CN113663884A - Selective deposition process based on electrostatic fluid technology - Google Patents
Selective deposition process based on electrostatic fluid technology Download PDFInfo
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- CN113663884A CN113663884A CN202110789683.3A CN202110789683A CN113663884A CN 113663884 A CN113663884 A CN 113663884A CN 202110789683 A CN202110789683 A CN 202110789683A CN 113663884 A CN113663884 A CN 113663884A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
- B05D1/045—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field on non-conductive substrates
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Abstract
The invention relates to the technical field of selective polymer particle deposition, in particular to a selective deposition process based on an electrostatic fluid technology, which comprises the following specific steps: planning a sprayed area and a blank area on an object to be sprayed, designing a negative electrode and carrying out positive charge treatment on the object to be sprayed; placing and fixing the spray head on an insulating support, connecting the spray head with liquid feeding equipment by using an insulating pipeline, and injecting the prepared coating solution into the liquid feeding equipment; starting the liquid feeding equipment, emptying air in the insulated pipeline, and closing the liquid feeding equipment when the spray head stably forms liquid drops; and placing the negative electrode on the back surface of the object to be sprayed, wherein the surface of the object to be sprayed, which is subjected to positive charge treatment, faces upwards and is placed under the spray head. The invention simplifies the processing steps of the spraying surface, reduces the damage to the surface to be sprayed, simultaneously supports multi-level spraying, and can more conveniently, quickly and accurately implement the spraying requirements of different coatings and different structures.
Description
Technical Field
The invention relates to the technical field of selective polymer particle deposition, in particular to a selective deposition process based on an electrostatic fluid technology.
Background
The electrostatic fluid technology is used as a technology for preparing micro-nano particles. At present, the method is widely applied to the fields of micro-nano structure preparation, drug slow release, surface treatment and the like.
The electrostatic fluid refers to mist (mist), fog (fog), jet flow (plume) or spray (spray) which is formed by filaments, particles, liquid drops and the like which are sprayed out of a polar solution under the action of an electrostatic field and can be guided by the electric field, and common applications such as electric atomization, electrostatic spinning and the like are listed here.
Droplets, particles or filaments formed from the electrostatic fluid typically carry a positive charge as they fly off the positive electrode, so that the negative electrode can stably receive the resulting particles in a directed orientation. The characteristic enables the polymer to have wide application prospect in selective polymer particle deposition. The directional deposition on the surface of the cathode has the advantages of safety, difficulty in generating electric arcs, more stable electric field and the like, and various processes have been developed at the present stage to enable the surface of the cathode to be selectively deposited.
The existing cathode surface selective deposition process mostly achieves the purpose of changing an electric field by methods such as a mask plate or a sputtering electrode on a substrate, and the like above the substrate, but when the surface has adhesiveness or is very easy to damage, the above methods often cause damage to the receiving substrate; if a metal hollow mask (stencil) is used to avoid contact with the surface, form and position tolerance is generated, and practical application scenes are greatly limited. In addition, when the metal hollow mask is manufactured for the annular pattern, the requirement of the pattern is difficult to achieve perfectly, because the mask part in the middle of the ring needs to be connected by about 2mm to ensure the support, as shown in fig. 6.
It was studied that CN109428506B uses a patterned electrode to shield part of the charges with different signs between the triboelectric layer and the assembly to achieve selective self-alignment, and this method can omit the application of electric field, but the design of the assembly and the patterned electrode has great limitations. The patterned electrodes are required to be distributed in a grid-like and array-like manner, so that the distribution can ensure that the electric field generated by the electrodes affects all self-assembly parts. The patented process is not suitable for use with the selective deposition of the present invention. The electrostatic fluid solvent is selectively deposited on the surface to be sprayed under the combined action of the electric field and the gravity field, the electrostatic shielding effect of the surface to be sprayed is not damaged, the negative electrode pattern can be changed, and the spraying solvent can be replaced to carry out multilayer deposition.
