CN113059808B - Method for selectively processing 3D printing model by functionalized digital light - Google Patents
Method for selectively processing 3D printing model by functionalized digital light Download PDFInfo
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- CN113059808B CN113059808B CN202110390306.2A CN202110390306A CN113059808B CN 113059808 B CN113059808 B CN 113059808B CN 202110390306 A CN202110390306 A CN 202110390306A CN 113059808 B CN113059808 B CN 113059808B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/379—Handling of additively manufactured objects, e.g. using robots
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
Abstract
The invention provides a method for selectively functionalizing a digital light processing 3D printing model, which comprises the following steps: preparing a neutral photosensitive resin containing a photocurable monomer (a); preparing a positively charged group-carrying photosensitive resin containing a cationic monomer, a diluent and a photocurable monomer (B); introducing a model to be printed into a digital light processing 3D printer, and respectively printing and curing by using neutral photosensitive resin and photosensitive resin with positive charge groups according to the design of the model to obtain the model; cleaning the obtained model, and removing uncured monomers; dispersing a functional material in a solution containing an anionic surfactant to obtain a negatively charged functional material dispersion liquid; the mold was immersed in the functional material dispersion liquid and taken out after a predetermined period of time. The method has the characteristics of simplicity, convenience, high efficiency and low cost, and has wide application prospect in the preparation of 3D printing electronic devices.
Description
Technical Field
The invention belongs to the technical field of additive manufacturing, and particularly relates to a method for selectively processing a 3D printing model by functionalized digital light based on electrostatic adsorption.
Background
Additive manufacturing (also known as 3D printing) refers to a set of techniques for manufacturing three-dimensional objects in a layer-by-layer manner directly from a Computer Aided Design (CAD) model, and almost any arbitrary complex object can be produced in a simple and cost-effective manner. Many 3D printing technologies such as Fused Deposition (FDM), Selective Laser Melting (SLM), Stereolithography (SLA), Digital Light Processing (DLP) have been developed today, and these technologies have significant applications in the fields of metal parts, aerospace, biomedical engineering, sensors, and microelectronics. The basic principle of the digital light processing 3D printing technology is that a digital light source projects layer by layer on the surface of liquid photosensitive resin in a surface light mode, and the layer is solidified and molded layer by layer. DLP-3D printing has its unique advantages over other types of 3D printing technologies: the light beam is not moved, the vibration deviation is little, no movable spray head is arranged, the problem of material blockage is completely avoided, no heating part is arranged, the electrical safety is improved, the printing preparation time is short, the energy is saved, the first consumable addition is far less than other equipment, and the user cost is saved.
For 3D printing of electronic equipment, the step of functionalization is indispensable, and for the functionalization of digital light processing 3D printing model, two routes can be mainly divided: firstly, functional materials are mixed into resin raw materials to directly print a model, but the defects of uneven dispersion and poor printing quality exist; secondly, the active layer is prepared after the model is printed by using the raw materials, the operation is complex, the cost is high, and the selective functionalization cannot be carried out.
Therefore, there is a need for a simple, efficient, and cost effective method of selectively functionalizing digital light processing 3D printed models.
Disclosure of Invention
The invention is made to solve the problems existing in the prior art, and aims to provide a simple and efficient digital light processing 3D printing model selective functionalization method based on electrostatic adsorption with low cost.
In order to achieve the above object, the inventor prepares neutral photosensitive resin and photosensitive resin with positive charge groups, and respectively loads the neutral photosensitive resin and the photosensitive resin with positive charge groups into a material box of a digital light processing 3D printer, introduces a model drawn by three-dimensional drawing software into the digital light processing 3D printer, prints the model by using the two photosensitive resins through the digital light processing 3D printer, then disperses a functional material by using an anionic dispersant to obtain a negatively charged functional material dispersion liquid, and finally immerses the obtained model into the dispersion liquid to combine the functional material to a part of the model, which is formed by curing the photosensitive resin with positive charge groups, through electrostatic adsorption (adsorption of positive and negative charges), so that the digital light processing 3D printing model can be functionalized simply, conveniently and efficiently, thereby completing the invention.
