CN111809205A - Three-dimensional alloy micro-nano structure printing device and method based on micro-area electrochemical deposition - Google Patents
Three-dimensional alloy micro-nano structure printing device and method based on micro-area electrochemical deposition Download PDFInfo
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- CN111809205A CN111809205A CN202010706557.2A CN202010706557A CN111809205A CN 111809205 A CN111809205 A CN 111809205A CN 202010706557 A CN202010706557 A CN 202010706557A CN 111809205 A CN111809205 A CN 111809205A
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- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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Abstract
The invention discloses a three-dimensional alloy micro-nano structure printing device and a method based on micro-area electrochemical deposition, belonging to the field of electrochemistry, wherein the device comprises a hollow micro-tube for filling plating solution, and the plating solution contains at least one first type metal ion suitable for electroplating; the electric control displacement platform is used for bearing a conductive sample and is also used for driving the sample to move according to a preset track; the voltage source is used for connecting the plating solution and the sample in the hollow microtube into an electric loop through a lead; and the controller is used for controlling the voltage source and enabling the bias voltage value on the sample to be in a voltage range enabling ions of at least one first type of metal to be deposited when the electric control displacement platform moves relative to the hollow microtube according to a preset track. According to the invention, the power supply controller controls the voltage source, so that at least one first type of metal ions are deposited under the action of electroplating voltage to realize the printing operation of the three-dimensional alloy micro-nano structure.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a three-dimensional alloy micro-nano structure printing device and method based on micro-area electrochemical deposition.
Background
Three-dimensional printing technology of metal substrates is the hot spot of current research. There are five main types of metal three-dimensional printing technologies that have been commercialized currently: selective laser sintering, nano-particle metal injection molding, selective laser melting, near-net laser molding and selective electron beam melting. The technologies belong to a macroscopic metal three-dimensional manufacturing technology relatively, the printing precision of the technologies is generally in the order of tens of micrometers or even hundreds of micrometers, and the printing of a metal micro-nano structure with a smaller size cannot be realized.
The electrochemical deposition is a technology in which current is transferred through positive and negative ions in an electrolyte solution under the action of an external electric field, and oxidation-reduction reaction of gain and loss electrons occurs on an electrode to form a plating layer. In recent years, the three-dimensional micro-area electrochemical deposition technology based on the hollow micro-tube is widely concerned by the industry and academia, and can realize the accurate printing of various elementary metal three-dimensional micro-nano structures, such as the printing of complex three-dimensional micro-nano structures of copper, platinum and the like.
For example, chinese patent application publication No. CN111088518A discloses a closed-loop control system for three-dimensional micro-area electrochemical deposition, which can be used to manufacture elemental metals with three-dimensional micro-nano structures.
However, printing of three-dimensional micro-nano structures of alloy components has not been achieved. The method has the difficulty that electrochemical deposition process parameters of different metals are completely different, and simple mixing and three-dimensional printing of several different metal salt solutions can cause that part of metals cannot be deposited, and finally alloy micro-nano three-dimensional structures with uniform materials cannot be manufactured. And for metals that are difficult to plate, the device is difficult to manufacture and has a large use limitation.
Disclosure of Invention
Aiming at the problem that the three-dimensional alloy micro-nano structure is difficult to manufacture in the prior art, the invention aims to provide a three-dimensional alloy micro-nano structure printing device and method based on micro-area electrochemical deposition.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a three-dimensional alloy micro-nano structure printing device based on micro-area electrochemical deposition comprises,
the micro-tube plating device comprises a hollow micro-tube, a plating solution and a plating solution, wherein the hollow micro-tube is used for filling the plating solution, the plating solution contains at least one first type metal ion, and the first type metal is suitable for electroplating;
the electric control displacement platform is used for bearing a conductive sample and driving the sample to move according to a preset track;
the voltage source is used for connecting the plating solution in the hollow microtube and the sample into an electric loop through a lead;
and the controller is electrically connected with the voltage source and the electric control displacement table, and is used for controlling the voltage source and enabling the bias voltage value on the sample to be within a voltage range enabling the ions of the at least one first type of metal to be deposited when the electric control displacement table is controlled to move relative to the hollow microtube according to a preset track.
Furthermore, the device also comprises a manual adjusting platform, and the manual adjusting platform and the electric control displacement platform are fixedly installed.