Through research, the technology of directly spraying a substrate to be sprayed with uneven charge distribution by using a charge neutralizing agent as a coating material, which is mentioned in patent CN1277623C, has a defect in practical implementation. The surface coating has limited charge amount, and charges can be continuously neutralized in the process of contacting with charged particles, so that the actual surface spraying effect is difficult to control. Furthermore, since the pre-pattern in patent CN1277623C was created by pre-painting the electrode neutralizer. The surface charged coating is easy to transfer and difficult to carry out complex operation, so that the feasibility is limited in the actual use process.
Disclosure of Invention
In order to solve the above technical problems, the present invention proposes a selective deposition process based on an electrostatic fluid technology. The aim is to selectively deposit the electrostatic fluid on the treated non-conductive surface under the guidance of an electric field of a special negative electrode. Compared with the traditional mask and electrode sputtering process, the selective deposition process has the advantage that other auxiliary tools are not used for directly contacting the surface in the spraying process.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a selective deposition process based on an electrostatic fluid technology comprises the following specific steps:
(A) planning a sprayed area and a blank area on an object to be sprayed, designing a negative electrode and carrying out positive charge treatment on the object to be sprayed;
(B) placing and fixing the spray head on an insulating support, connecting the spray head with liquid feeding equipment by using an insulating pipeline, and injecting the prepared coating solution into the liquid feeding equipment;
(C) starting the liquid feeding equipment, emptying air in the insulated pipeline, and closing the liquid feeding equipment when the spray head stably forms liquid drops;
(D) placing the negative electrode on the back of the object to be sprayed, wherein the surface of the object to be sprayed, which is subjected to positive charge treatment, faces upwards and is placed under the spray head;
(E) clamping the crocodile clip on a needle tube of a spray head, connecting the crocodile clip with a positive voltage power supply through a lead, and simultaneously connecting a negative electrode with a negative voltage power supply, wherein the positive voltage power supply is set to be 11KV, and the negative voltage power supply is set to be-7 KV;
(F) starting the anode and cathode power supplies to form a stable electric field, starting the liquid feeding equipment, observing a Taylor cone formed at the tail end of the spray head through an industrial camera, and spraying fine jet flow;
(G) after a period of time, the power supply and the liquid supply equipment are turned off, and the object to be sprayed with the coating solution is obtained after the object is taken down.
As a preferable mode of the present invention, the object to be sprayed in the step (A) is specifically a glass slide.
As a preferred embodiment of the present invention, the amount of charge on the slide glass in the step (A) is 2.27X 10-7C/m2。
As a preferable scheme of the invention, the coating solution in the step (B) is specifically a solution with the concentration of 50mg/ml, wherein the solvent is acetone and the solute is PLGA.
As a preferable embodiment of the present invention, the solvent of the coating solution in the step (B) may be any one of ethyl acetate, glacial acetic acid, and formaldehyde; the solute can also be any one of PLA, PCL, coumarin 6 and curcumin.
As a preferable mode of the present invention, the flow rate of the liquid feeding means in the step (C) is set to 0.2 to 2 ml/h.
As a preferable mode of the present invention, the flow rate of the liquid feeding means in the step (C) is set to 1 ml/h.
As another preferable aspect of the present invention, the object to be sprayed in step (a) is specifically an anti-sticking silica gel tape.
As another preferred embodiment of the present invention, the coating solution in step (B) is specifically prepared by using polyurethane as an auxiliary binder and erythromycin in a ratio of 1: 1 as solute to be dissolved in ethanol to prepare solution with the concentration of 50 mg/ml.
The invention has the beneficial effects that:
the invention simplifies the processing steps of the spraying surface, reduces the damage to the surface to be sprayed, simultaneously supports multi-level spraying, and can more conveniently, quickly and accurately implement the spraying requirements of different coatings and different structures. Compared with the traditional mask and electrode sputtering process, the method has the advantage that other auxiliary tools are not used for directly contacting the surface in the spraying process.
