Three-dimensional continuous net-shaped composite functional material and preparation method and application thereof

Abstract

The present application belongs to the technical field of reticular structure materials, and discloses a three-dimensional continuous reticular composite functional material and a preparation method and application thereof, steps of which are as follows: (1) Ti powder is soaked in a nitric acid solution for 3-5 min and then taken out; (2) the powder obtained in step (1) is placed in a sensitization solution and stirred for 5-10 min and then taken out; (3) the powder obtained in step (2) is placed in an activation solution and stirred for 6-8 min and then taken out; (4) the powder obtained in step (3) is added into a plating solution, and water bath heating and stirring are carried out, then 80 ml of formaldehyde solution is added and deionized water is added to 1000 ml, and chemical plating is started; (5) the powder obtained in step (4) is cleaned and dried, and then sintered to obtain a three-dimensional continuous reticular composite functional material. The present application greatly reduces the difficulty of preparation of a metal net structure and improves the efficiency.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of reticular structure materials, and more particularly relates to a three-dimensional continuous reticular composite functional material and a preparation method and application thereof. BACKGROUND

[0002] Titanium is a new type of structural material, which has excellent comprehensive performance, such as low density (4.5 g / cm 3 ), high specific strength and fracture toughness, good fatigue strength and crack propagation resistance, good low-temperature toughness, and excellent corrosion resistance. At the same time, the working temperature of some titanium alloys is about 550 ℃, and the highest is expected to reach 700 ℃. Therefore, titanium alloys are increasingly widely used in the aviation, aerospace, chemical, shipbuilding and other industrial sectors. About 80% of the titanium output is used in the aerospace industry. For example, in the United States, titanium accounts for about 1% of the B-21 bomber fuselage structural material, mainly used to manufacture fuselage, wings, skin and load-bearing parts. For the F-15 fighter structural material, titanium alloy accounts for 7000 kg, about 34% of the weight of the fuselage structure.

[0003] Cu element has the advantage of excellent toughness, and Cu belongs to β-stabilizing element, part of copper in titanium alloy exists in solid solution state, and another part forms Ti2Cu or TiCu2 compound, TiCu2 has thermal stability and plays a role in improving the thermal strengthening property of the alloy. Copper is a common alloying element of biological materials, and has osteogenesis and angiogenesis promoting functions due to its good antibacterial activity. Alloying pure titanium with Cu can promote the antibacterial property and biological activity of the matrix. Therefore, the new antibacterial Ti-Cu alloy has become a hot topic in the world today. Generally, it is believed that the antibacterial property of Ti-Cu alloy is positively correlated with the content of Cu alloy. The dispersion of Ti2Cu phase on the surface and the leaching of Cu 2+The mechanical mixing of different filling alloy powders can lead to uneven distribution of elements, while coating technology is often used as a metallization method for preparing uniform composite materials. By chemical plating, electroplating, evaporation, ion plating and other processes on the surface of the powder, the surface morphology, roughness and mechanical properties of the powder can be improved, thereby improving the uniformity of element distribution and the comprehensive performance of the composite material. Hongmei et al. prepared Cu-coated multi-walled carbon nanotubes (MWCNTs) as a reinforcing agent to optimize the mechanical properties of the Zn matrix. Microstructure results show that MWCNTs are uniformly dispersed in the Zn matrix, and the Cu coating forms a tight interfacial connection between Zn and MWCNTs. In order to overcome the poor wettability and mutual immiscibility of W and Cu elements, Li et al. prepared double-layer composite powders of Cu and Ni-coated W powder, and then prepared dense W-Cu composite powder. The use of core-shell structure composite filling metals can achieve uniform distribution of composite filling metal elements. Chemical plating is widely used in the preparation of coating powders for composite materials due to its less shape and substrate limitations during electroplating. In order to prevent segregation of Cu elements, improve the interface strength of the material and inhibit bacterial growth, it is necessary to design Cu coating on the surface of Ti powder, and more attention should be paid to the fact that Ti-Cu is prone to chemical reaction under heating conditions. SUMMARY

[0004] In view of the above defects or improvement needs of the prior art, the present application provides a three-dimensional continuous network composite functional material and a preparation method and application thereof, which aims to solve the problems of low uniformity and efficiency of traditional three-dimensional network structure materials.

