阅读说明：本技术 一种全自动喷雾式制备薄膜的装置 (Full-automatic spray type device for preparing film ) 是由 谷志刚 田一博 康遥 张健 于 2019-03-18 设计创作，主要内容包括：本发明提供一种全自动喷雾式制备薄膜的装置,所述装置是利用全自动交替喷雾液相外延法在基底表面制备薄膜的装置,包括：供气系统,气体调节系统,压力容器,数控系统,雾化喷头,基底支撑架,外部箱体。所述装置可以根据需求对控制系统设置相应参数,能够准确、均匀地喷洒不同原料来覆盖基底,并可调控每种原料与基底接触反应时间,从而有效地制备形貌优异、取向一致的薄膜,特别是层层自组装薄膜材料,具有全自动、精度高、省人力等优点,尤其适合大面积、多层重复、成分复杂的金属-有机框架(MOFs)薄膜制备。(The invention provides a full-automatic spray type device for preparing a film, which is a device for preparing the film on the surface of a substrate by using a full-automatic alternative spray liquid phase epitaxy method and comprises the following steps: the device comprises a gas supply system, a gas regulating system, a pressure container, a numerical control system, an atomizing spray head, a substrate support frame and an external box body. The device can set corresponding parameters for a control system according to requirements, can accurately and uniformly spray different raw materials to cover the substrate, and can regulate and control the contact reaction time of each raw material and the substrate, so that the thin film with excellent appearance and consistent orientation can be effectively prepared, particularly, the thin film material is self-assembled layer by layer, the device has the advantages of full automation, high precision, labor saving and the like, and is particularly suitable for preparing the metal-organic framework (MOFs) thin film with large area, multiple layers of repetition and complex components.)

1. A full-automatic spray type device for preparing a film is a device for preparing the film on the surface of a substrate by utilizing a full-automatic alternative spray liquid phase epitaxy method;

the device comprises: the device comprises a gas supply system, a gas regulating system, a pressure container, a numerical control system, an atomizing spray head, a substrate support frame and an external box body;

the air supply system is used as main power and is used for providing air pressure required in the spraying process;

the gas regulating system is used for regulating and controlling the gas flow flux of each part;

the numerical control system is arranged between the gas regulating system and the atomizing spray head and used for receiving a pre-programmed instruction signal and controlling the atomizing spray head to work through the pre-programmed instruction signal;

the pressure containers are used for containing reaction raw materials, the gas supply system provides pressure, and the gas regulating system regulates the pressure in each container;

the atomizing nozzles correspond to the pressure containers one by one and are used for generating uniform spraying;

the substrate support frame is used for supporting the substrate;

the external box body is used as a sealing device, so that the influence of external conditions on the growth process of the film is prevented, and the environment is prevented from being polluted by atomized raw materials.

2. The apparatus according to claim 1, wherein the gas species provided by the gas supply system is an inert gas, such as nitrogen, argon, helium;

preferably, the pressure generated when the air supply system supplies air is not lower than 0.15 MPa.

3. The device according to claim 1 or 2, wherein the gas regulating system consists of 3-10 regulating valves, including a main valve, a pressure vessel valve and a spray head pressure valve, wherein the pressure vessel valve is used for pressurizing raw materials, and the spray head pressure valve is regulated by the numerical control system to be opened and closed and used for delivering power to the atomizing spray head to generate spray;

preferably, the regulating valve comprises a pressure display part and a gas flow adjusting part;

preferably, the gas flow rate is adjusted in a rotary or press type manner.

4. The apparatus according to any one of claims 1 to 3, wherein the pressure vessel is subjected to a pressure of from 0.1MPa to 5 MPa;

preferably, the pressure container is made of polytetrafluoroethylene and stainless steel;

preferably, the reaction starting materials are solutions.