Drawings
The invention is further illustrated with reference to the following figures and examples:
FIG. 1 is a schematic diagram of the principles of the present invention;
FIG. 2 is a schematic view of a process flow of the present invention;
FIG. 3 is a schematic flow chart of the operation of the embodiment of the present invention;
FIG. 4 is a schematic illustration of nine sets of differently resistive electrodeposited particles in accordance with the present invention;
FIG. 5 is a schematic diagram showing a comparison of two different gray levels in an application of the present invention;
FIG. 6 is a schematic diagram illustrating design limitations of a metal stencil mask in the prior art.
In the figure: 1. a spray head; 2. an object to be sprayed; 3. a negative pole block; 4. atomized particles adhering to the spray area; 5. there are no atomized particles falling on the spray area, which fall outside the object to be sprayed.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further explained in the following with the accompanying drawings and the embodiments.
As shown in figures 1, 4 and 5, the selective deposition process based on the electrostatic fluid technology is characterized in that a negative electrode with a special shape is arranged on the other side of a surface to be sprayed, the surface to be sprayed is pretreated to be charged with positive charges, under the action of an electric field, gravity and liquid pushing equipment, a Taylor cone is formed at the tail end of a needle tube of a spray head 1, electrostatic fluid is sprayed out, the electrostatic fluid is deposited towards a negative electrode under the guidance of the electric field, and under the combined action of an insulating receiving substrate with the positive charges and the negative electrode with the special shape, the electrostatic fluid is guided to be deposited to form a pattern related to the special shape of the negative electrode.
The surface to be painted is desirably an insulating material as described above, and may be treated to attach and retain a certain amount of positive charge for a period of time. Only the insulating material can be stabilized by the positive charge treatment, which occurs after the transfer of charge in the case of a conductor.
The negative electrode is made of a conductive metal material such as gold, silver, copper, etc., and is patterned by machining or the like. After the insulated electrode is prepared based on 3D printing, the surface of the insulated electrode can be uniformly coated with conductive silver paste, a conductive copper foil is attached, and the insulated electrode has conductivity in a magnetron sputtering mode and the like.
As shown in FIG. 4, (9 groups of the particles deposited by the electrodes with different resistances are shown in the figure, the abscissa is the number of the electrode, the ordinate is the deposition state of the particles, the No. 1 electrode is an insulator, and the resistance is 1.28X 108Omega, 2 electrode is 6.6 x 107Omega, 3 electrode 9.9 x 107The number 4 electrode is 421 Ω, the number 5 electrode is 6167 Ω, the number 6 electrode is 55933 Ω, the number 7 electrode is 14.7 Ω, the number 8 electrode is 52.3 Ω, and the number 9 electrode is 0.5 Ω. ) The resistivity of the material from which the negative electrode is made as described above can affect the deposition of the electrostatic fluid. When the negative electrode is an insulator (resistance greater than 1 hundred million Ω), very few particles are deposited on the surface of the negative electrode. When the negative electrode is a semiconductor or a conductor, the deposited particles fluctuate with changes in resistance.
Finally, as shown in fig. 5, (in the figure, two different gray-scale comparison graphs are shown, the middle strip part of each graph is a selective deposition area, the left side is a dark color deposition sample with more deposition particles obtained by using the conductive material as the negative electrode, and the right side is a light color deposition sample with less deposition particles obtained by using the insulating material as the negative electrode), the insulating material and the conductive material are obviously distinguished in gray scale according to the selective deposition result of the electrostatic fluid obtained by using the conductive material as the negative electrode.
If gaps exist between the patterned electrodes, the patterned electrodes can be filled with some dielectric materials, and the difference of the dielectric materials can affect the distribution of an electric field to a certain extent, so that the deposition of particles is affected, and the effect of changing the gray scale of the pattern is achieved.