[0005] To achieve the above-mentioned purpose, according to one aspect of the present application, a preparation method of a three-dimensional continuous network composite functional material is provided, which comprises the following steps:

[0006] (1) immerse the Ti powder in a nitric acid solution for 3-5 min, and then take it out;

[0007] (2) take 10 g of stannous chloride and add 960 ml of deionized water, then add 40 ml of 36% concentrated hydrochloric acid solution, and finally add deionized water to 1 L, stir until dissolved to obtain a sensitization solution; then, the powder obtained in step (1) is placed in the sensitization solution and stirred for 5-10 min, and then taken out;

[0008] (3) take 0.25 g of palladium chloride, add 800 ml of deionized water, then add 10 ml of 36% concentrated hydrochloric acid solution, and finally add deionized water to 1 L, stir until dissolved to obtain an activation solution; then, the powder obtained in step (2) is placed in the activation solution and stirred for 6-8 min, and then taken out;

[0009] (4) 2,2'-dipyridyl 0.2 g, potassium ferrocyanide 0.2 g, copper sulfate pentahydrate 50 g, disodium ethylenediaminetetraacetate 15 g, sodium tartrate tetrahydrate 15 g are added into 850 ml of deionized water and stirred until dissolved, then the solution is adjusted to a pH of 12 by adding sodium hydroxide to obtain a plating solution, then the powder obtained in step (3) is added to the plating solution, and water bath heating and stirring are carried out, then 80 ml of formaldehyde solution is added and deionized water is added to 1000 ml to start the chemical plating;

[0010] (5) The powder obtained in step (4) is washed and dried and then sintered to obtain a three-dimensional continuous network composite functional material.

[0011] Further, the sintering condition in step (5) is 1300℃ for 3h.

[0012] Further, in step (5), the sample powder is sintered by a spark plasma system, the pressure is 40MPa-200MPa, the sintering temperature is 500℃-800℃, and the holding time is 5min-10min.

[0013] Further, the mass of the Ti powder is 100g.

[0014] Further, the temperature of the water bath heating is 43℃.

[0015] Further, the pH of the plating solution during the chemical plating process is maintained between 11-13.5.

[0016] Further, before sintering, the obtained powder is ultrasonically cleaned with deionized water for three times, cleaned with alcohol for one time, and then dried in a vacuum drying oven at 70-100℃ for 12h.

[0017] The application also provides a three-dimensional continuous network composite functional material prepared by the preparation method of the three-dimensional continuous network composite functional material.

[0018] The application also provides the use of the three-dimensional continuous network composite functional material in aerospace, chemical industry, and shipbuilding.

[0019] Overall, compared with the prior art, the three-dimensional continuous network composite functional material and the preparation method and use thereof provided by the application have the following beneficial effects:

[0020] 1. The method for modifying powder by electroless plating to achieve the construction of metal network structure. A layer of metal Cu plating can be obtained on the surface of Ti powder by electroless plating, and the thickness of the plating layer can be controlled by the content of chemical reagent, the particle size of powder and the electroless plating time to obtain different network metal structures. This method can be applied to various powders to obtain metal network structures of different matrix materials, greatly reducing the difficulty of preparing metal network structure and improving the efficiency.

[0021] 2. Ti-Cu is prone to react at high temperature, and different composite materials can be constructed by changing the sintering process. Under the ordinary sintering process, Cu will completely diffuse, and under the SPS low-temperature rapid sintering, a three-dimensional network structure containing Cu can be formed, and a stable interface is formed by Ti-Cu, so as to meet the high strength requirement of the composite material.