5. The device according to any one of claims 1 to 4, wherein the atomizer is an automatically controllable atomizer, preferably a two-fluid atomizer, a three-fluid atomizer, more preferably a three-fluid atomizer;

preferably, the working pressure of the atomizing spray head is not lower than 0.1 MPa;

preferably, the angle between the spray outlet of the atomizing nozzle and the substrate is 30-90 degrees, and the distance is 5-50 cm.

6. The device according to any one of claims 1 to 5, wherein the shape of the substrate is any one of a rectangle, a square and a circle; the substrate is made of any one of metal, silicon, glass, mica, glass, quartz glass, metal foam and high polymer materials; the size of the substrate is 30 x 30cm²The content of the compound is less than the content of the compound;

preferably, the substrate is a modified substrate;

preferably, the modification is an organic group modification.

7. The device according to any one of claims 1 to 6, wherein the numerical control system consists of a microcomputer and an electronic valve, and the opening and closing of each atomizing nozzle, the spraying duration and the cycle number can be controlled by controlling the opening and closing of the electronic valve according to a set program;

the microcomputer adopts a programmable controller, stores instructions for executing logical operation, sequence control, timing, counting and arithmetic operation in the microcomputer, and controls the opening and closing of the electronic valve through digital and analog input and output;

the outer box body is made of metal and/or plastic; the shell is preferably made of transparent plastic materials and metal materials, wherein one side of the shell is made of metal, and the other side of the shell is made of transparent plastic;

preferably, the outer box body is provided with a box door, and the type of the box door is a push-pull type or an opening-closing type.

8. A method for preparing a thin film based on the full-automatic spray type apparatus for preparing a thin film according to any one of claims 1 to 7, comprising the steps of:

1) sequentially placing the reaction raw materials in the pressure container;

2) fixing the substrate on the substrate support frame, connecting the gas supply system, and adjusting the appropriate gas pressure;

3) and controlling the spraying sequence and the spraying time of the atomizing nozzle through the numerical control system to prepare the film.

9. A method for preparing a layer-by-layer self-assembled film based on the fully automatic spray type apparatus for preparing a film according to any one of claims 1 to 7, comprising the steps of:

1) sequentially placing the reaction raw materials in the pressure container;

2) fixing the substrate on the substrate support frame, connecting the gas supply system, and adjusting the appropriate gas pressure;

3) controlling the spraying sequence and the spraying time of the atomizing nozzle through the numerical control system to prepare a film;

4) and 3) circularly performing the step 3) to obtain the layer-by-layer self-assembled film.

10. The method according to claim 9, characterized in that it comprises the steps of:

1) preparing a metal salt solution, an organic ligand solution and a pure solvent, and sequentially placing the metal salt solution, the organic ligand solution and the pure solvent in different pressure containers;

2) fixing the substrate on a substrate support frame, connecting a gas supply system, and adjusting appropriate gas pressure;

3) controlling the spraying sequence and the spraying time of the atomizing nozzles corresponding to the metal salt solution, the organic ligand solution and the pure solvent respectively through the numerical control system to prepare a film;

4) and 3) circularly performing the step 3) to obtain the layer-by-layer self-assembled metal organic framework film.

Technical Field

The invention belongs to the technical field of full-automatic film manufacturing, and particularly relates to a full-automatic spray type film preparation device.

Background

The film material is widely applied to the fields of sensors, devices and the like due to the good performance and applicability of the film material. Particularly, the film material assembled layer by layer has good surface appearance and controllable film thickness, so the film material has better application prospect in the fields of electricity, optics, catalysis and protection. However, how to efficiently prepare a layer-by-layer film with excellent quality still remains a great challenge. At present, the methods for preparing the film are mainly divided into two methods: spin coating and hand dipping. The two methods have more defects, such as the spin coating method cannot control the thickness of the film well, the manual soaking method cannot obtain good appearance under the influence of the edge tension of the substrate, the two methods are time-consuming and labor-consuming, the preparation time is difficult to control accurately, the repeatability of the prepared film is poor, and the large-scale preparation cannot be realized. Therefore, a device for preparing the film in a full-automatic spraying manner is needed, the film with good appearance and controllable thickness is prepared while the error is reduced by replacing manual work to carry out standardized operation, and a foundation is laid for further popularizing the application of the film material.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a full-automatic spray type device for preparing a thin film, which is a device for preparing the thin film on the surface of a substrate by using a full-automatic alternative spray liquid phase epitaxy method.

