WO2021036091A1

WO2021036091A1 - 3d printing method for preparing biomimetic smart metal material surface

Info

Publication number: WO2021036091A1
Application number: PCT/CN2019/124462
Authority: WO
Inventors: 张勇
Original assignee: 广州番禺职业技术学院
Priority date: 2019-08-23
Filing date: 2019-12-11
Publication date: 2021-03-04
Also published as: CN110434337A

Abstract

Disclosed is a 3D printing method for preparing a biomimetic smart metal material surface, comprising: S1, using 3D metal laser sintering to prepare a metal surface having different microscopic morphologies; and S2, using surface chemical reaction processing to treat the metal surface having different surface microscopic morphologies to obtain a metal functional surface having different surface chemical compositions and surface roughnesses. By using the 3D metal laser sintering and surface chemical reaction processing together to prepare the metal functional surface, a metal surface having different surface chemical compositions, surface roughnesses, and surface geometrical morphologies can be obtained. Furthermore, each of the chemical composition, surface roughness, and surface geometrical morphology of the metal surface exhibits a continuous, monotonous variation. The surface contact angle of the metal surface exhibits a gradient variation in the range of 150°±15° to 10°±5°.

Description

3D printing method for preparing bionic smart metal material surface

Technical field

The invention belongs to the technical surface treatment technology, and specifically relates to a preparation method for preparing the surface of a bionic smart metal material by 3D printing.

Background technique

Bionic smart materials are based on the principles of bionics, imitating various characteristics or characteristics of organisms, and are prepared through structural bionics and functional bionics, new materials with perception, response and special functional capabilities. As an important functional material, metal is widely used in various engineering fields. The preparation of multi-scale ordered metal surfaces with molecular, nano, and micron structures is an inherent requirement to realize the surface of bionic smart metal materials. At present, the surface of bionic smart metal materials is mainly prepared by adjusting the chemical composition of the metal surface and constructing the microscopic morphology of the metal surface.

The prior art method regulates the surface chemical composition of the metal surface based on the microscopic morphology or constructs the surface morphology based on a certain surface chemical composition, or both methods are used at the same time; however, the method of constructing the microscopic morphology of the metal surface is relatively It is complicated and difficult to achieve effective control of the micro-topography of the metal surface. In addition, as the microscopic morphology of the metal surface changes, it is not easy to control the surface chemical composition.

Summary of the invention

In order to solve the above technical problems, the present invention provides a simple and easy preparation method for the construction of the micro-topography of the metal surface and the control of the surface chemical composition.

In order to achieve the above objectives, the technical solutions adopted by the present invention are as follows:

A preparation method for preparing the surface of a bionic smart metal material by 3D printing includes the following steps:

S1 uses three-dimensional modeling software and drawing software to create a metal surface three-dimensional model with a geometric surface micro-topography, and obtains three-dimensional data of the model; processes the three-dimensional data after obtaining the three-dimensional data, and uses the obtained 3D printing process files for rapid prototyping printing equipment Complete the preparation of metal materials with geometric surface micro-topography.

S2 Place the metal surface obtained in step S1 in a container, and add solution C dropwise to ensure that the upper edge of the metal piece surface is completely infiltrated by solution C when the drop is completed in 10 to 60 minutes to obtain a pre-functional metal surface; The functional metal surface is washed in heated distilled water and then dried to obtain a metal functional surface; the metal functional surface is heated in distilled water at 60 to 150°C for 1 to 4 hours.

Further, the rapid prototyping printing device in the step S1 is a 3D metal laser sintering printing device.

Further, the processing of the three-dimensional data in the step S1 is realized by the following methods: first, the data format from the software is converted into an STL data format suitable for the generation of 3D printing process files; secondly, the STL data is checked and error analyzed; Then, estimate the amount of printing consumables and sample size according to the requirements of the metal sample; finally, edit the STL file to obtain the 3D printing process file.

Further, in step S2, before placing the metal surface obtained in step S1 in the container, the method further includes the following steps: placing the metal surface obtained in step S1 in a cleaning solution, soaking and cleaning for 10-40 minutes, to obtain clean metal surface.

Further, the cleaning liquid is one or more of acetone, ethanol, hydrochloric acid solution, nitric acid solution, sulfuric acid solution, phosphoric acid solution or distilled water.