[0022] 3. The metal material prepared by the method can be applied to many fields and scenes. The antibacterial property of Cu element combined with the high strength and biocompatibility of Ti element makes the metal material prepared by the method applicable to the fields of biological medicine and marine engineering; the Cu-containing network structure titanium alloy prepared by short process rapid sintering is expected to make up for the defects of titanium, realize high heat transfer of titanium-based composite material, and has broad application prospect in industrial and military fields. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 is a flow chart of a method for preparing a three-dimensional continuous network composite functional material provided by the application;

[0024] Figure 2 is a schematic diagram of electroless copper plating involved in the application;

[0025] Figure 3 (a), (b) and (c) in are respectively the powder morphology, surface EDS analysis and XRD diagram of the powder after electroless copper plating in Example 1 of the application;

[0026] Figure 4 (a) and (b) in are respectively a schematic diagram of the SPS sintering state morphology and surface EDS analysis of Example 1;

[0027] Figure 5 is a schematic diagram of the microstructure morphology after conventional sintering obtained in Example 2 of the application;

[0028] Figure 6 (a) and (b) in are respectively a schematic diagram of the SPS sintering state morphology and surface EDS analysis of Example 3 of the application;

[0029] Figure 7 (a) and (b) in are respectively a schematic diagram of a three-dimensional network structure containing Cu and a schematic diagram of heat transfer path simulation. DETAILED DESCRIPTION

[0030] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application will be further described in details below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and should not be used to limit the present application. In addition, the technical features involved in the various embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0031] Referring to Figure 1 and Figure 2 , the present application provides a preparation method of a three-dimensional continuous network composite functional material, which realizes the stable existence of pure Cu in Ti-based composite material by controlling the sintering process, and further meets the engineering service requirements in some special environments. Titanium alloy has high specific strength and is widely used in various complex environments, but the thermal conductivity of pure titanium is only about 17 W / m·K, which is difficult to achieve application in heat transfer materials. However, the thermal conductivity of pure Cu can reach 410 W / m·K, and by adding copper to titanium alloy, the excellent performance of Ti-Cu can be realized at the same time. The existence of pure Cu improves the thermal conductivity of the composite material, and Ti makes the composite material adapt to extreme environments due to its excellent specific strength and corrosion resistance. The reaction of Ti-Cu at the interface generates a compound to ensure the basic connection strength of the material, and the titanium-based composite material with three-dimensional network structure of Cu has more application possibilities, such as heat dissipation pipes on ships and heat transfer vessels in factories.

[0032] At the same time, traditional titanium alloy products rely on forging, casting and rolling of bulk raw materials, and then subsequent processing to achieve the final shape and size, resulting in a large amount of material waste, high manufacturing cost and long delivery time, and there is little research on the construction of internal three-dimensional network structure. In contrast, the present application studies a new type of Ti composite filler metal coated with a pure Cu layer, prepares a core-shell composite structure powder of Cu-coated Ti, and obtains a three-dimensional continuous network composite structure functional material by powder metallurgy method, which has great application prospect in many fields.

[0033] The preparation method mainly includes the following steps:

[0034] Step one, put the Ti powder in a beaker and ultrasonically clean it with alcohol for 10-15 min; then take out the powder and ultrasonically clean it with deionized water for 3-5 min three times to remove surface impurities and improve the quality of the plated film. The mass of the Ti powder is 100 g.

[0035] Step two, configure nitric acid solution: take 900ml of deionized water in a beaker, add 100ml of 30% concentration nitric acid to 1L, immerse the Ti powder in step one in the nitric acid solution for 3-5min (provide plating adhesion points, increase Cu-Ti binding force), and take out (provide plating adhesion points, increase Cu-Ti binding force), ultrasonic clean with deionized water for 3 times.

[0036] Step three, configure sensitization solution: take 10g of stannous chloride, add 960ml of deionized water, then add 40ml of 36% concentration hydrochloric acid solution, and finally add deionized water to 1L, stir until dissolved; put the powder obtained in step two into the sensitization solution, stir for 5-10min, then take out (provide activation sites for electroless plating, improve binding force), and clean with deionized water once.

[0037] Step four, configure activation solution: take 0.25g of palladium chloride, add 800ml of deionized water, then add 10ml of 36% hydrochloric acid solution, and finally add deionized water to 1L, stir until dissolved; put the powder obtained in step three into the activation solution, stir for 6-8min, then take out (improve the adhesion of the powder to the plating layer).