The invention also provides a preparation method of the three-dimensional alloy micro-nano structure, which is based on the printing device, the three-dimensional alloy micro-nano structure comprises at least one first type of metal in components, the first type of metal is suitable for electroplating, the method comprises the following steps,
filling a plating solution comprising ions of at least one of the first type of metal into the hollow microtubes;
the sample is close to the tip of the hollow microtube until the surface of the sample is contacted with the plating solution;
controlling the voltage source by a controller to bring the bias voltage value on the sample within a voltage range enabling deposition of ions of the at least one first type of metal;
the electric control displacement table is controlled by a controller to drive the sample to move relative to the hollow microtube according to a preset track, so that a base material is obtained on the surface of the sample;
depositing a build-up layer on the surface of the base material through a deposition process to obtain an intermediate;
carrying out high-temperature heat treatment on the intermediate to enable part or all of the added layer to be fused with the base material, so that a three-dimensional alloy micro-nano structure is obtained;
wherein the build-up layer is metallic or non-metallic.
Particularly, when the three-dimensional alloy micro-nano structure comprises at least two first type metals, before filling a plating solution comprising ions of the at least two first type metals into the hollow micro-tube, the method also comprises a step of preparing the plating solution,
determining an electroplating voltage according to the types of the at least two first type metals contained in the three-dimensional alloy micro-nano structure and the Nernst equation, wherein the electroplating voltage is a bias voltage value on the test sample;
according to the component proportion relation of the at least two first type metals contained in the three-dimensional alloy micro-nano structure, prefabricating a plating solution containing ions of the at least two first type metals;
and regulating the concentration of each first type of metal ion in the plating solution to ensure that the proportional relation of the deposition speed of each first type of metal ion in the plating solution under the plating voltage is the same as the component proportional relation of each first type of metal in the three-dimensional alloy micro-nano structure.
Preferably, the build-up layer comprises at least two layers of structures, the at least two layers of structures being obtained by performing the deposition process a plurality of times.
Preferably, the at least two layers of structures are made of different materials, and each layer of structure is obtained by a deposition process adapted to the structure.
By adopting the technical scheme, due to the arrangement of the hollow micro-tube, the plating solution can flow out in a fine mode, so that a fine micro-nano structure is realized; due to the arrangement of the electric control displacement table, the metal ions in the plating solution are deposited to form a required three-dimensional model on the sample by moving the sample; due to the arrangement of the controller, the voltage source is adjusted to adjust the bias voltage value of the sample, effective deposition of various metal ions needing to be deposited in the plating solution can be guaranteed, and the manufacture of the three-dimensional alloy micro-nano structure is guaranteed.
Drawings
FIG. 1 is a schematic illustration of a first embodiment of the present invention when not in use;
FIG. 2 is a schematic view of a first embodiment of the present invention;
FIG. 3 is a flowchart of a method according to a second embodiment of the present invention;
FIG. 4 is a schematic view of the build-up layer fully alloyed with the substrate in a method according to a second embodiment of the invention;
FIG. 5 is a schematic view of the alloying of the build-up portion with the substrate in a method according to a second embodiment of the invention;
FIG. 6 is a flow chart of a plating solution preparing method according to a second embodiment of the present invention.
In the figure, 1-a hollow micro-tube, 2-plating solution, 3-an electric control displacement table, 4-a sample, 5-a voltage source, 6-a controller, 7-a manual adjusting table, 8-an ammeter, 10-a base material, 20-a build-up layer and 30-an alloy layer.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
It should be noted that in the description of the present invention, the terms "upper", "lower", "left", "right", "front", "rear", and the like indicate orientations or positional relationships based on structures shown in the drawings, and are only used for convenience in describing the present invention, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the technical scheme, the terms "first" and "second" are only used for referring to the same or similar structures or corresponding structures with similar functions, and are not used for ranking the importance of the structures, or comparing the sizes or other meanings.
In addition, unless expressly stated or limited otherwise, the terms "mounted" and "connected" are to be construed broadly, e.g., the connection may be a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; the two structures can be directly connected or indirectly connected through an intermediate medium, and the two structures can be communicated with each other. To those skilled in the art, the specific meanings of the above terms in the present invention can be understood in light of the present general concepts, in connection with the specific context of the scheme.
The invention provides an embodiment of a first aspect, and provides a three-dimensional alloy micro-nano structure printing device based on micro-area electrochemical deposition, as shown in fig. 1 and fig. 2, which specifically comprises,
the plating system comprises a hollow microtube 1 and a plating solution 2, wherein the hollow microtube 1 is used for filling the plating solution 2, and the plating solution 2 contains ions of at least one first type metal which is suitable for electroplating;
the hollow microtube 1 can be various tubular objects with hollow structures, such as microtubes and microtube arrays processed based on MEMS manufacturing technology; or the hollow microtube 1 can be various capillaries and cluster arrays, for example, when the hollow microtube is a glass capillary, the hollow microtube 1 with various tip diameters can be obtained by adopting a fusion and stretching process. In the present embodiment, the diameter of the tip of the hollow microtube 1 varies from several tens of nanometers to several hundreds of micrometers, and is specifically selected according to the size of the printed structure. The first type of metal is suitable for electroplating, and the first type of metal is characterized in that ions of the first type of metal can be deposited in a solution under a certain electroplating voltage.