Further, in the step S2, the solution C is prepared by mixing 1-50 parts of alkaline solution A, 0-30 parts of oxidizing solution B, and 10-80 parts of distilled water, and then uniformly stirring; The concentrations of the alkaline solution A and the oxidizing solution B are both 0.01 mol/L to 10 mol/L.

Further, the alkaline solution A is one or more of sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide solution, potassium carbonate solution, potassium bicarbonate solution, sodium carbonate solution or sodium bicarbonate solution The oxidizing solution B is one or more of ammonium persulfate solution, potassium persulfate solution, sodium persulfate solution, hydrogen fluoride solution, ammonium fluoride solution or hydrogen peroxide solution.

Further, the temperature of the distilled water heated in the step S2 is 60-150° C. in distilled water for 1 to 4 hours.

Further, the drying temperature in the step S2 is 20°C to 80°C.

Further, the metal is one or more of gold, silver, copper, cobalt-chromium alloy, stainless steel, nickel alloy, aluminum alloy, and titanium alloy.

Further, the geometric figure is one or more of a triangle, a quadrilateral, a pentagon, a hexagon, a flat surface, and a hemisphere.

The present invention also provides the metal functional surface prepared by the above preparation method, the surface chemical composition, surface roughness and surface geometric morphology continuity monotonously change.

Further, the continuous monotonic change of the surface geometric morphology is that the surface contact angle changes gradually within the range of 150°±15°-10°±5°.

In the present invention, the surface chemical composition refers to metals and their metal oxides and metal hydroxides, the gold surface refers to gold and gold oxides and gold hydroxides, and the silver surface refers to silver and silver oxides and silver hydroxides. Copper surface refers to copper and copper oxide and copper hydroxide, cobalt-chromium alloy surface refers to cobalt-chromium alloy and cobalt-chromium alloy oxide and cobalt-chromium alloy hydroxide, stainless steel surface refers to stainless steel and stainless steel oxide and stainless steel Hydroxide, nickel alloy surface refers to nickel alloy and nickel alloy oxide and nickel alloy hydroxide, aluminum alloy surface refers to aluminum alloy and aluminum alloy oxide and aluminum alloy hydroxide, titanium alloy surface refers to titanium alloy and titanium alloy oxidation And titanium alloy hydroxides. In the present invention, the continuous monotonic change of the surface geometric morphology means that the geometric morphology of the metal surface presents a continuous change from simple to complex, and the change is shown in FIG. 1.

The beneficial effects of the present invention: the present invention uses 3D metal laser sintering technology and surface chemical reaction treatment technology to prepare metal functional surfaces, and obtain metal surfaces with different surface chemical compositions, surface roughness and surface geometric morphologies. In addition, the chemical composition, surface roughness and surface geometry of the metal surface showed continuous and monotonous changes, and the surface contact angle showed a gradient change in the range of 150°±15°～10°±5°.

Description of the drawings

Figure 1 is a schematic diagram of the continuity and monotonic change of the geometric morphology of the metal surface.

Figure 2 is a schematic diagram of a copper-based material with a triangular arrangement on the surface.

Figure 3 is a schematic diagram of a silver-based material with a quadrilateral arrangement on the surface.

Figure 4 is a schematic diagram of a gold-based material with a pentagonal arrangement on the surface.

Fig. 5 is a schematic diagram of an aluminum alloy-based material with a hexagonal surface arrangement.

Fig. 6 is a schematic diagram of a stainless steel-based material with a hemispherical surface arrangement.

Figure 7 is a schematic diagram of a nickel alloy-based material with a flat surface.

detailed description

In order to show the technical solutions, objectives and advantages of the present invention more concisely and clearly, the present invention will be further described in detail below in conjunction with specific embodiments and the accompanying drawings.

Example 1 Copper-based material with a triangular arrangement on the surface

The first step is to use three-dimensional modeling software and CAD (Computer-Aided Design) workstations to create a three-dimensional model of a copper-based surface with a three-sided surface micro-morphology, and obtain three-dimensional data and 3D printing of the model. Process file: First, convert the data format from the software into an STL data format suitable for the generation of 3D printing process files; secondly, check the STL data and analyze errors; then, pre-process the printing consumables consumption and sample size according to the metal sample requirements. Estimate; Finally, edit the STL file to obtain the 3D printing process file. 3D metal laser sintering printing equipment was selected to complete the preparation of metal materials with a triangular arrangement on the copper-based surface.