The method for selectively processing the 3D printing model by the functionalized digital light comprises the following steps:
preparing a neutral photosensitive resin containing a photocurable monomer (a);
preparing a positively charged group-carrying photosensitive resin containing a cationic monomer, a diluent and a photocurable monomer (B);
introducing a model to be printed into a digital light processing 3D printer, and respectively printing and curing by using the neutral photosensitive resin and the photosensitive resin with the positive charge groups according to the design of the model to obtain the model;
cleaning the obtained model, and removing uncured monomers;
dispersing a functional material in a solution containing an anionic surfactant to obtain a negatively charged functional material dispersion liquid;
the mold is immersed in the functional material dispersion liquid, and taken out after a predetermined time.
In some preferred embodiments, the photocurable monomer (a) is at least one selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, and trimethylolpropane triacrylate. For flexible devices, the photocurable monomer (a) is more preferably an aliphatic monofunctional acrylate such as EBECRYL 113, EBECRYL 114.
In some preferred embodiments, the cationic monomer is at least one selected from the group consisting of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloylpropyl trimethyl ammonium chloride, acryloylpropyltrimethyl ammonium chloride, methacryloyloxyethyl benzyl dimethyl ammonium chloride, and acryloyloxyethyl benzyl dimethyl ammonium chloride.
In some preferred embodiments, the diluent is at least one selected from the group consisting of diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, and tri (ethylene glycol) divinyl ether.
In some preferred embodiments, the photocurable monomer (B) is any one selected from the group consisting of bisphenol a glycerol dimethacrylate, bisphenol a glycerol diacrylate, ethoxylated bisphenol a diacrylate, propoxylated ethoxylated bisphenol a diacrylate, ethoxylated bisphenol a dimethacrylate.
In some preferred embodiments, the neutral photosensitive resin and the photosensitive resin having a positively charged group further include a photoinitiator, and the photoinitiator is at least one selected from the group consisting of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and benzoin anisole.
In some preferred embodiments, the anionic surfactant is at least one of sodium lauryl sulfate, and sodium cetyl sulfate.
In some preferred embodiments, the functional material is any one of carbon nanotubes, graphene, silver nanowires, and copper nanowires.
In some preferred embodiments, when the digital light processing 3D printer is used for printing, the exposure parameter is set to be 7-10.
In some preferred embodiments, the mold is immersed in the functional material dispersion for 10 to 30 minutes.
In some preferred embodiments, the mold is cleaned using a cleaning agent, preferably at least one selected from the group consisting of ethanol, propanol, and acetone.
In some preferred embodiments, after the mold is removed from the functional material dispersion, it is washed with deionized water.
Effects of the invention
According to the invention, the prepared neutral photosensitive resin and the photosensitive resin with the positive charge groups are cured and molded by a digital light processing 3D printer to obtain a model with partial positive charges, and then the obtained model is immersed into a dispersion liquid of a functional material with negative charges, so that the functional material is combined to the part, cured and molded by the photosensitive resin with the positive charge groups, in the model through electrostatic adsorption, and a conductive layer is formed in a specific area of the model, thereby providing a convenient, efficient and low-cost method for selectively functionalizing the 3D printing model based on electrostatic adsorption.
Other advantages of the present invention will be further explained in the following detailed description of the invention.
Drawings
Fig. 1 is a flow chart of a selectively functionalized DLP-3D printing model of the present invention, wherein fig. 1(a) shows an interdigital electrode printed by a digital light processing 3D printer, the interdigital portion of which is printed by a photosensitive resin having a positively charged group, and the substrate portion is printed by a neutral photosensitive resin, fig. 1(b) shows the interdigital electrode being selectively functionalized by immersing it in a dispersion of a negatively charged functional material, and fig. 1(c) shows the model after selective functionalization, the interdigital portion being formed with a layer of the functional material.
FIG. 2 is a zeta potential of a positively charged model of the surface and a negatively charged functional material (CNT) dispersion at different pH for DLP-3D printing according to the present invention.
Fig. 3 is an SEM image (fig. 3a) of the surface of the DLP-3D printing model prepared in example 1 of the present invention after being selectively functionalized with carbon nanotubes and an EDS image (fig. 3b) of S elements.
Fig. 4 is an SEM image of the surface of the DLP-3D printing model prepared in example 2 of the present invention after being selectively functionalized by nano silver wires.
Detailed Description
The technical features of the present invention will be described below with reference to preferred embodiments and drawings, which are intended to illustrate the present invention and not to limit the present invention. The figures are greatly simplified for illustration and are not necessarily drawn to scale.