The device is characterized by further comprising an electric control displacement platform 3, wherein the electric control displacement platform 3 is used for bearing a conductive sample 4, and the electric control displacement platform 3 is further used for driving the sample 4 to move according to a preset track;
the electric control displacement table 3 can be a piezoelectric displacement table, the movement of the electric control displacement table can be controlled by a displacement controller during working, the displacement controller receives control from an upper computer, and the piezoelectric displacement table can also be a one-dimensional, two-dimensional or three-dimensional piezoelectric displacement table according to the complexity of the shape of a printing structure. In this embodiment, the upper computer is generally a computer.
The electric control displacement platform is characterized by further comprising a manual adjusting platform 7, wherein the manual adjusting platform 7 is fixedly installed with the electric control displacement platform 3;
for example, the manual adjustment stage 7 is fixedly mounted on a test stand or a production platform, and the electrically controlled displacement stage 3 is fixedly mounted on an output end (working surface) of the manual adjustment stage 7. Because the device of the embodiment is used for printing the micro-nano structure, it can be understood that the motion precision of the electric control displacement table 3 is high, and therefore the device has the characteristics of small stroke and low moving speed. However, before the actual production process begins, because the hollow micro tube 1 needs to be installed, the hollow micro tube 1 usually has a longer distance from the sample 4, and it is usually difficult to make the two quickly approach by the electrically controlled displacement table 3, so the manual adjustment table 7 is introduced in this embodiment to increase the movement speed of the sample on the macro scale, for example, in this embodiment, the manual adjustment table 7 may be a manual displacement table, the manual displacement table may be provided with a first rack sliding along a first direction on a base platform in a sliding manner, and the first rack is driven by a manually controlled first gear to move, and the electrically controlled displacement table 3 only needs to be fixedly installed on the first rack, so that the one-dimensional manual adjustment table 7 can be formed; by analogy, if a second base station is arranged on the rack, a second rack sliding along a second direction is arranged on the second base station in a sliding manner, a manually controlled second gear drives the second rack to move, and the electric control displacement table 3 only needs to be fixedly arranged on the second rack, so that the two-dimensional manual adjusting table 7 can be formed; similarly, the manual adjustment stage 7 may further have a third rack sliding in a third direction and a third gear controlling the third rack, so as to form the three-dimensional manual adjustment stage 7, wherein the first direction, the second direction and the third direction form a rectangular spatial coordinate system.
While the above description has explained that the position of the specimen 4 is adjusted in three spatial dimensions by the manual adjustment stage 7, in another embodiment, the manual adjustment stage 7 may also have a function of adjusting an angle, such as a tilt adjustment stage, a manual deflection stage, or a combination of a three-dimensional adjustment stage and a tilt adjustment stage.
The device also comprises a voltage source 5, wherein the voltage source 5 is used for connecting the plating solution in the hollow microtube 1 and the sample 4 into an electric loop through a lead; the voltage source 5 is a voltage-adjustable and wave-adjustable power source, and the voltage source 5 also receives control from an upper computer, such as a computer.
It will be understood that one pole of the voltage source 5, for example the positive pole, is connected to a wire, the free end of which projects into the bath 2 stored in the hollow microtube 1; and the negative electrode of the voltage source 5 is connected to the sample 4 through a wire, so that an electric circuit is formed when the plating solution 2 on the tip of the hollow microtube 1 contacts the sample 4.
The device further comprises a controller 6, wherein the controller 6 is electrically connected with the voltage source 5, and the controller 6 is used for controlling the voltage of the voltage source 5 and enabling the bias voltage value on the sample 4 to be in the common electroplating potential when the electric control displacement table 3 drives the sample 4 to move relative to the hollow microtube 1 according to a preset track. In the present embodiment, a computer program is loaded in the controller 6, and the voltage source 5 and the electrically controlled displacement stage 3 are operated in response to the computer program, and the controller 6 is typically a computer.