In the second step, the copper-based surface obtained in the first step is placed in acetone, soaked and cleaned for 15 minutes, to obtain a clean copper-based surface;

The third step is to mix 10 grams of 1mol/L sodium hydroxide solution, 10 grams of 1mol/L ammonium persulfate solution and 15 grams of distilled water, and stir at 15 rpm for 7 minutes to obtain solution C;

In the fourth step, the clean copper-based surface obtained in the second step is vertically placed in an open container, and solution C is gradually added dropwise to the container to ensure that the upper edge of the clean copper-based surface is just Solution C is completely infiltrated to obtain a pre-functional surface;

In the fifth step, the pre-functional surface obtained in the fourth step is washed twice in distilled water and dried at 50°C. After drying, the preparation of the copper-based functional surface is completed. The surface chemical composition and surface roughness of the copper-based surface are continuous The performance changes monotonously; after the obtained copper-based functional surface is heated in distilled water at 90°C for 2 hours, the surface chemical composition and surface roughness have not changed significantly, and the functional surface has good water resistance and heat resistance.

Example 2 Silver-based material with quadrilateral arrangement on the surface

The first step is to use three-dimensional modeling software and CAD (Computer-Aided Design) workstations to create three-dimensional models of silver-based surface quadrilateral arrangements with different surface micro-topography, to obtain model three-dimensional data and 3D printing process files, select The 3D metal laser sintering printing equipment completes the preparation of metal materials arranged in quadrangles on the silver-based surface.

In the second step, the silver-based surface obtained in the first step is respectively placed in acetone and ethanol, and soaked and cleaned for 10 minutes in sequence for a total of 20 minutes to obtain a clean silver-based surface;

The third step is to mix 5 grams of 0.1 mol/L potassium hydroxide solution, 2 grams of 0.01 mol/L sodium persulfate solution and 10 grams of distilled water, and stir at 10 rpm for 5 minutes to obtain solution C;

In the fourth step, the clean silver-based surface obtained in the second step is vertically placed in an open container, and solution C is gradually added dropwise to the container to ensure that the upper edge of the clean silver-based surface is just Solution C is completely infiltrated to obtain a pre-functional surface;

In the fifth step, the pre-functional surface obtained in the fourth step is washed twice in distilled water and dried at 40°C. After drying, the preparation of the silver-based functional surface is completed. The surface chemical composition and surface roughness of the silver-based surface are continuous. Monotonous changes in properties; after the obtained silver-based functional surface is heated in distilled water at 80°C for 1 hour, the surface chemical composition and surface roughness have not changed significantly, and the functional surface has good water resistance and heat resistance.

Example 3 Gold-based material with pentagonal arrangement on the surface

The first step is to use 3D modeling software and CAD (Computer-Aided Design, computer-aided design) workstations to create a three-dimensional model of the pentagonal arrangement of the gold-based surface with different surface micro-topography, and obtain the model three-dimensional data and 3D printing process files , Choose 3D metal laser sintering printing equipment to complete the preparation of metal materials with pentagonal arrangement on the surface of the gold base.

In the second step, put the gold-based surface obtained in the first step in ethanol and distilled water respectively, and soak and wash for 12 minutes for a total of 24 minutes to obtain a clean gold-based surface;

The third step is to mix 4 grams of potassium hydroxide solution with a concentration of 3mol/L and 9 grams of sodium bicarbonate solution with a concentration of 5mol/L, 3.5 grams of 4mol/L potassium persulfate solution and 27 grams of distilled water at 14 revolutions per minute. Stir at a speed of 6 minutes to obtain solution C;

In the fourth step, the clean gold surface obtained in the second step is vertically placed in an open container, and solution C is gradually added dropwise to the container to ensure that the upper edge of the clean gold surface is just covered by the dripping in 36 minutes. Solution C is completely infiltrated to obtain a pre-functional surface;

In the fifth step, the pre-functional surface obtained in the fourth step is washed twice in distilled water and dried at 42°C. After drying, the preparation of the gold-based functional surface is completed. The surface chemical composition and surface roughness of the gold-based surface are continuous. The properties change monotonously; after the obtained gold-based functional surface is heated in distilled water at 100°C for 4 hours, the surface chemical composition and surface roughness have not changed significantly, and the functional surface has good water resistance and heat resistance.