According to the invention, the device comprises: the device comprises a gas supply system, a gas regulating system, a pressure container, a numerical control system, an atomizing spray head, a substrate support frame and an external box body;

the air supply system is used as main power and is used for providing air pressure required in the spraying process;

the gas regulating system is used for regulating and controlling the gas flow flux of each part;

the numerical control system is arranged between the gas regulating system and the atomizing spray head and used for receiving a pre-programmed instruction signal and controlling the atomizing spray head to work through the pre-programmed instruction signal;

the pressure containers are used for containing reaction raw materials, the gas supply system provides pressure, and the gas regulating system regulates the pressure in each container;

the atomizing nozzles correspond to the pressure containers one by one and are used for generating uniform spraying;

the substrate support frame is used for supporting the substrate;

the external box body is used as a sealing device, so that the influence of external conditions on the growth process of the film is prevented, and the environment is prevented from being polluted by atomized raw materials.

According to the embodiment of the present invention, the gas species provided by the gas supply system may be an inert gas, such as nitrogen, argon, helium.

According to the embodiment of the invention, the pressure generated when the air supply system supplies air is not lower than 0.15 MPa.

According to the embodiment of the invention, the air supply pipeline of the air supply system can select the hose or the hard pipe with the corresponding diameter according to the size of the air flow.

According to the embodiment of the invention, the gas regulating system consists of 3-10 regulating valves and comprises a main valve, a pressure container valve and a spray head pressure valve, wherein the pressure container valve is used for pressurizing raw materials, and the spray head pressure valve is regulated by the numerical control system to be opened and closed and is used for conveying power to the atomizing spray head to generate spray.

According to the embodiment of the invention, the regulating valve comprises a pressure display part and a gas flow adjusting part, and the gas flow adjusting mode can be a rotary type or a pressing type.

According to an exemplary embodiment of the invention, the regulating valve comprises a gas flow meter, a rotary regulator.

According to the embodiment of the invention, the pressure container is a container with certain structural strength and bears the pressure of 0.1-5 MPa; the material of the pressure vessel should be selected from materials which have no influence on the internal reaction raw materials, such as polytetrafluoroethylene, stainless steel and the like; the size of the pressure container can be adjusted according to the needs, for example, the pressure container can be a conventional container in a laboratory, and also can be a large-capacity container adopted by industrial amplification production; the number of the pressure vessels can be adjusted according to the types of the reaction raw materials; the placing position of the pressure container can be further adjusted according to the position parameters set by the control system.

According to an embodiment of the present invention, the reaction raw material is preferably a solution.

According to exemplary embodiments of the present invention, the reaction raw material may be one or more of a metal salt solution, an organic ligand solution, and a pure solvent.

According to the embodiment of the invention, the atomizing nozzle is an automatic regulating nozzle, and can be a two-fluid atomizing nozzle or a three-fluid atomizing nozzle, preferably a three-fluid atomizing nozzle; the number of the atomizing nozzles can be adjusted according to the number of the types of raw materials required for film preparation, and each raw material corresponds to one nozzle.

According to the embodiment of the invention, the working pressure of the atomizing nozzle is not lower than 0.1 MPa.

According to the embodiment of the invention, the atomizer heads are all mounted on the same support, all spray outlets are aligned to the substrate by the angle adjustment of the atomizer heads, and the angle between the spray outlets and the substrate can be 30-90 degrees.

According to an embodiment of the invention, the spray outlet to substrate distance can be controlled by adjusting the position of the holder.