When the device is used, a sample 4 is fixed on an electric control displacement table 3, the sample 4 is connected to a voltage source 5 through a lead, then the plating solution 2 is filled into a hollow microtube 1, the hollow microtube 1 is usually fixed, one end of another lead is connected with the other pole of the voltage source, and the other end of the other lead extends into the plating solution 2. The manual adjustment stage 7 is operated to bring the sample 4 close to the tip of the hollow microtube 1 and bring the plating solution 2 on the tip of the hollow microtube 1 into contact with the sample 4, and it is generally preferable that a meniscus is formed at the junction of the plating solution 2 and the sample 4. Since the size of the tip of the hollow microtube 1 is not easily observed by naked eyes, the device of this embodiment further provides an ammeter 8 connected in the electric circuit to determine whether the sample 4 is in contact with the plating solution 2 by the presence or absence of the generation of the ion current, and provides a microscope to observe. Thereafter, the voltage of the voltage source 5 is adjusted by the controller 6 such that the voltage output by the voltage source 5 onto the sample 4 is generally referred to as the bias voltage value that enables deposition of all ions of the first type of metal in the bath, at which time the various ions of the first type of metal in the bath 2 begin to deposit within the meniscus as described above. And then, the controller 6 controls the electric control displacement table 3 to drive the sample 4 to move, and the ion deposition of the first type of metal is still continued in the moving process of the sample 4, so that the required three-dimensional alloy micro-nano structure is deposited on the sample 4. And it can be understood that the apparatus of the embodiment provides a hardware device for solving the corresponding problem under the concept of the solution.
On the other hand, the invention provides an embodiment of a second aspect, and a method for preparing a three-dimensional alloy micro-nano structure is performed based on the above three-dimensional alloy micro-nano structure printing apparatus based on micro-area electrochemical deposition, where the three-dimensional alloy micro-nano structure to be printed includes at least one first type metal in components, and the first type metal is suitable for electroplating, as shown in fig. 3, the method specifically includes the following steps:
wherein the concentration of ions of at least one first type metal in the plating solution is generally maintained between 0.001Mol/L and 1Mol/L, and the ions of each first type metal are configured in the form of metal salt, and the first type metal ions can be iron, copper, nickel, palladium, zinc, indium, lead, tin, titanium, chromium, gold and silver. The plating solution also comprises acid and alkali for adjusting the pH value of the solution, and the pH value adjustment can not only enhance the conductivity of the plating solution, but also improve the chemical stability of the metal salt. In another embodiment, the plating solution further comprises an additive, such as one or more of a surfactant and a buffer, and the plating solution regulates the viscosity, volatility, surface tension and wettability with the sample surface through the metal salt concentration and the additive. Or in another embodiment, the plating solution may contain both an acid and base and an additive.
the above embodiment has given specific example devices, for example, the process of approaching the sample to the tip of the hollow microtube is performed by a manual adjustment stage; the judgment of the contact of the sample surface with the plating solution is carried out by direct observation with a microscope or by detecting the occurrence of current with an ammeter.
the preset track in the step is determined by the shape of the three-dimensional alloy micro-nano structure which needs to be provided, for example, the shape is linear, and the preset track is also linear. Besides the trajectory, the sample has a limitation of moving speed, for example, too fast speed may cause deposition interruption, too slow speed may cause the tip of the hollow microtube 1 to be blocked, the specific moving speed of the sample needs to be determined according to the deposition speed of the metal ions, and the deposition speed of the metal is related to the plating voltage and the concentration of the metal ions, and the moving speed of the sample is usually between 0.01um/s and 10 um/s.
And it is understood that the sequence of step 202 and step 203 is not fixed, and in another embodiment, step 203 may be performed first and then step 202 may be performed, which does not affect the implementation of the method of the present embodiment, and usually the voltage source is turned on along with the previous step.
the deposition process in step 205 may be further subdivided and described, and may be specifically divided into a physical vapor deposition process, a chemical vapor deposition process, and a solution deposition process, where the physical vapor deposition process, the chemical vapor deposition process, and the solution deposition process all include multiple specific deposition processes, which are specifically as follows:
a physical vapor deposition process, comprising, in combination,
(1) vacuum evaporation coating
In a vacuum chamber containing a substrate 10 (gas pressure lower than 10)-2Pa), the metal material needed by the alloy is heated, atoms or molecules of the metal material are evaporated and escaped, and the metal material is deposited on the surface of the base material 10 to obtain an intermediate.
The evaporation temperature is generally in the range of 1000 ℃ and 2500 ℃, and the average speed of the evaporated ions is about 103m s-1The corresponding average kinetic energy is about 0.1-0.2 eV.
According to different evaporation sources, the vacuum evaporation coating method can be divided into the following methods: the electron beam evaporation source evaporation method is that evaporation materials are placed in a crucible and then heated by electron beams; a resistance evaporation source evaporation method, which is an evaporation source made of high melting point metal such as tungsten, molybdenum and the like, on which a material to be evaporated is placed, and evaporates the material by heating the evaporation source with electric current; a high-frequency induction evaporation source evaporation method is characterized in that a graphite or ceramic crucible filled with evaporation materials is placed in a water-cooling high-frequency spiral coil, so that the evaporation materials generate strong eddy current and hysteresis loss under the induction of a high-frequency magnetic field, and the evaporation materials are heated and gasified for evaporation; the evaporation method of laser beam evaporation source uses the high energy of high power density pulse laser and makes it pass through the prism or concave mirror to focus and heat and evaporate the material.
