Preparation method of metal matrix composite material with enamel-like modification layer

Abstract

The present invention belongs to the field of materials, involving technical fields such as nanoscience, bionics, and mechanics, and particularly relates to a preparation method of a metal matrix composite material with an enamel-like modification layer. This method takes metal as the research object, selects alkali, metal salt, and buffer reagent as raw materials, and in-situ constructs an enamel-like ceramic strengthening layer on the metal substrate surface through hydrothermal treatment, controlled hydrolysis, and calcination processes successively. The specific method is as follows: (1) Prepare a NaOH solution with a target concentration, and place the cut metal foil in the alkali solution for hydrothermal treatment; (2) Prepare a buffer solution with a target pH, then add an appropriate metal salt, and place the sample obtained in (1) in the above solution for low-temperature reaction for a certain period of time; (3) Place the sample obtained in (2) in a muffle furnace for calcination for a certain period of time, and finally obtain a uniform and dense enamel-like modification layer on the metal substrate surface, obtaining a high-stiffness and corrosion-resistant metal matrix composite material, realizing the strengthening and anti-corrosion of the metal.

Description

Technical Field

[0001] The present invention belongs to the field of materials, and relates to the technical fields of nanomaterials, bionics, mechanics, anti-corrosion, etc. Specifically, it relates to a preparation method of a metal matrix composite material with an enamel-like modification layer. Background Art

[0002] High-stiffness and high-damping materials are widely used in frontier fields such as space shuttles and new energy vehicles due to their excellent sound conduction ability and the ability to resist ubiquitous environmental vibrations. Metals, due to their inherent durability, machinability, and relatively high stiffness (lower than ceramics), have become one of the most widely used engineering materials in real life. However, most high-stiffness metals (such as steel and brass) often exhibit weak damping behavior, which can be attributed to the fact that it is difficult for high-rigidity metals to achieve dislocation and deformation of grain boundaries during the energy dissipation process; for high-damping metals (such as zirconium and aluminum), their stiffness is difficult to meet the actual requirements, thus restricting the application scope of metal materials.

[0003] As a general strategy to improve the stiffness and damping behavior of metals, high-stiffness components and high-damping components are combined to form composite materials, but defects and interfaces will be introduced into the materials, thereby reducing the overall stiffness of the materials. Recently, high-entropy alloys or 3D printing to construct high-performance metals can achieve the simultaneous improvement of the strength and damping ability of metal materials, but there are few reports on strategies to simultaneously improve the stiffness and damping ability of metal materials. In addition, the hardness of most pure metals is relatively low and most structural metals are easily threatened by corrosion, which puts higher requirements on the monitoring and replacement of metal equipment, components, etc., resulting in huge economic losses.

[0004] Highly mineralized biological materials represented by enamel are a typical composite material that is both rigid and viscoelastic. It is assembled from parallel hydroxyapatite nanowires (96 wt%), inorganic amorphous interphase, and a very small amount of biopolymers. Although enamel contains a very high content of inorganic substances, its damping ability is one order of magnitude higher than that of pure hydroxyapatite crystals, which can be attributed to the vertical orientation of rigid ceramics in enamel and the unique energy dissipation behavior that occurs at the crystal-amorphous ceramic interface when stressed. At the same time, the dense and stable enamel layer has excellent corrosion resistance, thus ensuring that teeth can continuously serve in the human oral cavity for more than 60 years. Currently, scientific researchers have prepared a series of artificial hierarchical composite materials (such as ZnO / LBL and TiO2-polymer / GO) by simulating the enamel structure and reproduced the high stiffness and high damping behavior of enamel. Inspired by this, in-situ construction of an enamel-like modification layer on the surface of widely used metal materials is expected to obtain a metal matrix composite material with high stiffness, high hardness, high damping, and corrosion resistance. Summary of the Invention

[0005] The object of the present invention is to address the deficiencies of the prior art. By using widely applied metal materials as the substrate, an operationally simple, environmentally friendly, mild experimental condition and universal preparation method is innovatively proposed to in-situ construct an enamel-like modification layer on the metal surface, achieving the strengthening and anti-corrosion of the metal material. The present invention adopts a liquid-phase synthesis method combined with a low-temperature calcination process to in-situ construct an enamel-like ceramic modification layer on the metal surface. The rigid nanorod array structure and the closely connected crystal / amorphous interface in this layer act synergistically to optimize the mechanical properties of the metal while enhancing the corrosion resistance of the metal, ultimately obtaining a high-strength and corrosion-resistant metal matrix composite material. It includes the following steps:

[0006] First step, prepare a 60 mL aqueous solution of sodium hydroxide (NaOH) in a 100 mL beaker, stir at room temperature for 5 min to obtain a homogeneous, transparent and colorless solution, and then pour it into a 100 mL hydrothermal reaction kettle; the weight ratio of NaOH to water is 1:30 to 1:10;

[0007] Second step, cut the metal foil into strips with a length × width of 5 × 1 cm to 20 × 1 cm; the metal foil needs to be ultrasonically cleaned with acetone, ethanol and water for 15 min respectively;

[0008] Third step, place the cleaned metal foil into the solution system prepared in the first step, then place the hydrothermal reaction kettle in an oven, continuously heat at 160 - 200 °C for 18 - 36 h to obtain an enamel-like prismatic ceramic nanorod array on the metal foil surface;

[0009] Fourth step, add 70 mL of distilled water to a beaker, place it in a constant-temperature cold water bath to keep the solution temperature at 8 - 16 °C, configure a standard buffer solution according to experimental requirements to obtain the required pH range to form a colorless and transparent solution; the standard buffer solution is selected from a pure water system of tris(hydroxymethyl)aminomethane (Tris)-concentrated hydrochloric acid (HCl), and its pH buffering range is 6.5 - 9;

[0010] Fifth step, add an appropriate amount of metal salt to the solution prepared in the fourth step, and stir at 8 - 16 °C until completely dissolved; the concentration range of the metal salt powder in the colorless and transparent solution is 0.15 mg / mL to 0.25 mg / mL;

[0011] Sixth step, place the metal foil with the ceramic nanorod array structure prepared in the third step into the solution prepared in the fifth step, continuously stir in the cold water bath for 12 - 16 h to fill the precursor of amorphous metal oxide in the array gaps;

[0012] Seventh step, place the metal matrix composite material prepared in the sixth step in a muffle furnace, calcine at 200 - 400 °C for 2 - 4 h to prepare a dense enamel-like ceramic modification layer on the metal foil surface, achieving the strengthening and anti-corrosion of the metal material.

[0013] In the present invention, without special instructions, the drugs used can be directly used without further purification. For example, the metal salts required for experiments can be purchased from conventional drug manufacturers.

[0014] In the present invention, without special instructions, the devices, instruments, equipment, materials, processes, methods, steps, preparation conditions, etc. used are those commonly used in the art or can be easily obtained by those of ordinary skill in the art according to the techniques commonly used in the art.

[0015] Further, the ultrasonic frequency in the second step is 100 Hz.

[0016] Further, the ceramic nanorod array obtained on the surface of the metal foil in the third step is the corresponding metal oxide nanorod of the substrate.

[0017] Further, the pH range of the Tris-HCl buffer solution in the fourth step is preferably 7-8.

[0018] Further, in the fifth step, the metal salt is preferably a metal halide salt.

[0019] Further, the amorphous metal oxide precursor filled in the array gap in the sixth step is the metal hydroxide corresponding to the amorphous metal oxide.

[0020] Further, in the seventh step, the heating rate of the muffle furnace is 5 °C / min, the calcination temperature is preferably 250-350 °C, and the calcination time is preferably 1.5-2.5 h.

[0021] Further, in the enamel-like modification layer obtained on the metal surface, the thickness of the enamel-like modification layer is 50-100 nm; the ceramic nanorod array is regularly arranged by crystal metal oxide nanorods with a diameter of 25-40 nm and a height of 50-100 nm; the amorphous filler is an amorphous metal oxide.

[0022] Further, the Young's modulus of the metal matrix composite material prepared by this method is 100-140 GPa, the hardness is 5-6 GPa, the storage modulus is 105-130 GPa, the damping coefficient is 0.029-0.042, and the mass loss rate is 0.002 mg·cm -2 .day -1 。

[0023] Compared with the existing preparation strategies of high-strength and corrosion-resistant metal matrix composite materials, the present invention has the following advantages:

[0024] 1. The raw materials selected in the preparation process of the present invention are simple, easy to obtain, low in cost, pollution-free and non-toxic, and the whole preparation process is simple to operate.