It is to be understood that the preferred embodiments of the present invention are shown in the drawings only, and are not to be considered limiting of the scope of the invention. Various obvious modifications, variations and equivalents may be made to the present invention by those skilled in the art on the basis of the examples shown in the drawings, and the technical features in the different embodiments described below may be arbitrarily combined without contradiction, and these are within the scope of protection of the present invention.
The method for selectively processing the 3D printing model by the functionalized digital light comprises the following steps:
(1) preparing a neutral photosensitive resin containing a photocurable monomer (a);
(2) preparing a positively charged group-carrying photosensitive resin containing a cationic monomer, a diluent and a photocurable monomer (B);
(3) introducing a model to be printed into a digital light processing 3D printer, and respectively printing by using the neutral photosensitive resin and the photosensitive resin with the positive charge groups according to the design of the model to obtain the model;
(3) cleaning the obtained model to remove uncured monomers;
(4) dispersing a functional material in a solution containing an anionic surfactant to obtain a negatively charged functional material dispersion liquid;
(5) and immersing the model into the functional material dispersion liquid, and taking out the model after a set time.
Neutral photosensitive resin
The neutral photosensitive resin comprises a photocurable monomer (A) and a photoinitiator. The neutral photosensitive resin is used for a substrate for forming a mold or the like which is not required to be functionalized.
The photocurable monomer (a) may be a (meth) acrylate monomer having a hydroxyl group or an ether bond in the molecule, and examples thereof include polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, and trimethylolpropane triacrylate, and these monomers may be used alone or in combination of two or more of them, and among them, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate are preferably used. Aliphatic monofunctional acrylates such as EBECRYL 113, EBECRYL 114 may be selected for the flexible device. . The content of the photocurable monomer (a) in the neutral photosensitive resin is preferably 80% by weight or more, and more preferably 85 to 95% by weight.
The neutral photosensitive resin may contain other polymerizable monomers such as olefins, epoxy resins, and the like, without affecting the charging characteristics of the neutral photosensitive resin. The content of the other polymerizable monomer in the neutral photosensitive resin is preferably 10% by weight or less, and more preferably 5% by weight or less.
As the photoinitiator, a UV photoinitiator is preferably used, and examples thereof include phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and benzoin anisole. These photoinitiators may be used singly or in combination of two or more kinds, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide or (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide is particularly preferably used. The content of the photoinitiator in the neutral photosensitive resin is preferably 5 wt% or less, preferably 1 to 5 wt%, and more preferably 1 to 3 wt%.
In some preferred embodiments, in the preparation of the neutral photosensitive resin, a photoinitiator is added to the photocurable monomer (a), and then the mixture is shaken for 1 to 10 minutes by using a shaker, mixed uniformly and then kept stand for defoaming.
Photosensitive resin with positively charged groups
The photosensitive resin with positive charge groups comprises a cationic monomer, a diluent, a photocurable monomer (B) and a photoinitiator. The photosensitive resin with the positive charge groups is used for 3D printing, so that a part needing to be functionalized in a 3D printing model can be formed.
As the cationic monomer, a polymerizable monomer capable of generating cations and having an unsaturated bond can be used, and particularly, a quaternary ammonium salt of a water-soluble polymerizable monomer having an acryloyl group is preferably used, and specifically, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxypropyl trimethyl ammonium chloride, acryloylpropyltrimethyl ammonium chloride, methacryloyloxyethyl benzyl dimethyl ammonium chloride, and acryloyloxyethyl benzyl dimethyl ammonium chloride may be mentioned. Among them, methacryloyloxyethyl trimethyl ammonium chloride or acryloyloxyethyl trimethyl ammonium chloride is preferably used. The cationic monomer is preferably blended into the photosensitive resin in the form of an aqueous solution, and the concentration of the aqueous solution may be 60 to 85% by weight, preferably 80% by weight.
The diluent is added for reducing the viscosity of the photosensitive resin, and may be a diol acrylate, specifically, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tri (ethylene glycol) divinyl ether, and the like, and these may be used alone or in combination of two or more monomers. Among them, triethylene glycol dimethacrylate or triethylene glycol diacrylate is particularly preferably used. The content ratio of the diluent in the positively charged group-containing photosensitive resin is preferably 10 to 35% by weight, and more preferably 20 to 30% by weight.