(2) Sputtering coating technology
Bombarding the surface of the required metal material by using particles with certain energy, so that atoms/molecules on the surface of the metal are collided off the surface and sputtered on the surface of the base material 10, thereby forming the required intermediate.
Depending on the electrode, sputter coating can be subdivided into the following categories: direct current secondary sputtering, which is to utilize glow discharge between a cathode target (metal required by alloy) and an anode substrate to generate ions to bombard a target metal material, so that the target metal material is sputtered and deposited on the substrate to form an intermediate; magnetron sputtering/balanced magnetron sputtering, under the action of electric field, electron beam flies to the substrate and collides with argon atom to ionize it to obtain Ar+With new electrons, Ar+Accelerating the metal target surface under the action of an electric field, bombarding the metal target surface to sputter the metal target surface, and depositing the metal target surface on a base material to form an intermediate; the radio frequency sputtering is to replace a direct current power supply in a direct current secondary sputtering device with a radio frequency power supply. So that it can be applied to insulating materials; reactive magnetron sputtering, which is mainly used for depositing compound films, and during conventional sputtering, certain reaction gas, such as Ar and the like, is introduced to react with the reaction gas so as to deposit a compound; pulse magnetron sputtering, which is to use rectangular wave for DC power supplyA voltage pulse power supply replaces the magnetron sputtering; the medium-frequency magnetron sputtering is to replace a direct-current power supply with an alternating-current medium-frequency power supply.
(3) Ion plating
The substrate 10 is placed in a vacuum chamber (pressure < 6.65X 10)-3Pa), introducing inert gas to increase the pressure to 1.33-1.33X 10-1Pa. A low-temperature plasma is formed between the desired metal material (evaporation source) and the base material 10 by a high-voltage power supply. After the metal material is evaporated and enters the plasma region, the metal material is accelerated by an electric field, bombards the base material 10 in a high-energy state, and is deposited to form an intermediate body after a certain thickness.
The process can be further divided into two categories: the first is Activation Reactive Evaporation (ARE), which is to introduce gas (such as oxygen, nitrogen, etc.) capable of reacting with evaporated metal into a vacuum chamber, and to make the evaporated metal react with the gas by using a specific discharge mode, so as to obtain a compound build-up layer 20 on the substrate 10; the second is cathodic arc plasma deposition (multi-arc ion plating), which utilizes arc discharge to replace molten pool to evaporate metal.
Chemical vapor deposition process
The substrate 10 is placed in a reactor having a conduit through the mouth of which a gas is introduced which chemically reacts with the substrate to deposit the desired build-up layer 20 on the surface of the substrate 10, and the other gaseous products of the reaction are discharged from an outlet which includes,
(1) thermal chemical vapor deposition
The deposition process is performed at a high temperature, using a volatile metal compound to react with the substrate 10 and deposit, thereby generating a desired high melting point metal, semiconductor, non-metal compound, etc. Further, the method can be divided into atmospheric pressure chemical vapor deposition and low pressure chemical vapor deposition according to the pressure difference of the reaction chamber.
(2) Plasma Enhanced Chemical Vapor Deposition (PECVD)
In order to avoid the decrease of the bonding force between the base material 10 and the build-up layer 20 at high temperature, the glow discharge principle is used to activate the reaction, so that the reaction at high temperature can be carried out at lower temperature, thereby obtaining the intermediate with strong bonding force between the base material 10 and the build-up layer 20.
(3) By organic metal chemical vapour deposition
The decomposition of the organometallic compound under heating conditions is utilized to achieve epitaxial growth of the compound.
Solution deposition process
A build-up layer 20 of a certain thickness is deposited on the surface of the substrate 10 by means of a chemical or electrochemical reaction or the like, forming the desired intermediate, which comprises,
(1) electroplating of
The surface of the base material 10 is plated with a build-up layer 20 of a predetermined thickness by an electrochemical reaction using the base material 10 as a cathode and a desired metal ion compound aqueous solution as an electrolyte.
Electroplating is currently available to deposit copper metal on the substrate 10. The base material 10 is used as a cathode and is immersed in electrolyte copper sulfate, and a layer of copper can be plated on the surface of the base material 10 under the electrochemical action, wherein the corresponding anode is metal with low reaction activity such as platinum and the like.
(2) Chemical plating
And (4) electroplating without a power supply. Under the catalytic condition, metal ions in the metal salt solution are subjected to reduction reaction and deposited on the surface of the substrate 10 to obtain an intermediate.
(3) Anodic oxidation
According to the principle of anodic oxidation, an oxide build-up layer is deposited on the surface of the substrate 10.
(4) Spray pyrolysis
The build-up layer 20 is deposited by pyrolysis or hydrolysis by spraying droplets of the desired metal salt solution in the form of a spray onto the substrate 10 heated to the deposition temperature.