[0025] 2. The enamel-like modification layer prepared by the present invention is closely connected to the metal substrate, and the layer thickness is between 50 and 100 nm. The strong support of the enamel-like array structure, the slip mechanism at the crystal / amorphous interface, and the mechanical dissipation behavior of the amorphous interphase in this layer synergistically improve the stiffness and viscoelasticity of the metal matrix composite, breaking through the bottleneck that it is difficult to simultaneously improve the stiffness and viscoelasticity of metal materials.

[0026] 3. The enamel-like modification layer of the present invention is stable and dense. Combining with the long-range disordered atomic arrangement of the amorphous filler, the enamel-like modification layer can effectively resist the invasion of corrosive substances, thereby improving the corrosion resistance of metal materials and expanding the application scope of metal materials. Brief Description of the Drawings

[0027] Figure 1 It is a schematic diagram of the preparation process of the metal matrix composite with an enamel-like modification layer of the present invention.

[0028] Figure 2 It is an optical photograph of the zirconium foil and its surface and cross-section scanning electron microscope photographs in Example 1 of the present invention.

[0029] Figure 3 It is a cross-section transmission electron microscope photograph of the zirconium-based composite strengthened by enamel-like nanorod arrays obtained in Example 1 of the present invention.

[0030] Figure 4 It is an optical photograph of the metal matrix composite with an enamel-like modification layer obtained in Example 2 of the present invention and its surface and cross-section scanning electron microscope photographs.

[0031] Figure 5 It is the quasi-static mechanical test result of the metal matrix composite with an enamel-like modification layer obtained in Example 2 of the present invention.

[0032] Figure 6 It is the dynamic mechanical analysis result of the metal matrix composite with an enamel-like modification layer obtained in Example 2 of the present invention.

[0033] Figure 7 It is the electrochemical corrosion test result of the metal matrix composite with an enamel-like modification layer obtained in Example 2 of the present invention and zirconium foil.

[0034] Figure 8 It is the mass loss rate of the metal matrix composite with an enamel-like modification layer obtained in Example 2 of the present invention and zirconium foil in the salt spray test.

[0035] Figure 9 It is an optical photograph of the metal matrix composite with an enamel-like modification layer obtained in Example 3 of the present invention and its surface and cross-section scanning electron microscope photographs. Detailed implementation manners

[0036] The following will specifically describe the preparation method of the metal matrix composite material with an enamel-like modification layer in conjunction with the accompanying drawings and embodiments. It should be understood, however, that these embodiments are only used to illustrate the present invention and do not limit the protection scope of the present invention in any way.

[0037] Example 1

[0038] Preparation method of zirconium-based composite material strengthened by enamel-like nanorod arrays

[0039] First step, add 60 mL of distilled water into a beaker, then add 4 g of NaOH, stir at room temperature for 5 min to obtain a homogeneous, transparent and colorless solution, and then pour it into a 100 mL hydrothermal reaction kettle ( Figure 1 );

[0040] Second step, cut the zirconium foil into sheets with a length×width of 5×1 cm, and then ultrasonically clean it with acetone, ethanol and water for 15 min respectively ( Figure 2 );

[0041] Third step, place the cleaned zirconium foil in the solution system prepared in the first step, then place the hydrothermal reaction kettle in an oven, heat it continuously at 200 °C for 24 h, and obtain enamel-like prismatic ZrO2 nanorod arrays on the surface of the zirconium foil ( Figure 1 , 3).