The photocurable monomer (B) is a monomer for producing a photocurable product having toughness and heat resistance, and is preferably a (meth) acrylate having a bisphenol a skeleton, and specifically, bisphenol a glycerol dimethacrylate, bisphenol a glycerol diacrylate, ethoxylated bisphenol a diacrylate, propoxylated ethoxylated bisphenol a diacrylate, ethoxylated bisphenol a dimethacrylate may be mentioned. These may be used alone or in combination of two or more monomers. Among them, bisphenol a glycerin dimethacrylate and bisphenol a glycerin diacrylate are particularly preferable. The content ratio of the photocurable monomer (B) in the positively charged group-containing photosensitive resin is preferably 20 to 40% by weight, and more preferably 30 to 40% by weight.
As the photoinitiator in the photosensitive resin having a positively charged group, a uv initiator is preferably used, and examples thereof include phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and benzoin anisole. These photoinitiators may be used singly or in combination of two or more kinds, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide or (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide is particularly preferably used. In the positively charged group-containing photosensitive resin, the content ratio of the photoinitiator is preferably 5% by weight or less, preferably 1 to 5% by weight, and more preferably 1 to 3% by weight.
In some preferred embodiments, in the preparation of the photosensitive resin with positively charged groups, an aqueous solution of the photocurable monomer (B), the diluent, and the cationic monomer is put into a beaker in a predetermined ratio, stirred and mixed uniformly by using a glass rod, a predetermined amount of the photoinitiator is added, stirred for 1 to 2 hours at a rotation speed of 500 and 800rpm by using a magnetic stirrer, and then, the mixture is fully mixed and then is left to stand for defoaming.
Digital light processing 3D printing
The invention uses a digital light processing 3D printer to perform 3D printing and curing molding of the model. And designing a model to be printed by using 3D digital modeling software, introducing the model into a digital light processing 3D printer, and respectively printing and curing by using the prepared neutral photosensitive resin and the photosensitive resin with the positive charge groups according to the design of the model to obtain the model comprising the part (such as a substrate) which is formed by the neutral photosensitive resin and does not need to be functionalized and the part which is formed by the photosensitive resin with the positive charge groups and needs to be functionalized.
In some preferred embodiments, as the digital light processing 3D printer, a B9Core 530DLP-3D printer (B9 Creations) can be used, the wavelength of the used ultraviolet light is 405nm, and the exposure parameter is set to be 7-10. By adopting the device and the conditions, 3D printing of the model can be simply, conveniently and quickly carried out.
In some preferred embodiments, after removing the mold, the uncured monomer in the mold is dissolved and removed by flushing with a solvent such as absolute ethanol or isopropanol, and finally purging with nitrogen.
Negatively charged functional material dispersion
The negatively charged functional material dispersion liquid according to the present invention is obtained by dispersing a functional material in a solution containing an anionic surfactant.
The anionic surfactant is not particularly limited as long as it can be attached to the surface of the functional material to negatively charge the functional material, and examples thereof include sodium lauryl sulfate, and sodium cetyl sulfonate. Among them, sodium lauryl sulfate is particularly preferably used.
As the functional material, a nanomaterial having excellent conductivity is preferable, and for example, any one selected from a carbon nanotube, graphene, a silver nanowire, and a copper nanowire may be used. As the solvent for dispersing the functional material, deionized water, ethanol, or isopropyl alcohol may be used, and among these, deionized water is particularly preferably used as the dispersion solvent for the carbon nanotubes, and isopropyl alcohol is particularly preferably used as the dispersion solvent for the silver nanowires.
In some preferred embodiments, the functional material and the anionic surfactant are added to the dispersion solvent under the conditions that the concentration of the functional material is 0.1 to 2.0 mass% and the concentration of the anionic surfactant is 0.2 to 1.0 mass%, and the mixture is subjected to ultrasonic dispersion for 1 to 2 hours, then is allowed to stand, and the supernatant is taken for standby.
In some preferred embodiments, the 3D printing model obtained above is immersed in the functional material dispersion (supernatant) for 10 to 30 minutes, and then the model is taken out, rinsed with deionized water, and purged with nitrogen.
By immersing the 3D printing mold in the functional material dispersion liquid, the negatively charged functional material can be strongly bonded to the portion of the mold formed of the photosensitive resin having positively charged groups by electrostatic interaction, thereby forming a functionalized layer (e.g., a conductive layer) composed of the functional material on the surface of the mold. On the other hand, since the portion not to be functionalized formed of the neutral photosensitive resin is not charged, the functional material layer cannot be formed even if it is immersed in the functional material dispersion liquid, so that the selective functionalization of the mold can be realized.