Example 4 Aluminum alloy base material with hexagonal surface arrangement

The first step is to use 3D modeling software and CAD (Computer-Aided Design, computer-aided design) workstations to create a 3D model of hexagonal arrangement of aluminum alloy substrates with different surface microstructures to obtain 3D model data and 3D printing process File, select 3D metal laser sintering printing equipment to complete the preparation of the hexagonal arrangement of metal materials on the surface of the aluminum alloy base.

In the second step, the aluminum alloy base surface obtained in the first step is respectively placed in acetone and distilled water, and soaked and cleaned in sequence for 7 minutes for a total of 14 minutes to obtain a clean aluminum alloy base surface;

The third step is to mix 5 grams of sodium hydroxide solution with a concentration of 7mol/L, 6 grams of calcium hydroxide solution with a concentration of 6mol/L, and 20 grams of distilled water, and stir for 8 minutes at a speed of 17 rpm to obtain solution C;

In the fourth step, the clean aluminum alloy base surface obtained in the second step was vertically placed in an open container, and solution C was gradually added dropwise to the container to ensure that the upper edge of the clean aluminum alloy base surface was dripped in 32 minutes. Just completely infiltrated by solution C to obtain a pre-functional surface;

In the fifth step, the pre-functional surface obtained in the fourth step is rinsed in distilled water for 3 times, and then dried at 56°C. After drying, the preparation of the aluminum alloy-based functional surface is completed. The surface chemical composition and surface roughness of the aluminum alloy-based surface The degree of continuity changes monotonously; after the obtained aluminum alloy-based functional surface is heated in distilled water at 85°C for 1.5 hours, the surface chemical composition and surface roughness do not change significantly, and the functional surface has good water resistance and heat resistance.

Example 5 Stainless steel base material with hemispherical surface arrangement

The first step is to use three-dimensional modeling software and CAD (Computer-Aided Design) workstations to create a three-dimensional model of stainless steel base surface hemispherical arrangements with different surface micro-morphologies, and obtain model three-dimensional data and 3D printing process files. Select 3D metal laser sintering printing equipment to complete the preparation of metal materials arranged in a hemispherical shape on the surface of the stainless steel base.

In the second step, the stainless steel base surface obtained in the first step is respectively placed in acetone and ethanol, and soaked and cleaned in sequence for 6 minutes, for a total of 12 minutes, to obtain a clean stainless steel base surface;

The third step is to mix 7 grams of 9mol/L sodium hydroxide solution, 4 grams of 4mol/L sodium persulfate solution and 24 grams of distilled water, and stir at 13 rpm for 6 minutes to obtain solution C;

In the fourth step, the clean stainless steel base surface obtained in the second step is vertically placed in an open container, and solution C is gradually added dropwise to the container to ensure that when the dripping is completed in 17 minutes, the upper edge of the clean stainless steel base surface is just covered. Solution C is completely infiltrated to obtain a pre-functional surface;

In the fifth step, the pre-functional surface obtained in the fourth step is washed 3 times in distilled water and dried at 53°C. After drying, the preparation of the stainless steel-based functional surface is completed. The surface chemical composition and surface roughness of the stainless steel-based surface are continuous Monotonous changes in performance; after the obtained stainless steel-based functional surface is heated in distilled water at 95°C for 2.5 hours, the surface chemical composition and surface roughness have not changed significantly, and the functional surface has good water resistance and heat resistance.

Example 6 Nickel alloy-based material with flat surface

This embodiment adopts the preparation method of embodiment 1, and the difference from embodiment 1 is that this embodiment uses a nickel alloy material, and the surface is a flat surface.

Example 7 Aluminum alloy-based material with a triangular arrangement on the surface

This embodiment adopts the preparation method of embodiment 1, and the difference from embodiment 1 is that this embodiment uses an aluminum alloy material.

Example 8 Titanium alloy-based material with triangular surface arrangement

Example 9

The only difference between this embodiment and Embodiment 1 is that the cleaning liquid of this embodiment uses hydrochloric acid and nitric acid.

Example 10

The only difference between this embodiment and Embodiment 1 is that the cleaning liquid of this embodiment uses sulfuric acid and phosphoric acid.

Example 11

The only difference between this embodiment and embodiment 1 is that the alkaline solution A in this embodiment is potassium carbonate and potassium bicarbonate; the oxidizing solution B is potassium persulfate.