[0042] Example 2

[0043] Preparation method of zirconium-based composite material strengthened by a thick enamel-like modification layer

[0044] First step, add 60 mL of distilled water into a beaker, then add 4 g of NaOH, stir at room temperature for 5 min to obtain a homogeneous, transparent and colorless solution, and then pour it into a 100 mL hydrothermal reaction kettle;

[0045] Second step, cut the zirconium foil into sheets with a length×width of 5×1 cm, and then ultrasonically clean it with acetone, ethanol and water for 15 min respectively;

[0046] Third step, place the cleaned zirconium foil in the solution system prepared in the first step, then place the hydrothermal reaction kettle in an oven, heat it continuously at 200 °C for 24 h, and obtain enamel-like prismatic ZrO2 nanorod arrays on the surface of the zirconium foil;

[0047] Fourth step, add 70 mL of distilled water into a beaker, place it in a constant temperature cold water bath to keep the solution temperature at 8 °C, add Tris / concentrated HCl buffer reagent, where Tris is 0.848 g and concentrated HCl is 465 μL, and maintain the reaction pH at about 7.5 ( Figure 1 );

[0048] Step 5: Add 16 mg of ZrOCl2·8H2O powder into the solution prepared in Step 4, and stir at 8 °C until completely dissolved( Figure 1 );

[0049] Step 6: Place the zirconium foil with ZrO2 nanorod array structure prepared in Step 3 into the solution prepared in Step 5, continuously stir for 16 h, and fill amorphous Zr(OH)4 in the gaps of the array( Figure 1 );

[0050] Step 7: Place the composite material prepared in Step 6 in a muffle furnace, calcine at 300 °C for 2 h, and prepare a dense enamel-like ZrO2 modification layer with a thickness of about 100 nm on the surface of the zirconium foil, obtaining the final metal matrix composite material with an enamel-like thick modification layer( Figure 1 , 4).

[0051] In the present invention, a nanoindentation instrument is used to test the metal matrix composite material with an enamel-like modification layer in Example 1. In the quasi-static mechanical test mode, the loading rate is 1 mN / s, and the termination load is 10 mN. The test results show that the Young's modulus and hardness of the prepared metal matrix composite material with an enamel-like modification layer in Example 1 are ~125.7 GPa and ~5.5 GPa respectively, which are 1.3 and 1.6 times that of pure zirconium foil( Figure 5 ); in the dynamic mechanical test mode, the starting load is 20 μN, the termination load is 10 mN, the starting dynamic force is 30 μN, and the frequency is 45 Hz. The storage modulus and damping coefficient of the prepared metal matrix composite material with an enamel-like modification layer in Example 1 are ~121.3 GPa and ~0.038 respectively( Figure 6 ). The electrolyte for the electrochemical corrosion experiment of Test Example 1 is 3.5 wt.% NaCl solution, the constant potential is -600 mV vs. SCE, and it runs for 300 s. The results show that obvious corrosion holes are formed on the surface of the zirconium foil( Figure 7 a, b), while under the same conditions, there is no corrosion phenomenon on the surface of the metal matrix composite material with an enamel-like modification layer( Figure 7 c, d). In addition, the salt spray test results show that the mass loss rate of the metal matrix composite material with an enamel-like modification layer is ~0.002 mg.cm -2 .day -1 , which is 7.5 times lower than that of pure zirconium foil, indicating that the enamel-like ZrO2 modification layer can significantly improve the corrosion resistance of the metal( Figure 8 ).

[0052] Example 3

[0053] Preparation method of zirconium-based composite material strengthened by thin enamel-like modification layer

[0054] First step: Add 60 mL of distilled water into a beaker, then add 4 g of NaOH. After stirring at room temperature for 5 min to obtain a homogeneous, transparent and colorless solution, pour it into a 100 mL hydrothermal reactor.

[0055] Second step: Cut the zirconium foil into sheets with a length × width of 5 × 1 cm, and then ultrasonically clean it with acetone, ethanol and water for 15 min respectively.

[0056] Third step: Place the cleaned zirconium foil into the solution system prepared in the first step, then place the hydrothermal reactor in an oven and heat it continuously at 200 °C for 18 h to obtain enamel-like prismatic ZrO2 nanorod arrays on the surface of the zirconium foil.

[0057] Fourth step: Add 70 mL of distilled water into a beaker, place it in a constant-temperature cold water bath to keep the solution temperature at 8 °C, and add Tris / concentrated HCl buffer reagent, where Tris is 0.848 g and concentrated HCl is 465 μL, and maintain the reaction pH at about 7.5.

[0058] Fifth step: Add 16 mg of ZrOCl2·8H2O powder into the solution prepared in the fourth step and stir it at 8 °C until it is completely dissolved.