The length of the distance between the spray head 1 and the surface to be sprayed can influence the function of guiding the deposition electric field. When the distance is longer, the acting force of an electric field for guiding deposition is weak, particles falling on a specified position are reduced, and the gray scale of the pattern is lighter; when the distance is shorter, the acting force of an electric field for guiding deposition is strong, more electrostatic fluid can be guided to fall on a specified position, and the gray scale of the pattern is deeper.
The pretreatment is to make the surface to be sprayed carry positive charges by using a chemical and physical treatment mode and measure whether the positive charges meet the requirement, the sharpness of the pattern can be controlled by the amount of the positive charges on the surface to be sprayed, and when the positive charges on the surface to be sprayed are sufficient, the edge of the pattern is more distinct; when the surface to be painted carries an insufficient amount of positive charge, the edges of the pattern are more blurred.
The combined action of the surface electric field to be sprayed and the specially-shaped negative electrode electric field means that the attraction of the negative electrode to the static electricity fluid and the repulsion, the repulsion and the attraction of the insulating substrate processed by the positive charge to the static electricity fluid carrying the positive charge are mutually superposed, a attraction field is formed in the area where the static electricity fluid needs to be deposited, a repulsion field is formed in the area where the deposition is not needed, the repulsion field repels the static electricity fluid and the attraction field attracts the static electricity fluid, and the static electricity fluid is guided to be deposited only to the needed part together, so that the purpose of selective deposition is achieved.
In the using process, the positive charge processing layer is not actually contacted with the negative electrode, so that the charges are not transferred after one-time deposition. Thus, multiple spraying is thereby accomplished without the need for redundant steps.
The minimum line width of the process is 0.8 +/-0.05 mm.
The first embodiment is as follows: spraying a grid pattern on the glass slide; the method comprises the following specific steps:
planning a sprayed area and a blank area according to a pattern needing to be sprayed on the glass slide, and designing a negative electrode, wherein a grid type negative electrode is used in the embodiment.
And (II) placing the spray head 1 on an insulating support to be fixed, wherein the distance between the spray head 1 and the surface to be sprayed on the glass slide is 20cm-100 cm.
Specifically, too short distance can make the liquid drop can't volatilize totally and can't produce the particle, and too long distance can make the relative electric field effect weaken, can't effectively guide particle deposit, and the shower nozzle 1 is 80cm with the surperficial distance of waiting to spray on the slide in this example one.
And (III) connecting the insulated pipeline with liquid feeding equipment, wherein the flow rate of the liquid feeding equipment is set to be 0.2-2 ml/h.
Specifically, the flow rate set in the experiment is 1ml/h, when the flow rate is too low, a stable Taylor cone cannot be formed, so that the release of the particles is influenced, and when the flow rate is too high, the spraying solvent forms large liquid drops at the needle head, so that the micro liquid drops cannot be generated.
In order to facilitate observation of phenomena, the positive charge microscope slide glass treated by the positive charge treatment process is used as an object to be sprayed, and the surface charge quantity of the glass sheet is measured to be 2.27 multiplied by 10 < -7 > C/m2。
And (V) injecting the prepared coating into liquid feeding equipment, wherein in the embodiment, the solution with the concentration of 50mg/ml is prepared by PLGA as acetone solute, so that the observation and the spraying are convenient.
Specifically, the solvent can also be selected from organic solvents such as ethyl acetate, glacial acetic acid, formaldehyde and the like, the solute can also be selected from high polymer materials such as PLA, PCL and the like or oil-soluble substances such as coumarin 6, curcumin and the like, the concentration of the solution is controlled to be 1-50 mg/ml, and the concentration of the solution can be changed within a range according to different conditions.
And (VI) starting the liquid feeding equipment, emptying air in the insulated pipeline, and closing the liquid feeding equipment when the spray head 1 stably forms liquid drops.
