly mixed in the step S4, sintering and forming to finish the preparation.
2. The method for improving the mechanical property of the metal matrix composite material by using the titanium dioxide surface-modified graphene according to claim 1, wherein in S1, the graphene is specifically a graphene nanosheet, a graphene oxide, a redox graphene, a multi-layer graphene or a few-layer graphene; the acid solution is at least one of nitric acid, sulfuric acid and hydrochloric acid, and the acid concentration of the acid solution is 10-20%.
3. The method for improving the mechanical properties of the metal matrix composite material by using the titanium dioxide surface modified graphene as claimed in claim 1, wherein the deposition plate material is a thin plate with a smooth surfaceThe surface stacking mass of the graphene is less than 0.2 mg/cm 2 。
4. The method for improving the mechanical property of the metal-based composite material through the titanium dioxide surface modified graphene according to claim 1, wherein in S3, deposition raw materials of a chamber of atomic layer deposition equipment are titanium-containing tetraisopropanol titanate and deionized water, and TiO is settled through medium-high temperature oxidation hydrolysis reaction of an organic compound 2 ；
Wherein the titanium tetraisopropoxide cavity is heated to 60-100 ℃ according to the thickness of the deposition layer, the air flow is pumped in for 50 ml/min, and the titanium tetraisopropoxide cavity is required to be in a vacuum drying state.
5. The method for improving the mechanical property of the metal matrix composite material by modifying the graphene on the surface of the titanium dioxide according to claim 1, wherein in S3, the deposition generation process is a constant temperature process, and the holding temperature is 100 to 180 ℃; the theoretical deposition thickness is as follows:
where N is the number of deposition cycles.
6. The method for improving the mechanical property of the metal matrix composite material by using the titanium dioxide surface modified graphene according to claim 5, wherein the cycle of a single deposition process is as follows:
vacuumizing a sample bin of atomic layer deposition equipment, wherein the vacuum degree is 10-100 Pa, keeping the vacuum level for 20-50 s to remove excessive water vapor, pumping gasified tetraisopropanol titanate through pulses, keeping the vacuum level for 4-20 s, vacuumizing, keeping the vacuum level for 15-60s to remove excessive tetraisopropanol titanate, pumping deionized water vapor through pulses, keeping the vacuum level for 1-20 s to ensure that a titanium-containing organic substance is fully oxidized and hydrolyzed to generate H 4 TiO 4 Then pumping out excessive water vapor by pulse, and keeping the temperature for 20 to 50s to decompose the titanic acid at high temperature to generate TiO 2 。
7. The method for improving the mechanical property of the metal matrix composite material by using the titanium dioxide surface modified graphene as claimed in claim 1, wherein in S4, the grown TiO is deposited 2 In the preparation of composite powder material by low-energy ball milling of @ Gr and metal powder, tiO 2 The mass fraction of @ Gr is 0 to 10 wt%; the particle size of the metal powder is more than 10 μm, and the metal powder is iron, aluminum, magnesium, titanium, nickel or alloy powder.
8. The method for improving the mechanical property of the metal matrix composite material by modifying the graphene on the surface of the titanium dioxide according to claim 7 is characterized in that in S4, the ball milling is carried out by low-energy ball milling of vibration powder mixing, wherein the ball-to-material ratio is controlled to be 0.1 to 2, the diameter of a grinding ball is 5 to 15 mm, the vibration frequency is 40 to 80 Hz, and the powder occupies 20 to 30 percent of the volume of a container.
9. The method for improving the mechanical property of the metal matrix composite material by modifying the graphene on the surface of the titanium dioxide according to claim 1, wherein when the metal matrix composite material is subjected to heating and pressure sintering molding in S5, the powder can be subjected to pre-cooling and pressure treatment according to the type of a die before sintering, and the load-holding pressure of the powder is kept within 10-20 MPa when the powder is subjected to cold pressing; the vacuum degree is lower than 1 Pa during sintering, and the sintering pressure is 10 to 80 MPa;
when a graphite die is adopted, the sintering pressure is controlled to be 30 to 60 MPa.
10. The method for improving the mechanical properties of the metal-matrix composite material by using the titanium dioxide surface-modified graphene as claimed in claim 9, wherein in S5, the sintering temperature of the composite powder is T, and the melting point T of the metal material is T 0 Wherein:
T=(0.5~0.9)T 0 ，
the heat preservation time is 5 min to 6 h;
when the titanium-based composite material is prepared, the sintering temperature is controlled to be 900-1200 ℃, and the pressure is controlled to be 30-60 MPa;
when the aluminum matrix composite material is prepared, the sintering temperature is controlled to be 450-600 ℃, and the pressure is controlled to be 45-80 MPa;
when SPS sintering is adopted, the sintering time is controlled within 60 min.
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2022
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