Preparation method of few-layer MXene-coated titanium composite powder

Abstract

The application discloses a preparation method of a few-layer MXene-coated titanium composite powder. The preparation method uses titanium or titanium alloy powder as a base body, and realizes uniform coating of MXene material with a nano two-dimensional sheet structure on the surface of the powder by adopting a wet ball milling process in cooperation with an MXene intercalation technology. The preparation method has the advantages of not damaging the MXene structure and the original powder shape, introducing few impurities, and having a low MXene layer number, and the MXene coating layer has the advantages of structural integrity, a small layer number, low impurity content, strong bonding force with the titanium powder base body, and the like, and has a good application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of composite material powder, and particularly relates to a powder raw material preparation technology for high-performance titanium-based composite materials in the fields of powder metallurgy and 3D printing, and more particularly relates to a preparation method of few-layer MXene-coated titanium composite powder. BACKGROUND

[0002] Titanium-based composite materials take titanium or titanium alloy as a matrix, and by adding one or several reinforcing phases with excellent properties, the mechanical properties of the matrix material are improved or new functional characteristics are given on the basis of retaining the original metal properties, thereby meeting the urgent needs of engineering fields in high-performance and multi-functional titanium-based composite materials in more severe service conditions. For example, the materials of the ring body, fan and high-pressure compressor in the aero-engine disc, and other aviation and military products, all need titanium-based composite materials with excellent high-temperature strength, wear resistance and high thermal conductivity. At present, high-performance and multi-functional titanium-based composite materials have become an irreplaceable key material in important strategic fields such as modern aviation, aerospace, space technology and national defense technology.

[0003] The type, morphology and size of the reinforcing phase are key factors that determine the performance indicators and functions of titanium-based composite materials. Since the development of titanium-based composite materials, large-sized ceramic particles and whiskers have been used as the main alternative materials for the reinforcing phase of titanium-based composite materials, which mainly strengthen the matrix by pinning the grain boundaries. Although the strength of the titanium alloy matrix can be greatly improved, the addition of a large amount of materials causes the plasticity of the material to decrease significantly. Developing new reinforcing phases has become a research hotspot in the field. Compared with traditional reinforcing phases such as large-sized particles and whiskers, nanometer two-dimensional sheet reinforcing phases have a special strengthening mechanism of coexistence of load transfer and dislocation pile-up hindering, which is expected to further improve the strength without significantly affecting the plasticity of the material. At the same time, two-dimensional sheet materials usually also have special thermal and electrical conductivity functions, which are ideal reinforcing phases for giving titanium-based composite materials special functional characteristics.

[0004] Graphene was first proposed as a nano two-dimensional sheet reinforcement in metal matrix composites, and is currently the most widely used two-dimensional sheet material. However, graphene has a very high reactivity with titanium, and whether graphene / titanium-based composites are prepared by powder metallurgy or 3D printing technology, graphene will react to form titanium carbide after the material is formed, losing the nano two-dimensional sheet structure and its special functional properties. In recent years, a new type of nano ceramic two-dimensional material MXene has been developed, which has many advantages such as large specific surface area, high strength and modulus, excellent thermal and electrical conductivity, etc. At the same time, unlike graphene, as a ceramic reinforcing phase, MXene has high stability and reactivity in titanium, and is expected to retain its original two-dimensional sheet structure and functional properties in the titanium matrix after the powder forming parts. However, the lack of high-quality MXene / titanium composite powder production technology has become a major bottleneck restricting the development and application of MXene reinforced titanium matrix composites. Mechanical mixing method is the main technology for preparing MXene / titanium composite powder, that is, by mixing titanium powder with MAX phase powder or accordion-shaped MXene powder and dispersing by ball milling, but the following problems exist and high-performance titanium matrix composites cannot be obtained: (1) MXene has strong van der Waals force and is easy to agglomerate in the matrix, losing the advantages of nano two-dimensional sheet material; (2) The two-dimensional reinforcing phase MXene cannot be effectively exfoliated, and the high layer number leads to poor performance, and increasing the ball milling speed and time can reduce the number of MXene layers, but the intrinsic structure of MXene is destroyed; (3) The impurity content of MXene is high, such as O, F, etc.

[0005] In summary, it is urgent to develop a composite powder preparation technology that can obtain uniformly dispersed few-layer and pure MXene in titanium powder, providing important raw materials and technical support for the development of high-quality MXene / titanium composite powder for high-performance titanium matrix composites. SUMMARY

[0006] The purpose of the present application is to provide a preparation method of few-layer and high-purity MXene coated titanium composite powder, to obtain high-quality MXene / titanium composite powder. The powder preparation method solves the problems of agglomeration of the reinforcing phase, high impurity content, and easy loss of the function of the reinforcing phase in the traditional mixed powder, breaks through the technical bottleneck of the introduction of MXene two-dimensional sheet reinforcement in titanium matrix composites, and provides an important raw material preparation technology for the development of high-performance titanium matrix composites. The composite powder can be directly used as a powder raw material for high-performance titanium matrix composites in the fields of powder metallurgy and 3D printing, but its application is not limited to this.