Example 12

The only difference between this embodiment and embodiment 1 is that the alkaline solution A in this embodiment is sodium carbonate and sodium bicarbonate; the oxidizing solution B is ammonium fluoride.

After heating the metal functional surfaces prepared in Examples 6-12 in distilled water at 150°C for 2 hours, the surface chemical composition and surface roughness did not change significantly. The metal functional surfaces prepared in Examples 6-12 have good water resistance and resistance. Thermal.

The above-mentioned embodiments only express several embodiments of the present invention, and the descriptions are more specific and detailed, but they should not be understood as limiting the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims

A method for preparing the surface of a biomimetic smart metal material by 3D printing is characterized in that it comprises the following steps:

S1 uses three-dimensional modeling software and drawing software to create a metal surface three-dimensional model with a geometric surface micro-topography, and obtains three-dimensional data of the model; processes the three-dimensional data after obtaining the three-dimensional data, and uses the obtained 3D printing process files for rapid prototyping printing equipment Complete the preparation of metal materials with geometric surface micro-topography;

S2 Place the metal surface obtained in step S1 in a container, and add solution C dropwise to ensure that the upper edge of the metal piece surface is completely infiltrated by solution C when the drop is completed in 10 to 60 minutes to obtain a pre-functional metal surface; The functional metal surface is washed in heated distilled water and then dried to obtain a metal functional surface; the metal functional surface is heated in distilled water at 60 to 150°C for 1 to 4 hours.
The method for preparing the surface of the bionic smart metal material by 3D printing according to claim 1, wherein the rapid prototyping printing device in the step S1 is a 3D metal laser sintering printing device.
The method for preparing the surface of the biomimetic smart metal material by 3D printing according to claim 1, wherein the processing of the three-dimensional data in the step S1 is realized by the following method: first, the data format from the software is converted into a suitable 3D The STL data format generated by the printing process file; secondly, the STL data is checked and error analysis; then, the amount of printing consumables and the sample size are estimated according to the requirements of the metal sample; finally, the STL file is edited and processed to obtain the 3D printing process file.
The method for preparing the surface of a bionic smart metal material by 3D printing according to claim 1, characterized in that, in the step S2, before placing the metal surface obtained in step S1 in the container, the method further comprises the following steps: The obtained metal surface is placed in a cleaning solution, soaked and cleaned for 10-40 minutes to obtain a clean metal surface; the cleaning solution is one or one of acetone, ethanol, hydrochloric acid solution, nitric acid solution, sulfuric acid solution, phosphoric acid solution or distilled water More than species.
The method for preparing the surface of biomimetic smart metal materials by 3D printing according to claim 1, wherein the solution C in the step S2 is composed of 1-50 parts of alkaline solution A and 0-30 parts of oxidation The solution B is prepared by mixing and stirring 10 to 80 parts of distilled water evenly; wherein the concentration of the alkaline solution A and the oxidizing solution B are both 0.01 mol/L-10 mol/L.
The method for preparing the surface of bionic smart metal materials by 3D printing according to claim 5, wherein the alkaline solution A is sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide solution, potassium carbonate solution, carbonic acid One or more of potassium hydrogen solution, sodium carbonate solution or sodium hydrogen carbonate solution; the oxidizing solution B is ammonium persulfate solution, potassium persulfate solution, sodium persulfate solution, hydrogen fluoride solution, ammonium fluoride solution Or one or more of the hydrogen peroxide solutions.
The method for preparing the surface of biomimetic smart metal material by 3D printing according to claim 1, wherein the temperature of the distilled water heated in step S2 is 60-150°C and heated in distilled water for 1 to 4 hours; further, the The drying temperature in step S2 is 20°C to 80°C.
The method for preparing the surface of bionic smart metal materials by 3D printing according to claim 1, wherein the metal is one of gold, silver, copper, cobalt-chromium alloy, stainless steel, nickel alloy, aluminum alloy, and titanium alloy. One or more kinds.
The preparation method for preparing the surface of bionic smart metal material by 3D printing according to claim 1, wherein the geometric figure is one of a triangle, a quadrilateral, a pentagon, a hexagon, a flat surface, and a hemisphere. One or more kinds.
A metal functional surface prepared by the preparation method according to claim 1, wherein the surface chemical composition, surface roughness, and surface geometric morphology continuity change monotonously; the surface geometric morphology continuity changes monotonously The surface contact angle changes gradually within the range of 150°±15°～10°±5°.