(5) Sol-gel
The required oxide or other compounds are obtained after corresponding treatment by utilizing the hydrolytic polycondensation and the gelling process of the metal compounds.
the following two methods are commonly used in the art for high temperature heat treatment: (1) annealing process: heating the prepared intermediate to a certain temperature below the solidus temperature of the intermediate, and slowly cooling the intermediate after long-time heat preservation, thereby preparing the alloy with internal chemical components, namely the added layer 20 and the base material 10 which are partially uniformly distributed. (2) Solution treatment: the method is suitable for the alloy with the base material being solid solution and the solubility changing greatly along with the temperature. The operation needs to heat the alloy to a certain proper temperature between the solubility curve and the solid phase line, keep the temperature, and quickly cool the alloy in media such as water after a period of time, so as to obtain the required supersaturated solid solution. The applicable temperature range is about 980-1250 ℃, and the specific temperature is determined by the precipitation and dissolution rules of each alloy phase, the use requirement and the like.
In step 205, the build-up layer 20 may be a metal or a nonmetal.
In addition, different metal materials or non-metal materials are deposited on the surface of the substrate 10 by corresponding deposition processes, which is not difficult for those skilled in the art to implement, and can be obtained by known data, so that the method embodiment does not describe any combination of various situations.
It is to be understood that the time and process of the high temperature heat treatment are determined according to the specific type and size of the build-up layer and the substrate, and those skilled in the art can also obtain the parameters by querying the known data.
It should be noted that the build-up layer 20 may be attached directly to the outer surface of the substrate 10 by performing step 205 once, as is generally understood; in addition, it is also possible to deposit the substrate 10 in multiple times by performing the deposition process in multiple steps 205. That is, the build-up layer 20 includes at least two layers of structures, which are obtained by performing a plurality of deposition processes. The arrangement is such that the thickness of the build-up layer 20 can be controlled more conveniently and accurately so as to obtain the specified dimensions.
Meanwhile, the at least two-layer structure may be a single-layer structure made of the same material as is generally understood, or may be a single-layer structure made of different materials. The corresponding deposition process is different for each single layer structure composed of different materials. That is, the material of at least two layers of the build-up layer 20 is different, and each layer of the build-up layer is obtained by a deposition process adapted to the layer.
The significance of layer-by-layer manufacturing and adding is as follows:
1. for the build-up layer 20 of the multi-layer structure made of the same material, in step 206, when the build-up layer 20 needs to be completely fused with the substrate 10, the build-up layer 20 does not need to be manufactured in a layered manner, and at this time, the build-up layer 20 has only one layer structure, and the thickness thereof is usually thin, so that the complete fusion can be easily realized through the heat treatment process in step 206, as shown in fig. 4; when the added layer 20 needs to be partially fused with the substrate 10, the thickness of the added layer 20 needs to be increased, so that the intermediate can still remain part of the added layer 20 after heat treatment and is not fused into the substrate, and only part of the added layer is fused with the substrate 10 to form an alloy layer 30, as shown in fig. 5, while a thicker added layer 20 is usually difficult to obtain through one-time deposition process;
2. for the added layers 20 of the multilayer structure made of different materials, two adjacent materials in the intermediate can be alloyed, and by the arrangement, the finally obtained three-dimensional alloy micro-nano structure can have more complex and variable types and is suitable for different use environments. For example, the innermost side of the intermediate body is copper with a larger diameter, the middle of the intermediate body is thinner nickel, and the outer side of the intermediate body is thicker tungsten, after the heat treatment in the step 206, a three-dimensional alloy micro-nano structure with a copper simple substance at the innermost side, tungsten-nickel-copper alloy at the middle and tungsten at the outer side can be formed.
As is clear from the above description, the consumption of the added layer 20 and the base material 10 by the heat treatment are mutually related, and by setting the proportional relationship between the diameters and the thicknesses of the base material 10 and the added layer 20, the base material 10 and the added layer 20 can be completely alloyed after the high-temperature heat treatment without retaining the original composition, or the base material 10 or the added layer 20 alone can be consumed, thereby retaining a certain original composition; therefore, the three-dimensional alloy micro-nano structure with various types and functions can be obtained by controlling the thickness and the position of different materials in the added layer 20.