According to an embodiment of the present invention, the distance between the spray outlet and the substrate may be 5 to 50 cm.

According to the embodiment of the invention, the angle and the height of the substrate support frame can be adjusted, and preferably, the angle and the height of the substrate support frame are adjusted to enable the substrate to be perpendicular to the spray sprayed by the atomizing spray head as much as possible, so that the best contact effect is obtained.

According to the embodiment of the invention, the material of the substrate support frame can be metal or plastic;

the structure of the substrate support frame can adopt a support plate or a support frame, and a clamp can be arranged or viscose glue can be used for firmly placing the substrate, so that the influence of impact force caused by spraying is reduced.

According to the embodiment of the invention, the shape, the material and the size of the substrate can be selected according to the requirements of different tests and representations, and the shape of the substrate can be rectangular, square, circular and the like; the substrate can be made of metal, silicon, glass, mica, glass, quartz glass and metal foamAny of polymer materials; the substrate may have a size of 30 x 30cm²Within.

Preferably, the substrate is a modified substrate, the modification can be organic group modification, and the organic group can be one or more of hydroxyl, carboxyl, amino, sulfydryl, pyridyl, carbinyl and imidazolyl; illustratively, the substrate is a quartz glass substrate that has been modified with hydroxyl groups.

According to the embodiment of the invention, the numerical control system consists of a microcomputer and an electronic valve, and can realize the control of the opening and closing of each atomizing nozzle, the spraying duration and the cycle number by controlling the opening and closing of the electronic valve according to a set program.

According to an embodiment of the present invention, the microcomputer employs a programmable controller (PLC), such as a memory employing a programmable program, and stores therein instructions for performing operations such as logic operation, sequence control, timing, counting, and arithmetic operation, and controls opening and closing of the electronic valve through digital and analog inputs and outputs.

According to the embodiment of the invention, the material of the outer box body can be metal and/or plastic; in order to facilitate the observation of the movement of the internal device, the shell which is made of transparent plastic material and metal material and has one side of metal and one side of transparent plastic is preferably used; the transparent plastic may be Polymethylmethacrylate (PMMA) plastic, PC, MABS, PETG, AS, PS, NAS, PVC, PET, preferably PMMA.

Preferably, the external box body can be provided with a box door, so that the placing of the substrate, the angle of the bracket and other parameters can be conveniently adjusted at any time, and the type of the box door can be a push-pull type or an open-close type.

According to an embodiment of the invention, the device may have a size of 100cm³～100m³The ratio of the length, the width and the height can be 1:1: 1; for example, 60 × 60cm (length/width/height), and the size of the apparatus can be designed according to the purpose of preparing the thin film, the size of the space for operation, and the needs of the operator.

The invention also provides a method for preparing the film, which is based on the device for preparing the film in a full-automatic spray manner; the method comprises the following steps:

1) sequentially placing reaction raw materials in a pressure container;

2) fixing the substrate on a substrate support frame, connecting a gas supply system, and adjusting appropriate gas pressure;

3) and controlling the spraying sequence and the spraying time of each atomizing nozzle through a numerical control system to prepare the film.

The invention also provides a method for preparing the layer-by-layer self-assembled film, which is based on the device for preparing the film in a full-automatic spray manner, and the method comprises the following steps:

1) sequentially placing reaction raw materials in a pressure container;

2) fixing the substrate on a substrate support frame, connecting a gas supply system, and adjusting appropriate gas pressure;

3) controlling the spraying sequence and the spraying time of each atomizing nozzle through a numerical control system to prepare a film;

4) and 3) circularly performing the step 3) to obtain the layer-by-layer self-assembled film.

In the above method, the amount of the spray is preferably such that the substrate is uniformly covered and does not flow by gravity, and the amount of the spray can be adjusted by both the flow rate of the gas and the spraying time. The gas pressure comprises the pressure of the pressure container and the atomization pressure of the atomization nozzle, the pressure of the pressure container is used for supplying the raw material solution uninterruptedly, the interruption of the flow during the atomization period is preferably avoided, and the atomization pressure of the atomization nozzle is preferably used for ensuring that the airflow impact force is small and the atomization is uniform.