[0059] Sixth step: Place the zirconium foil with the ZrO2 nanorod array structure prepared in the third step into the solution prepared in the fifth step and stir continuously for 12 h to fill amorphous Zr(OH)4 in the gaps of the array.

[0060] Seventh step: Place the composite material prepared in the sixth step in a muffle furnace and calcine it at 300 °C for 2 h to obtain a dense enamel-like ZrO2 modification layer with a thickness of about 50 nm on the surface of the zirconium foil, and obtain the final metal matrix composite material with an enamel-like thin modification layer ( Figure 9 ).

Claims

1. A method for preparing a metal matrix composite with an enamel-like modification layer, characterized in that It includes the following steps: In the first step, prepare 60 mL of an aqueous NaOH solution in a 100 mL beaker. After stirring at room temperature for 5 min to obtain a homogeneous, transparent, colorless solution, then pour it into a 100 mL hydrothermal reaction kettle; the weight ratio of NaOH to water is 1:30 to 1:10; In the second step, cut the metal foil into long strips with a length × width of 5×1 cm to 20×1 cm; the metal foil needs to be ultrasonically cleaned with acetone, ethanol, and water for 15 min respectively; In the third step, place the cleaned metal foil into the solution system prepared in the first step. Then place the hydrothermal reaction kettle in an oven and continuously heat it at 160 - 200 °C for 18 - 36 h to obtain an enamel-like prismatic ceramic nanorod array on the surface of the metal foil; In the fourth step, add 70 mL of distilled water to a beaker, place it in a constant-temperature cold water bath to keep the solution temperature at 8 - 16 °C, and prepare a standard buffer solution according to experimental requirements to obtain the desired pH range to form a colorless, transparent solution; the standard buffer solution is selected from a pure water system of tris(hydroxymethyl)aminomethane - concentrated hydrochloric acid, and its pH buffering range is 6.5 - 9; In the fifth step, add an appropriate amount of metal salt to the solution prepared in the fourth step and stir at 8 - 16 °C until completely dissolved; the concentration range of the metal salt powder in the colorless, transparent solution is 0.15 mg / mL to 0.25 mg / mL; In the sixth step, place the metal foil with the ceramic nanorod array structure prepared in the third step into the solution prepared in the fifth step, and continuously stir in a cold water bath for 12 - 16 h to fill the precursor of amorphous metal oxide in the array gaps; In the seventh step, place the metal matrix composite material prepared in the sixth step in a muffle furnace and calcine it at 200 - 400 °C for 2 - 4 h to obtain a dense enamel-like ceramic modification layer on the surface of the metal foil, realizing the strengthening and anti-corrosion of the metal material.

2. The preparation method of a metal matrix composite material with an enamel-like modification layer according to claim 1, characterized in that: The surface of the composite material prepared in the third step has an enamel-like prismatic ceramic nanorod array. The nanorods are metal oxide nanorods corresponding to the metal foil, and their diameters are controllable within the range of 25 - 40 nm and their heights are within the range of 50 - 100 nm.

3. The preparation method of a metal matrix composite material with an enamel-like modification layer according to claim 1, characterized in that: The surface of the metal matrix composite material prepared in the seventh step has a uniform and dense enamel-like ceramic modification layer, and the layer thickness is controllable within the range of 50 - 100 nm.

4. The preparation method of a metal matrix composite material with an enamel-like modification layer according to claim 1, characterized in that: The enamel-like ceramic modification layer in-situ constructed on the surface of the metal substrate in the seventh step has an array structure arranged in parallel and an amorphous interphase inside.

5. The preparation method of a metal matrix composite material with an enamel-like modification layer according to claim 1, characterized in that: The Young's modulus and hardness of the metal matrix composite material with the enamel-like modification layer prepared in the seventh step are 100 - 140 GPa and 5 - 6 GPa respectively, and the storage modulus and damping coefficient are 105 - 130 GPa and 0.029 - 0.042 respectively.

6. The preparation method of a metal matrix composite material with an enamel-like modification layer according to claim 1, wherein: The mass loss rate of the metal matrix composite material with enamel-like modification layer prepared in the seventh step is 0.002 mg.cm -2 .day -1 .

7. The preparation method of a metal matrix composite material with an enamel-like modification layer according to claim 1, characterized in that: The ceramic component of the enamel-like modification layer is zirconia.

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