In the substrate of the above embodiment, when at least two first type metals are included, and only the kind of each first type metal in the alloy is considered, and the component proportion relationship of each first type metal is not considered, the above steps can easily realize the corresponding printing. However, in the case where the substrate to be printed contains at least two metals of the first type in a defined compositional relationship, the following steps are also required, as shown in figure 6,
that is, before the "filling the plating solution containing the ions of at least two metals of the first type into the hollow microtube" in step 201, a step of preparing the plating solution is required, specifically including,
in the step, the ion concentration proportional relation of each first type metal in the prefabricated plating solution is only consistent with the component proportional relation of at least two first type metals contained in the three-dimensional alloy micro-nano structure in order of magnitude, and certainly can be the same or similar.
it can be understood that the required three-dimensional alloy micro-nano structure can be deposited on the sample only when the proportional relation of the deposition speed of the ions of the first type of metal is the same as the component proportional relation of the first type of metal in the three-dimensional alloy micro-nano structure. The deposition rate of each metal ion is related to the ion movement rate and the ion concentration, the ion movement rate is related to the current, the current is related to the voltage, and the ion movement rate is usually fixed under the condition that the plating voltage is determined, so that if the deposition rate is required to be changed, only the ion concentration is required to be changed. The skilled person in the art can adjust the concentration of the ions of each first type of metal by only limited tests (changing the ion concentration of each first type of metal) to make the proportional relationship of the deposition speed the same as the component proportional relationship of each first type of metal in the three-dimensional alloy micro-nano structure. For example, when the deposition rate of the A ions is lower, the concentration of the A ions is increased, that is, a metal salt containing the A ions is added; when the deposition concentration of the A ions is larger, the concentration of other ions is correspondingly increased.
The invention provides a specific embodiment for preparing a three-dimensional alloy micro-nano structure (copper-tungsten nickel copper-tungsten alloy micron line) by the method, which comprises the following steps:
1. firstly, 0.1Mol/L CuSO is prepared as plating solution4And 1Mol/L H2SO4An aqueous solution; 2. the method comprises the following steps of (1) adopting a hollow microtube which is a glass microtube drawn by a commercial needle drawing instrument, wherein the outer diameter of the hollow microtube is 1mm, the inner diameter of the hollow microtube is 0.75mm, and the diameter of a tip is 2 mu m; 3. a commercial three-dimensional piezoelectric displacement platform is used as an electric control displacement platform, the displacement precision in the three-dimensional direction is 2nm, and the maximum stroke is 100 micrometers; a manual adjusting table with a Z-direction adjusting function is placed on the piezoelectric displacement table and used for roughly adjusting the distance between the hollow micro-tube and the surface of the sample; 4. the sample is a glass slide plated with a gold layer, so that the sample can conduct electricity.
According to steps 201 to 204 of the embodiment of the method, the sample is controlled to contact the tip of the hollow microtube through the manual adjusting platform, so that the plating solution is contacted with the sample; the voltage of the control voltage source is 1V, the piezoelectric displacement platform is controlled to move in the Z direction at the speed of 2um/s, the direct printing of the copper simple substance microwire in the vertical direction is realized, and the copper microwire structure with the diameter of 2um is prepared. Then a nickel metal thin layer with the thickness of 0.1um is plated on the surface of the copper micron wire in a chemical plating mode, and a tungsten metal layer with the thickness of 1um is plated on the surface of the nickel metal in a CVD (chemical vapor deposition) mode. After annealing at the high temperature of 1000 ℃, nickel, partial copper and partial tungsten are consumed and a tungsten-nickel-copper alloy layer is formed, and because the nickel component is less, the copper microwire and the tungsten outer layer still exist, so that a three-dimensional alloy micro-nano structure with the center being pure copper, the outer part being tungsten metal and the middle being tungsten-nickel-copper alloy is formed.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (6)
1. Three-dimensional alloy micro-nano structure printing device based on micro-area electrochemical deposition is characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
the micro-tube plating device comprises a hollow micro-tube, a plating solution and a plating solution, wherein the hollow micro-tube is used for filling the plating solution, the plating solution contains at least one first type metal ion, and the first type metal is suitable for electroplating;
the electric control displacement platform is used for bearing a conductive sample and driving the sample to move according to a preset track;
the voltage source is used for connecting the plating solution in the hollow microtube and the sample into an electric loop through a lead;
and the controller is electrically connected with the voltage source and the electric control displacement table, and is used for controlling the voltage source and enabling the bias voltage value on the sample to be within a voltage range enabling the ions of the at least one first type of metal to be deposited when the electric control displacement table is controlled to move relative to the hollow microtube according to a preset track.
2. The three-dimensional alloy micro-nano structure printing device based on micro-area electrochemical deposition according to claim 1, characterized in that: the electric control displacement platform is fixedly installed on the electric control displacement platform.