According to an exemplary embodiment of the invention, the method comprises the steps of:

1) preparing a metal salt solution, an organic ligand solution and a pure solvent, and sequentially placing the metal salt solution, the organic ligand solution and the pure solvent in different pressure containers;

2) fixing the substrate on a substrate support frame, connecting a gas supply system, and adjusting appropriate gas pressure;

3) controlling the spraying sequence and the spraying time of the corresponding atomizing nozzles of the metal salt solution, the organic ligand solution and the pure solvent through a numerical control system to prepare a film;

4) and 3) circularly performing the step 3) to obtain the layer-by-layer self-assembled metal organic framework film.

The invention has the beneficial effects that:

1. the full-automatic spray type device for preparing the film can set corresponding parameters for the control system according to requirements, can accurately and uniformly spray different raw materials to cover the substrate, and can regulate and control the contact reaction time of each raw material and the substrate, thereby effectively preparing the film with excellent appearance and consistent orientation, particularly the film material which is self-assembled layer by layer.

2. The full-automatic spray type device for preparing the film can accurately control the thickness of the film by controlling the circulating spray frequency, and the quality and the preparation efficiency of the film material can be greatly improved by standardized operation. The device has the advantages of full automation, high precision, labor saving and the like, and is particularly suitable for preparing the metal-organic framework (MOFs) film with large area, multiple layers of repetition and complex components.

3. The full-automatic spray type device for preparing the film layer by layer has the advantages of both human and machine in structure and performance, the whole production process is automatically controlled, the application of an intelligent machine in the field of chemical research is particularly reflected, and the device can replace manpower to prepare the film with high quality and good repeatability in large batch. Because of the accuracy of numerical control spraying work and the capability of completing operation in various environments (especially adopting a solvent harmful to human bodies), the invention has wide development prospect in the field of film preparation.

Drawings

FIG. 1 is a schematic diagram of the structure of an apparatus according to a preferred embodiment of the present invention;

FIG. 2 is a schematic diagram of a regulating valve in the apparatus according to a preferred embodiment of the present invention;

FIG. 3 is a schematic diagram of the pressure vessel configuration of the apparatus according to a preferred embodiment of the present invention;

FIG. 4 is a schematic view of the structure of an atomizing head in the apparatus according to a preferred embodiment of the present invention;

FIG. 5 is an operation interface of a numerical control system in the apparatus according to a preferred embodiment of the present invention;

FIG. 6 is an XRD spectrum of MOF HKUST-1 film prepared in example 2;

FIG. 7 is an AFM image of the MOF HKUST-1 thin film prepared in example 2;

FIG. 8 is a schematic diagram of the operation of the apparatus of the present invention;

the reference numerals in figures 1-4 are as follows:

1-a main valve; 2-an electronic valve; 3. 4, 8, 9-nozzle pressure valve; 5-a pressure vessel; 6-switch and indicator light; 7-a numerical control system operating platform; 10-an atomizing spray head; 11-a substrate support; 12-a rotary adjuster; 13-a container top cover; 14-a feedstock outlet; 15-a spray outlet; 16-fixed screw; 17-spray flow regulating valve; 18-switching the gas flow inlet; 19-feedstock inlet; 20-atomizing gas stream inlet.

Note:

1) to ensure the structure of the drawings is clear, the connecting hose is omitted, and the specific connecting mode is explained in the following embodiment 1.

2) The solid arrows in the drawings indicate the liquid flow direction and the open arrows indicate the gas flow direction.

Detailed Description

The working principle of the invention is explained in more detail in example 1 and the process of preparing MOF HKUST-1 film by using the apparatus of the invention is illustrated in example 2 for further illustrating the advantageous effects of the invention. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.