[0007] To achieve the above purpose, the specific technical solutions of the present application are as follows:

[0008] A preparation method of a few-layer MXene-coated titanium composite powder, the preparation method comprising the following main steps:

[0009] The accordion-shaped MXene powder and the titanium powder are mixed in proportion, wet ball milling, sieving and high-temperature vacuum reduction to obtain the MXene-coated titanium composite powder.

[0010] Specifically, the above preparation method comprises the following main steps:

[0011] 1) Put the accordion-shaped MXene powder and the titanium powder into a ball mill tank according to the required addition amount of the reinforcing phase, add the milling balls according to the preset ball-to-material ratio, then add the intercalation agent and the ball milling solvent medium, vacuum seal the ball mill tank, and then start the ball milling modification according to the set parameters;

[0012] 2) After the ball milling is completed, the modified MXene-coated titanium composite powder material is sieved out, and a high-temperature vacuum furnace is used for reduction treatment to remove the impurities introduced in the ball milling process, and then the treated powder is vacuum sealed and stored.

[0013] Preferably, the titanium powder in step 1) is one or more of Ti, Ti-6Al-4V alloy, Ti-10V-2Fe-3V alloy, Ti-Ni alloy, Ti-Nb-Zr-Sn alloy, Ti-Al-Sn alloy, Ti-Al-Mn alloy, Ti-Al-Mo-V alloy, with a purity of ≥98%.

[0014] Preferably, the accordion-shaped MXene powder in step 1) is obtained by etching a ternary carbide or nitride MXene MX (n+1) AX n (M represents a transition metal element, A represents a main group element, and X represents carbon or nitrogen) to obtain a layered metal carbide, metal nitride or composite metal carbide with a specific stoichiometric ratio, such as any one or a combination of two or more of Ti3C2, Ti3N2, Ti4N3, (Ti, Nb)4C3, Zr2C, Zr3C2, etc.

[0015] Preferably, the addition amount of the reinforcing phase in step 1) is the mass fraction of the accordion-shaped MXene powder in the powder mixture, ranging from 0.05 to 25.00 wt.%.

[0016] Preferably, the ball mill tank and the milling ball medium in step 1) are ceramic or stainless steel materials, such as 316L, zirconia, tungsten carbide, etc.

[0017] Preferably, the intercalation agent in step 1) is an organic solvent capable of expanding the interlayer spacing of the accordion-shaped MXene powder and peeling off the two-dimensional sheet layer; further preferably, the intercalation agent is one or several of N2H4-H2O (HM), N,N-dimethylformamide (DMF), dimethyl sulfoxide solvent (DMSO), and the intercalation agent can also be an organic base solution, and the organic base includes any one or a combination of two or more of trimethylphenyl ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide solution.

[0018] Preferably, the ball milling solvent medium in step 1) is a solvent capable of dissolving the intercalation agent, and further preferably, the solvent is deionized water or ethanol.

[0019] Preferably, the ball milling in step 1) uses a planetary ball mill, and the ball milling parameters are a rotation speed range of 50-200 rpm and a ball milling time range of 15-180 min.

[0020] Preferably, the high-temperature impurity removal device in step 2) can be a high-temperature vacuum furnace reduction device with uniform speed heating and cooling and low vacuum degree. The vacuum reduction parameters are a temperature range of 400-800℃ and a reduction time of 15-180 min.

[0021] The present application provides a MXene-coated titanium-based composite powder, wherein the powder has a titanium powder or titanium alloy powder as a matrix, and a coating layer containing MXene, preferably, the MXene accounts for 0.05-20.00wt.% of the total weight of the powder.

[0022] According to a preferred embodiment of the present application, the present application provides a preparation method of a few-layer MXene-coated titanium-based composite powder, comprising the following steps:

[0023] 1) A certain amount of Ti3C2 type accordion-shaped MXene powder is weighed, and then a corresponding proportion of titanium powder required is weighed and added into a ball mill tank in sequence, zirconia grinding balls are added according to a preset ball-to-material ratio, then dimethyl sulfoxide solvent (DMSO) intercalation agent and a certain amount of deionized water ball milling solvent medium are added, and then the ball mill tank is sealed after being vacuumed for multiple times, and when the vacuum degree is 10 -2 Pa, the ball milling modification is started according to the set ball milling parameter rotation speed of 100 rpm / min and the ball milling time of 60 min.