An example of the selective functionalization process of the model is illustrated with reference to fig. 1, in which fig. 1(a) shows a schematic view of a model 1 comprising an interdigital electrode obtained by digital light processing 3D printing, a portion 2 (substrate) not to be functionalized formed of a neutral photosensitive resin, and a portion 3 (interdigital portion) to be functionalized formed of a photosensitive resin having a positively charged group; FIG. 1(b) shows that a mold 1 is immersed in a functional material dispersion liquid 4; fig. 1(c) shows the resultant interdigital electrode having the functionalized layer 3' formed on the surface thereof. It should be noted that fig. 1(a) - (c) are only examples for facilitating understanding of the selective functionalization process of the present invention, and do not limit the scope of the present invention.
Examples
The method and advantages of the present invention are further illustrated by the following examples, but it should be understood that the following examples are only illustrative for carrying out the present invention and are not to be construed as limiting the scope of the present invention.
Example 1
5 parts by mass of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide serving as a photoinitiator is added to 95 parts by mass of polyethylene glycol diacrylate, the mixture is shaken for 5 minutes by using an oscillator, and the mixture is uniformly mixed and then is kept stand for defoaming to prepare the neutral photosensitive resin.
40 parts by mass of bisphenol A glycerol dimethacrylate (BisGMA), 30 parts by mass of triethylene glycol dimethacrylate and 30 parts by mass of 80% aqueous solution of methacryloyloxyethyl trimethyl ammonium chloride are put into a beaker and stirred and mixed uniformly by using a glass rod, 5 parts by mass of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide serving as a photoinitiator is added, the mixture is stirred for 2 hours at the rotating speed of 800rpm by using a magnetic stirrer, and the mixture is fully mixed and then stands for defoaming, so that the photosensitive resin with the positive charge group is prepared.
And (3) designing and drawing a model to be printed by utilizing three-dimensional modeling software, introducing the model into a B9Core 530DLP-3D printer, and respectively printing and curing by utilizing the prepared neutral photosensitive resin and the photosensitive resin with positive charge groups according to the design of the model, wherein the wavelength of ultraviolet light is set to 405nm, and the exposure is set to 7, so as to obtain the required model. After the mold is taken out, the mold is cleaned by absolute ethyl alcohol, uncured monomers in the mold are dissolved and removed, and finally, the mold is blown clean by nitrogen and dried.
Then, 0.3g of Carbon Nanotube (CNT) and 0.4g of sodium dodecyl sulfate were added to 100g of deionized water, and after 1 hour of ultrasonic dispersion, the mixture was allowed to stand to obtain a carbon nanotube dispersion solution, and the supernatant was taken for use.
The cleaned 3D printing mold was immersed in the carbon nanotube dispersion (supernatant) for 30 minutes, and then the mold was taken out, rinsed with deionized water, purged with nitrogen, and dried.
In order to characterize the positive charge characteristics of the sample printed with the positively charged photosensitive resin and the negative charge characteristics of the carbon nanotubes dispersed with the anionic dispersant, zeta potential tests were performed at different pH (6, 7, 8), respectively, and the results are shown in fig. 2. In FIG. 2, the positive and negative reaction charge types of the zeta potential values reflect the charge amount in absolute value. As can be seen from fig. 2, the zeta potentials (solid lines in the figure) of the samples printed from the positively charged photosensitive resins were all positive and greater than 30mV in absolute value, indicating that the surfaces thereof carry a certain amount of positive charges; the zeta potential (dotted line in the figure) of the carbon nanotube dispersion is negative and the absolute value is more than 20mV, which indicates that the surface of the carbon nanotube in the dispersion has a certain amount of negative charges. This result indicates the feasibility of using electrostatic adsorption to perform selective functionalization.
The surface of the DLP-3D printing model finally obtained is characterized, the SEM image of the surface of the DLP-3D printing model after being selectively functionalized by the carbon nanotubes is shown in the SEM image of fig. 3a, and in order to show the selective functionalization more clearly, the EDS surface scan image characterization of the S element is performed on the surface of the area where the SEM is shot (fig. 3 b). The reason why the S element is selected for EDS surface scanning is that since the CNT is dispersed by SDS (containing S) and SDS is wound around the CNT, only the portion where the CNT is adsorbed has S, and thus the EDS image of S can clearly reflect the functionalization and its selectivity, as can be seen from the EDS image of the S element of fig. 3b, the right half contains a large amount of S element, indicating that a large amount of carbon nanotubes are adsorbed on the surface, while the left half has only sporadic S element distribution, and almost no carbon nanotubes remain.