[0038] Step five, configure plating solution: 2,2'-dipyridyl 0.2g, potassium ferrocyanide 0.2g, copper sulfate pentahydrate 50g, disodium ethylenediaminetetraacetate 15g, sodium tartrate tetrahydrate 15g, add 850ml of deionized water and stir until dissolved, then add sodium hydroxide to adjust the pH value of the solution to 12, add the powder in step four to the plating solution, heat in a water bath at 43℃ and stir, finally add 80ml of formaldehyde solution and make up with deionized water to 1000ml to start electroless plating, and the pH value must be kept between 11-13.5 during the electroless plating process.

[0039] Step six, after the powder obtained in step five is filtered, ultrasonic clean with deionized water for three times, clean with alcohol once, then put it in a vacuum drying oven and dry at 70-100℃ for 12h.

[0040] Step seven, by controlling different sintering processes, different structures can be built to obtain three-dimensional continuous network composite functional materials. Method one of the two sintering methods: conventional sintering, heat at 1300℃ for 3h; method two: use a discharge plasma system to sinter the sample powder, pressure 40-200MPa, sintering temperature 500-800℃, heat preservation time 5-10min.

[0041] The application also provides a three-dimensional continuous network composite functional material prepared by the preparation method of the three-dimensional continuous network composite functional material as described above.

[0042] The application also provides the application of the three-dimensional continuous network composite functional material as described above in aerospace, chemical industry, shipbuilding.

[0043] The present application is further described in detail below with specific examples.

[0044] Example 1:

[0045] Example 1 of the present application includes the following steps:

[0046] Step 1, take 100g Ti powder into a beaker, ultrasonic cleaning with alcohol for 15min; then take out the powder and ultrasonic clean with deionized water for 5min three times to remove surface impurities and improve the quality of the coating.

[0047] Step 2, take 100ml of 30% concentration nitric acid and add to 900ml of deionized water, put the powder obtained in step 1 into the solution, stir for 3min, then take out and ultrasonic clean with deionized water for 3 times.

[0048] Step 3, take 10g of stannous chloride, add 960ml of deionized water, then add 40ml of 36% hydrochloric acid solution, stir until dissolved; put the powder obtained in step 2 into the sensitization solution, stir for 5min, then take out and clean with deionized water once.

[0049] Step 4, take 0.25g of palladium chloride, add 990ml of deionized water, then add 10ml of 36% hydrochloric acid solution, stir until dissolved; put the powder obtained in step 3 into the activation solution, stir for 8min, then take out.

[0050] Step 5, take 0.2g of 2,2'-dipyridyl, 0.2g of potassium ferrocyanide, 50g of copper sulfate pentahydrate, 15g of disodium ethylenediaminetetraacetate, 15g of sodium tartrate tetrahydrate, add 850ml of deionized water and stir until dissolved, then add sodium hydroxide to adjust the pH value of the solution to 12, add the powder in step 4 to the plating solution, heat to 43℃ in a water bath and stir, finally add 80ml of formaldehyde solution and make up to 1000ml with deionized water to start electroless plating, and keep the pH value at 12 during electroless plating (by adding NaOH).

[0051] Step 6, filter the powder obtained in step 5 and ultrasonic clean with deionized water for three times, then clean with alcohol once, then put it in a vacuum drying oven at 70℃ for 12h.

[0052] Step 7, use a discharge plasma system to sinter the sample powder, pressure 50MPa, sintering temperature 700℃, holding time 5min. Take out the sample to obtain a three-dimensional metal mesh structure material.

[0053] Please refer to Figure 3It can be clearly observed that the Cu uniformly covers the core Ti to obtain the core-shell structure titanium-based composite powder. Figure 4 It can be seen that the Cu element forms a continuous network structure in the material.

[0054] Example 2

[0055] The example 2 of the present application comprises the following steps:

[0056] Step 1, the copper-plated powder in example 1 is used for conventional sintering, the powder is packed and cold isostatic pressing is performed.

[0057] Step 2, conventional pressureless sintering is performed, the heating speed is 5℃ / min, the temperature is kept at 1300℃ for 3h, the complete diffusion of the Cu element is realized, and the microstructure after conventional sintering is shown in Figure 5 .

[0058] Example 3

[0059] The copper-plated powder in example 1 is used for spark plasma sintering, the pressure is 50MPa, the sintering temperature is 650℃, and the holding time is 5min. The sample is taken out to obtain a three-dimensional metal network structure material. Through SEM contrast, reducing the sintering temperature can effectively reduce the reaction between Cu and Ti, and more pure copper exists in the network structure, so as to prepare a Ti-based composite material containing Cu network, as shown in Figure 6 .