[0024] 2) After the ball milling is completed, the modified MXene-coated titanium-based composite powder material is sieved out by using a 100-mesh sieve, the modified coated powder is placed in a porcelain boat, and the porcelain boat is placed in a high-temperature vacuum furnace for high-temperature reduction and impurity removal treatment to remove the impurities introduced in the ball milling process, the furnace temperature is set to 750 DEG C, the temperature rising speed is 10 DEG C / min, the holding time is 30 min, then the vacuum furnace is cooled according to the program, when the program temperature reaches 500 DEG C, the cooling program is turned off, and the furnace is naturally cooled down, when the temperature drops to 50 DEG C, the vacuum is turned off, and the powder is taken out, the coated powder after impurity removal is sieved according to different particle sizes, and is packed and stored in a vacuum.

[0025] The present application is aimed at the problems of poor dispersibility of MXene in the composite powder, difficulty in layer number control, and high impurity content, and is realized by a wet ball milling process combined with MXene intercalation and powder impurity removal technology.

[0026] Compared with mechanical mixing or high-energy ball milling technology, the present application has the advantages of not damaging the MXene structure, maintaining the original powder shape, introducing less impurities, and having low MXene layer number, and has good application prospect.

[0027] The surface coating layer of the present application mainly comprises two-dimensional MXene, and the MXene / titanium composite powder has the advantages of complete structure, few layers (generally less than 10 layers), and strong bonding force with the titanium powder matrix.

[0028] Compared with the MXene / titanium composite powder prepared by traditional mechanical ball milling technology, the present application has the following advantages:

[0029] The MXene / titanium composite powder prepared by the present application has the advantages of complete structure, few layers (generally less than 10 layers), and strong bonding force with the titanium powder matrix, and the coating content is accurately controllable and has a wide adjustable range (0.05-20.00wt.%). BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 SEM image of the MXene-coated Ti hydrogenation-dehydrogenation composite powder in Example 1 of the present application;

[0031] Figure 2 SEM image of MXene-coated Ti hydrogenation-dehydrogenation composite powder in Example 1 of the present application;

[0032] Figure 3 SEM image of MXene-coated Ti spherical composite powder in Example 2 of the present application;

[0033] Figure 4 High-magnification SEM image of MXene-coated Ti spherical composite powder in Example 2 of the present application;

[0034] Figure 5 SEM image of MXene-coated Ti hydrogenation-dehydrogenation composite powder in Example 3 of the present application;

[0035] Figure 6 High-magnification SEM image of MXene-coated Ti hydrogenation-dehydrogenation composite powder in Example 3 of the present application;

[0036] Figure 7 SEM image of MXene-coated Ti-6Al-4V spherical composite powder in Example 4 of the present application;

[0037] Figure 8 SEM image of MXene-coated Ti-6Al-4V spherical composite powder in Example 5 of the present application. DETAILED DESCRIPTION

[0038] The technical solutions of the present application will be described in detail below in combination with the drawings and examples.

[0039] Example 1

[0040] 1) 2g of Ti3C2 type accordion-shaped MXene powder was weighed using a weighing paper, and then 200g of hydrogenation-dehydrogenated titanium powder was weighed and added into the ball mill jar in sequence, zirconium oxide grinding balls were added according to the preset mass ratio of 1:1, and then 20mL of dimethyl sulfoxide solvent (DMSO) intercalating agent and 80ml of deionized water ball milling solvent medium were added, and then the ball mill jar was repeatedly vacuum sealed, and when the vacuum degree was 10 -2 Pa, the ball milling modification was started according to the set ball milling parameters of 100rpm and 60min.

[0041] 2) After the ball milling is completed, the modified MXene-coated titanium-based composite powder material is sieved through a 100-mesh sieve, the obtained modified coated powder is placed in a porcelain boat, and the porcelain boat is placed in a high-temperature vacuum furnace for high-temperature reduction and impurity removal treatment. The furnace temperature is set to 750 DEG C, the heating rate is 10 DEG C / min, the holding time is 30 min, after the holding time reaches, the vacuum furnace is cooled according to the program, when the program temperature reaches 500 DEG C, the cooling program is turned off, and the furnace is naturally cooled down, when the temperature drops to 50 DEG C, the vacuum is turned off, and the powder is taken out, the impurity-removed coated powder is sieved into different particle sizes, and is vacuum-sealed and stored in a bag.

[0042] Figure 1 For the SEM image of the MXene-coated Ti hydrogenation-dehydrogenation composite powder in Example 1, the main component of the powder surface coating layer is MXene, and the irregular Ti powder surface is uniformly coated with MXene;

[0043] Figure 2 For the high-magnification SEM image of the MXene-coated Ti hydrogenation-dehydrogenation composite powder in Example 1, it can be seen that the surface sheet material is thin and has fewer layers, and is no longer arranged like an accordion.