And (seventhly) placing the negative electrode on the back surface of the glass slide to be sprayed, wherein the front surface which is subjected to positive charge adhesion treatment faces upwards, and the negative electrode is placed under the spray head 1.
And (eight), clamping the crocodile clip on the needle tube of the spray head 1, connecting the crocodile clip with a positive-pressure power supply through a lead, and simultaneously connecting a negative electrode with a negative-pressure power supply, wherein the positive-pressure power supply is set to be 11KV, and the negative-pressure power supply is set to be-7 KV.
And (nine) starting a positive electrode power supply and a negative electrode power supply, starting the liquid feeding equipment after a stable electric field is formed, observing a Taylor cone formed at the tail end of the spray head 1 through an industrial camera, and spraying fine jet flow.
After 2min from step (ten), it can be observed that a pattern coinciding with the negative electrode is formed on the glass slide, and after 40min, the particle deposition amount reaches 10mg and does not increase, indicating that the maximum deposition amount has been reached, because the surface potential of the receiving substrate at this time is no longer selective because the neutralization of the charged particles has been kept consistent, and only the positive charge attached to the receiving substrate plays a shielding role, the charged particles are no longer deposited. And turning off the power supply and the liquid feeding equipment, and taking down the glass slide to obtain the glass slide after spraying, and forming a pattern which is superposed with the shape of the negative electrode on the sprayed surface of the glass slide.
Example two: spraying an anti-sticking silica gel tape, and spraying granular medicine on the anti-sticking silica gel tape. Fig. 3 is a simplified schematic diagram of the present embodiment. In the figure: the bandage is characterized in that firstly, the bandage is not attached with medicine, secondly, the blended erythromycin is sprayed on the bandage according to the shape of a wound by utilizing the electric atomization spraying mode of the invention, thirdly, the bandage is attached with medicine, fourthly, the bandage is attached to the wound of a patient by utilizing the bandage attached with medicine, and fifthly, the bandage is taken down, and the medicine is found to be attached to the wound of the leg of the patient. The method comprises the following specific steps:
and (a) planning a region needing medicine administration on the anti-sticking silica gel tape, and designing a corresponding negative electrode.
And (b) placing the spray head 1 on an insulating support to be fixed, and connecting the spray head with liquid feeding equipment by using an insulating pipeline.
And (c) carrying out positive charge treatment on the anti-sticking silica gel tape.
Step (d) using polyurethane as a co-binder with erythromycin in a ratio of 1: 1 as solute dissolved in ethanol to prepare solution with concentration of 50mg/ml, and injecting the solution into liquid feeding equipment.
Step (e) starting the liquid supply equipment, evacuating air in the insulated pipeline, and closing the liquid supply equipment when the spray head 1 stably forms liquid drops
And (f) placing the negative electrode on the back surface of the anti-sticking silica gel tape, wherein the adhesion surface subjected to positive charge adhesion treatment is upward and is placed under the spray head.
And (g) clamping the crocodile clip on a nozzle needle tube, connecting the crocodile clip with a positive voltage power supply through a lead, and simultaneously connecting a negative electrode with a negative voltage power supply, wherein the positive voltage power supply is set to be 11KV, and the negative voltage power supply is set to be-7 KV.
And (h) starting a power supply, starting the liquid feeding equipment after a stable electric field is formed, observing a Taylor cone formed at the tail end of the spray head through an industrial camera, and spraying fine jet flow.
And (i) after a period of time, turning off the power supply, taking down the anti-sticking silica gel tape, and placing the anti-sticking silica gel tape at the wound of the patient.
Specifically, because the drug particles and the anti-sticking silica gel tape are positively charged and have mutually repulsive coulomb force, when the anti-sticking silica gel tape is attached to the affected part of a patient, the drug is more easily dropped from the anti-sticking silica gel tape and is attached to the wound of the patient.
And (j) taking down the anti-sticking silica gel tape, and finding out that the erythromycin particles are adhered to the wound of the patient by the medicine adhered to the wound of the patient.