[0060] According to the above examples, the doping of the Cu network in the Ti has been realized, and the subsequent process can be optimized on the basis. It can be found from the above examples that reducing the sintering temperature and increasing the sintering pressure can obtain a higher quality of Cu-containing three-dimensional network titanium-based composite material. Due to the limitation of the current experimental conditions, the optimal process is not prepared, so the simulation analysis of the thermal conductivity of the Cu network structure in the Ti-based composite material is performed. It can be seen that the connected Cu structure provides an effective path for the efficient heat transfer of the Ti-based composite material. When the powder particle size of Ti is 60um and the chemical plating Cu layer is 3um, the theoretical thermal conductivity of the titanium-based composite material can reach 79W / m·K through simulation, as shown in Figure 7 .

[0061] Example 4

[0062] The example 4 of the present application comprises the following steps:

[0063] Step 1, first, 100g of Ti powder is weighed into a beaker, 300ml of anhydrous ethanol is added, and ultrasonic cleaning is performed for 10min, the obtained powder is taken out, and then ultrasonic cleaning is performed with deionized water for 3 times, each time for 5min.

[0064] Step 2, 100ml of 30% nitric acid was added to 900ml of deionized water, and the powder obtained in step 1 was placed in the obtained solution and stirred for 3min, then taken out and cleaned with deionized water for 3 times.

[0065] Step 3, 10g of stannous chloride was added to 960ml of deionized water, followed by 40ml of 36% hydrochloric acid solution, and stirred until dissolved to obtain a sensitization solution; the powder obtained in step 2 was placed in the sensitization solution and stirred for 5min, then taken out and cleaned with deionized water once.

[0066] Step 4, 0.25g of palladium chloride was added to 990ml of deionized water, followed by 10ml of 36% hydrochloric acid solution, and stirred until dissolved to obtain an activation solution; the powder obtained in step 3 was placed in the activation solution and stirred for 8min, then taken out.

[0067] Step 5, 0.1g of 2,2'-dipyridyl, 0.1g of potassium ferrocyanide, 25g of copper sulfate pentahydrate, 25g of ethylenediaminetetraacetic acid disodium salt, 15g of sodium tartrate tetrahydrate were added to 960ml of deionized water and stirred until dissolved, followed by adding sodium hydroxide and adjusting the pH value of the solution to 12 to obtain a plating solution, and the powder obtained in step 4 was added to the plating solution, and after water bath heating to 43℃, stirring was started, and finally 40ml of formaldehyde solution was added to start electroless plating, and the pH value was maintained at 12 during electroless plating.

[0068] Step 6, the powder obtained in step 5 was filtered and cleaned with deionized water for 3 times, and then cleaned with alcohol once, and then placed in a vacuum drying oven at 60℃ for 12h.

[0069] Step 7, the obtained powder was sintered by a discharge plasma system to obtain a three-dimensional metal mesh structure material. The sintering conditions are: pressure is 50MPa, sintering temperature is 700℃, and holding time is 5min.

[0070] Figure 3 The EDS spectrum of the Ti powder after chemical copper plating and the surface Cu element distribution can clearly observe that the Cu uniformly covers the core Ti to obtain a core-shell structure titanium-based composite powder. Figure 4 The sintered state morphology of the core-shell structure composite powder after SPS can be seen that the Cu element forms a continuous mesh structure in the material.

[0071] Example 5

[0072] The example 5 of the present application comprises the following steps:

[0073] Step 1, first take Ti powder 100g into a beaker, add 300ml anhydrous ethanol, ultrasonic clean for 10min, take out the powder after ultrasonic cleaning and then ultrasonic clean with deionized water for 3 times, each time for 5min.

[0074] Step 2, take 100ml 30% concentration nitric acid into 900ml deionized water, put the powder obtained in step 1 into the obtained solution, stir for 5min, then take out and ultrasonic clean with deionized water for 3 times.