[0044] Example 2

[0045] The difference between this example 2 and example 1 is that the hydrogenation-dehydrogenation titanium powder is replaced by spherical titanium powder, and the particle size distribution is 25-53 μm.

[0046] Figure 3 For the SEM image of the MXene-coated Ti spherical composite powder in the present application example 2, the rough surface of the Ti powder is coated with sheet-like MXene;

[0047] Figure 4 For the high-magnification SEM image of the MXene-coated Ti spherical composite powder in the present application example 2, the MXene is uniformly distributed on the spherical powder.

[0048] Example 3

[0049] The difference between this example 3 and example 1 is that the intercalation agent is selected as trimethylphenyl ammonium hydroxide solvent.

[0050] Figure 5 For the SEM image of the MXene-coated Ti hydrogenation-dehydrogenation composite powder in the present application example 3;

[0051] Figure 6 For the high-magnification SEM image of the MXene-coated Ti hydrogenation-dehydrogenation composite powder in the present application example 3.

[0052] Example 4

[0053] The difference between the present embodiment 4 and embodiment 2 is that the spherical titanium powder is replaced by spherical Ti-6Al-4V powder, the purity of the powder is 99.0%, the particle size distribution is 25-53 μm, and the ball milling speed is 200 rpm.

[0054] Figure 7 The SEM image of the MXene-coated Ti-6Al-4V spherical composite powder in the present embodiment 4 shows that the few-layer MXene is still uniformly coated on the surface of the powder, which proves that the MXene coating method has no obvious selectivity for the titanium alloy powder substrate.

[0055] Embodiment 5

[0056] The difference between the present embodiment 5 and embodiment 4 is that the ball milling parameters are set as a speed of 200 rpm / min and a ball milling time of 180 min.

[0057] Figure 8 The SEM image of the MXene-coated Ti-6Al-4V spherical composite powder in the present embodiment 5 shows that the MXene can be more uniformly distributed by increasing the ball milling speed, but the MXene can also be decomposed into multiple nanoscale layers with smaller areas.

[0058] The upper and lower limits of the process parameters (such as temperature, time, etc.) of the present application and the interval values can all achieve the present method, and therefore, the embodiments are not listed one by one.

[0059] The contents not described in detail in the present application can all adopt the conventional technical knowledge in the art.

[0060] Finally, it should be pointed out that the above embodiments are only used to illustrate the technical solutions of the present application but not to limit. Although the present application has been described in detail with reference to the embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced equivalently without departing from the spirit and scope of the technical solutions of the present application, and all of them should be covered in the scope of the claims of the present application.

Claims

1. A method for preparing a few-layer MXene-coated titanium composite powder, the method comprising the following main steps: mixing an accordion-shaped MXene powder with titanium powder in a certain proportion, and obtaining a MXene-coated titanium composite powder through wet ball milling, sieving and high-temperature vacuum reduction.

2. The production method according to claim 1, characterized by, The titanium powder is one or more of Ti, Ti-6Al-4V alloy, Ti-10V-2Fe-3V alloy, Ti-Ni alloy, Ti-Nb-Zr-Sn alloy, Ti-Al-Sn alloy, Ti-Al-Mn alloy and Ti-Al-Mo-V alloy, with a purity of ≥98%.

3. The production method according to claim 1, characterized by, The few layers in the few-layer MXene-coated titanium composite powder refer to a coating layer number ≤10.

4. The preparation method according to claim 1, characterized in that, The accordion-shaped MXene powder is Ti3C2, Ti3N2, Ti4N3, (Ti, Nb)4C3, Zr2C or Zr3C2.

5. The preparation method according to claim 1, characterized in that, The mass fraction of the accordion-shaped MXene powder in the powder mixture is 0.05-25.00 wt.%.

6. The method of claim 1, wherein, The medium of the ball milling tank and the grinding ball used in the wet ball milling is ceramic or stainless steel material.

7. The preparation method according to claim 1, characterized in that, An intercalation agent is added during the wet ball milling, and the intercalation agent is one or more of N2H4-H2O, N,N-dimethylformamide, dimethyl sulfoxide, trimethylphenyl ammonium hydroxide solution, tetramethyl ammonium hydroxide solution, tetraethyl ammonium hydroxide solution, tetrapropyl ammonium hydroxide solution and tetrabutyl ammonium hydroxide solution.

8. The method of claim 1, wherein, A ball milling solvent medium is added during the wet ball milling, and the ball milling solvent medium is deionized water or ethanol.

9. The method of claim 1, wherein, The wet ball milling adopts a planetary ball mill, and the ball milling rotation speed is 50-200 rpm, and the ball milling time is 15-180 min.

10. The method of claim 1, wherein, The temperature of the high-temperature vacuum reduction is 400-800℃, and the reduction time is 15-180 min.

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