The invention simplifies the processing steps of the spraying surface, reduces the damage to the surface to be sprayed, simultaneously supports multi-level spraying, and can more conveniently, quickly and accurately implement the spraying requirements of different coatings and different structures. Compared with the traditional mask and electrode sputtering process, the method has the advantage that other auxiliary tools are not used for directly contacting the surface in the spraying process.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A selective deposition process based on electrostatic fluid technology, characterized by: the method comprises the following specific steps:
(A) planning a sprayed area and a blank area on an object (2) to be sprayed, designing a negative electrode and carrying out positive charge treatment on the object (2) to be sprayed;
(B) the spray head (1) is arranged on an insulating bracket to be fixed, an insulating pipeline is connected with liquid feeding equipment, and the prepared coating solution is injected into the liquid feeding equipment;
(C) starting the liquid feeding equipment, emptying air in the insulated pipeline, and closing the liquid feeding equipment when the spray head (1) stably forms liquid drops;
(D) placing a negative electrode on the back surface of the object (2) to be sprayed, wherein the surface of the object (2) to be sprayed, which is subjected to positive charge treatment, faces upwards and is placed under the spray head (1);
(E) clamping the crocodile clip on a needle tube of the spray head (1), connecting the crocodile clip with a positive voltage power supply through a lead, and simultaneously connecting a negative electrode with a negative voltage power supply, wherein the positive voltage power supply is set to be 11KV, and the negative voltage power supply is set to be-7 KV;
(F) starting the anode and cathode power supplies, starting the liquid feeding equipment after a stable electric field is formed, observing a Taylor cone formed at the tail end of the spray head (1) through an industrial camera, and spraying fine jet flow;
(G) after a period of time, the power supply and the liquid supply equipment are turned off, and the object (2) to be sprayed with the coating solution is obtained after being taken down.
2. A selective deposition process based on electrostatic fluid technology according to claim 1, characterized in that: the object (2) to be sprayed in the step (A) is specifically a glass slide.
3. A selective deposition process based on electrostatic fluid technology according to claim 2, characterized in that: the amount of charge on the slide glass in the step (A) was 2.27X 10-7C/m2。
4. A selective deposition process based on electrostatic fluid technology according to claim 2, characterized in that: the coating solution in the step (B) is a solution with the concentration of 50mg/ml, and the solvent is acetone and the solute is PLGA.
5. A selective deposition process based on electrostatic fluid technology, according to claim 4, characterized in that: the solvent of the coating solution in the step (B) can be any one of ethyl acetate, glacial acetic acid and formaldehyde; the solute can also be any one of PLA, PCL, coumarin 6 and curcumin.
6. A selective deposition process based on electrostatic fluid technology according to claim 2, characterized in that: the flow rate of the liquid feeding equipment in the step (C) is set to be 0.2-2 ml/h.
7. A selective deposition process based on electrostatic fluid technology according to claim 6, characterized in that: the flow rate of the liquid feeding means in the step (C) was specifically set at 1 ml/h.
8. A selective deposition process based on electrostatic fluid technology according to claim 1, characterized in that: the object (2) to be sprayed in the step (A) is specifically an anti-sticking silica gel tape.
9. A selective deposition process based on electrostatic fluid technology according to claim 8, characterized in that: the coating solution in step (B) is specifically prepared by using polyurethane as an auxiliary binder with erythromycin in a ratio of 1: 1 as solute to be dissolved in ethanol to prepare solution with the concentration of 50 mg/ml.
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Citations (1)
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| US20040050701A1 (en) * | 2002-09-13 | 2004-03-18 | Mcentee John Francis | Electrostatically guiding ionized droplets in chemical array fabrication |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040050701A1 (en) * | 2002-09-13 | 2004-03-18 | Mcentee John Francis | Electrostatically guiding ionized droplets in chemical array fabrication |
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