[0075] Step 3, take stannous chloride 10g into 960ml deionized water, then add 40ml 36% concentration hydrochloric acid solution, stir until dissolved to obtain a sensitization solution; put the powder obtained in step 2 into the sensitization solution, stir for 5min, then take out and clean with deionized water once.

[0076] Step 4, take palladium chloride 0.5g, add 990ml deionized water, then add 10ml 36% concentration hydrochloric acid solution, stir until dissolved to obtain an activation solution; put the powder obtained in step 3 into the activation solution, stir for 10min, then take out.

[0077] Step 5, take 2,2'-dipyridyl 0.4g, potassium ferrocyanide 0.4g, copper sulfate pentahydrate 100g, ethylenediaminetetraacetic acid disodium salt 100g, sodium tartrate tetrahydrate 60g, add 840ml deionized water, stir until dissolved, then add sodium hydroxide to control the PH value of the obtained solution to 12 to obtain a plating solution, put the powder obtained in step 4 into the plating solution, heat to 43℃ in a water bath and then stir, finally add formaldehyde solution 160ml to start electroless plating, and keep the PH value at 12.5 during electroless plating.

[0078] Step 6, take out the powder obtained in step 5 by suction filtration, ultrasonic clean with deionized water for 3 times, alcohol clean once, then put into a vacuum drying oven and dry at 40℃ for 12h.

[0079] Step 7, use a discharge plasma system to sinter the obtained powder to obtain a three-dimensional metal mesh structure material. The sintering conditions are: pressure 50MPa, sintering temperature 650℃, holding time 5min.

[0080] Those skilled in the art can easily understand that the above description is only a preferred embodiment of the present application and is not intended to limit the present application, and any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a three-dimensional continuous network composite functional material, characterized in that, The method includes the following steps: (1) Soak 100g of Ti powder in nitric acid solution for 3-5 minutes and then remove it; (2) Take 10g of stannous chloride and add it to 960mL of deionized water, then add 40mL of 36% hydrochloric acid solution, and finally add deionized water to 1L. Stir until dissolved to obtain a sensitized solution. Then, put the powder obtained in step (1) into the sensitized solution and stir for 5min-10min before taking it out. (3) Take 0.25g of palladium chloride, add 800mL of deionized water, then add 10mL of 36% hydrochloric acid solution, and finally add deionized water to 1L. Stir until dissolved to obtain an activation solution. Then, place the powder obtained in step (2) into the activation solution and stir for 6min-8min before taking it out. (4) 0.2g of 2,2'-bipyridine, 0.2g of potassium ferrocyanide, 50g of copper sulfate pentahydrate, 15g of disodium ethylenediaminetetraacetate and 15g of sodium tartrate tetrahydrate were added to 850mL of deionized water and stirred until dissolved. Then sodium hydroxide was added to adjust the pH of the solution to 12 to obtain the plating solution. Next, the powder obtained in step (3) was added to the plating solution and heated and stirred in a water bath. Then 80mL of formaldehyde solution was added and deionized water was added to 1000mL to start chemical plating. (5) The powder obtained in step (4) is cleaned and dried and then sintered to obtain a three-dimensional continuous network composite functional material; The sintering conditions in step (5) are: holding at 1300℃ for 3 hours; or, using a discharge plasma system to sinter the sample powder at a pressure of 40 MPa - 200 MPa, a sintering temperature of 500℃ - 800℃, and a holding time of 5 min - 10 min.

2. The method for preparing the three-dimensional continuous network composite functional material as described in claim 1, characterized in that: The water bath heating temperature is 43℃.

3. The method for preparing the three-dimensional continuous network composite functional material according to any one of claims 1-2, characterized in that: During the electroless plating process, the pH value of the plating solution is maintained between 11 and 13.

5.

4. The method for preparing the three-dimensional continuous network composite functional material as described in claim 1, characterized in that: Before sintering, the obtained powder is ultrasonically cleaned three times with deionized water and cleaned once with alcohol, and then placed in a vacuum drying oven at 70-100℃ for 12 hours.

5. A three-dimensional continuous network composite functional material, characterized in that: The composite functional material is prepared using the preparation method of the three-dimensional continuous network composite functional material according to any one of claims 1-4.

6. The application of the three-dimensional continuous network composite functional material according to claim 5 in aerospace, chemical industry and shipbuilding.

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