Example 2
A 3D printing model in which a silver nanowire was selectively bonded to the surface of the model was manufactured in the same manner as in example 1, except that the silver nanowire (AgNWs) was used as a functional material. As the silver nanowire dispersion, an isopropyl alcohol dispersion having a silver nanowire concentration of 2.0 mass% was used.
SEM analysis is carried out on the finally obtained 3D printing model, as can be seen from figure 4, a selective functionalized area (with AgNWs) and an unfunctionalized area (without AgNWs) are formed on the surface of the DLP-3D printing model, and the boundary is clear and visible, so that the nano silver wire layer can be selectively formed on the surface of the 3D printing model simply and conveniently by the method.
Finally, it should be understood that the above description of the embodiments and examples is illustrative in all respects, not restrictive, and that various modifications may be made without departing from the spirit of the invention. The scope of the invention is indicated by the claims rather than by the foregoing description of the embodiments or examples. The scope of the present invention includes all modifications within the meaning and range equivalent to the claims.
Availability in industry
The method for selectively functionalizing the digital light processing 3D printing model is simple to operate, and the 3D printing model can be selectively functionalized at low cost. The functional DLP-3D printing model obtained by the invention has excellent electrochemical performance and mechanical performance, and the excellent performance has wide application prospects in the fields of preparation of 3D printing electronic devices, biological medicine, robots and the like.
Claims (9)
1. A method of selectively functionalizing a digital light processing 3D printing model, comprising:
preparing a neutral photosensitive resin containing a photocurable monomer (a);
preparing a positively charged group-carrying photosensitive resin containing a cationic monomer, a diluent and a photocurable monomer (B);
introducing a model to be printed into a digital light processing 3D printer, and respectively printing and curing by using the neutral photosensitive resin and the photosensitive resin with the positive charge groups according to the design of the model to obtain the model;
cleaning the obtained model, and removing uncured monomers;
dispersing a functional material in a solution containing an anionic surfactant to obtain a negatively charged functional material dispersion liquid;
and immersing the model into the functional material dispersion liquid, and taking out after a set time, wherein the cationic monomer units in the model are dissociated in the functional material dispersion liquid to be positively charged, and are combined with the functional materials with negative charges in the functional material dispersion liquid through electrostatic adsorption, so that the selective functionalization of the model is realized.
2. The method of selectively functionalizing a digital light processing 3D printing model according to claim 1, wherein the photo-curable monomer (a) is at least one selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, and aliphatic monofunctional acrylate.
3. The method of selectively functionalizing a digital light processing 3D printing model of claim 1, wherein the cationic monomer is at least one selected from methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxypropyl trimethyl ammonium chloride, acryloylpropyl trimethyl ammonium chloride, methacryloyloxyethyl benzyl dimethyl ammonium chloride, and acryloyloxyethyl benzyl dimethyl ammonium chloride.
4. The method of selectively functionalizing a digital light processing 3D printing model of claim 1, wherein the diluent is at least one selected from the group consisting of diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, and tri (ethylene glycol) divinyl ether.
5. The method of selectively functionalizing a digital light processing 3D printing model according to claim 1, wherein the photo-curable monomer (B) is any one selected from bisphenol a glycerol dimethacrylate, bisphenol a glycerol diacrylate, ethoxylated bisphenol a diacrylate, propoxylated ethoxylated bisphenol a diacrylate, ethoxylated bisphenol a dimethacrylate.
6. The method of selectively functionalizing a digital light processing 3D printing model according to claim 1, wherein the neutral photosensitive resin and the positively charged group photosensitive resin further comprise a photoinitiator, and the photoinitiator is at least one selected from the group consisting of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin anisole.
7. The method of selectively functionalizing a digital light processing 3D printing model of claim 1, wherein the anionic surfactant is at least one of sodium dodecyl sulfate, sodium hexadecyl sulfonate.
8. The method of selectively functionalizing a digital light processing 3D printing model of claim 1, wherein the functional material is any one of carbon nanotubes, graphene, nano silver wires, nano copper wires.
9. The method of selectively functionalizing a digital light processing 3D printed model according to claim 1, wherein the immersion time when the model is immersed in the functional material dispersion is 10 to 30 minutes.
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