3. A preparation method of a three-dimensional alloy micro-nano structure is characterized by comprising the following steps: the method is based on the printing device of any one of claims 1-2, the three-dimensional alloy micro-nano structure comprises at least one first type of metal on the component, the first type of metal is suitable for electroplating, the method comprises,
filling a plating solution comprising ions of at least one of the first type of metal into the hollow microtubes;
the sample is close to the tip of the hollow microtube until the surface of the sample is contacted with the plating solution;
controlling the voltage source by a controller to bring the bias voltage value on the sample within a voltage range enabling deposition of ions of the at least one first type of metal;
the electric control displacement table is controlled by a controller to drive the sample to move relative to the hollow microtube according to a preset track, so that a base material is obtained on the surface of the sample;
depositing a build-up layer on the surface of the base material through a deposition process to obtain an intermediate;
carrying out high-temperature heat treatment on the intermediate to enable part or all of the added layer to be fused with the base material, so that a three-dimensional alloy micro-nano structure is obtained;
wherein the build-up layer is metallic or non-metallic.
4. The preparation method of the three-dimensional alloy micro-nano structure according to claim 3, which is characterized by comprising the following steps: when the three-dimensional alloy micro-nano structure comprises at least two first type metals, before filling a plating solution containing ions of the at least two first type metals into the hollow micro-tube, the method also comprises a plating solution configuration step,
determining an electroplating voltage according to the types of the at least two first type metals contained in the three-dimensional alloy micro-nano structure and the Nernst equation, wherein the electroplating voltage is a bias voltage value on the test sample;
according to the component proportion relation of the at least two first type metals contained in the three-dimensional alloy micro-nano structure, prefabricating a plating solution containing ions of the at least two first type metals;
and regulating the concentration of each first type of metal ion in the plating solution to ensure that the proportional relation of the deposition speed of each first type of metal ion in the plating solution under the plating voltage is the same as the component proportional relation of each first type of metal in the three-dimensional alloy micro-nano structure.
5. The preparation method of the three-dimensional alloy micro-nano structure according to claim 3, which is characterized by comprising the following steps: the build-up layer comprises at least two layers of structures obtained by performing the deposition process a plurality of times.
6. The preparation method of the three-dimensional alloy micro-nano structure according to claim 5, which is characterized by comprising the following steps: the at least two layers of structures are made of different materials, and each layer of structure is obtained through a deposition process matched with the structure.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887478A (en) * | 2011-07-20 | 2013-01-23 | 厦门大学 | Micro-nano machining method based on electrochemical micro-nano system for functional material and device thereof |
| CN105189826A (en) * | 2013-03-15 | 2015-12-23 | 莫杜美拓有限公司 | Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes |
| CN106757234A (en) * | 2016-11-10 | 2017-05-31 | 西安电子科技大学 | The preparation method of 3D nano porous metal materials |
| CN107414221A (en) * | 2017-04-14 | 2017-12-01 | 哈尔滨工业大学 | A kind of three-dimensional micro-nano structure electrochemistry induces processing method |
| CN109913930A (en) * | 2019-03-03 | 2019-06-21 | 吉林大学 | Array compound field electrochemical metal micro/nano-scale increasing material manufacturing device and method |
| CN110565130A (en) * | 2019-09-11 | 2019-12-13 | 张家港博发纳米材料科技有限公司 | Laser-enhanced three-dimensional micro-area electrodeposition method and corresponding device |
| CN111088518A (en) * | 2020-01-09 | 2020-05-01 | 橙河微系统科技(上海)有限公司 | Closed-loop control system for three-dimensional micro-area electrochemical deposition |
-
2020
- 2020-07-21 CN CN202010706557.2A patent/CN111809205A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887478A (en) * | 2011-07-20 | 2013-01-23 | 厦门大学 | Micro-nano machining method based on electrochemical micro-nano system for functional material and device thereof |
| CN105189826A (en) * | 2013-03-15 | 2015-12-23 | 莫杜美拓有限公司 | Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes |
| CN110273167A (en) * | 2013-03-15 | 2019-09-24 | 莫杜美拓有限公司 | Pass through the composition and nanometer layer pressing gold of the electro-deposition of the product of addition manufacturing process preparation |
| CN106757234A (en) * | 2016-11-10 | 2017-05-31 | 西安电子科技大学 | The preparation method of 3D nano porous metal materials |
| CN107414221A (en) * | 2017-04-14 | 2017-12-01 | 哈尔滨工业大学 | A kind of three-dimensional micro-nano structure electrochemistry induces processing method |
| CN109913930A (en) * | 2019-03-03 | 2019-06-21 | 吉林大学 | Array compound field electrochemical metal micro/nano-scale increasing material manufacturing device and method |
| CN110565130A (en) * | 2019-09-11 | 2019-12-13 | 张家港博发纳米材料科技有限公司 | Laser-enhanced three-dimensional micro-area electrodeposition method and corresponding device |
| CN111088518A (en) * | 2020-01-09 | 2020-05-01 | 橙河微系统科技(上海)有限公司 | Closed-loop control system for three-dimensional micro-area electrochemical deposition |
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