CN114350158A - Photo-thermal dual-curing composite direct-writing 3D printing medium, preparation method and application - Google Patents
Photo-thermal dual-curing composite direct-writing 3D printing medium, preparation method and application Download PDFInfo
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Abstract
The invention provides a photo-thermal dual-curing composite direct-writing 3D printing medium, a preparation method and application, wherein the viscosity of the composite direct-writing 3D printing medium is 200-1000 Pa.s, the viscosity change value is less than or equal to 10% after the composite direct-writing 3D printing medium is placed and stored in a dark place at room temperature for more than 30 days, the Shore hardness after curing is more than 30A, the curing mode is that the pre-curing is performed by illumination firstly, and the full curing is performed by heating, and the preparation method comprises the following steps: mixing polysiloxane containing carbon double bonds, hydrogen-containing polysiloxane, a photosensitive resin monomer, a tackifier, a polymerization inhibitor and inorganic nano filler to obtain a first mixture; heating the first mixture for a first time to obtain a second mixture; cooling the second mixture, mixing the second mixture with a platinum catalyst and a photoinitiator, and mixing under a dark condition to obtain a third mixture; and sequentially carrying out vacuum defoaming and pressure filtration on the third mixture, and being applicable to direct-writing 3D printing of line printing with the aspect ratio larger than 0.5.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a composite direct-writing 3D printing medium with photo-thermal dual curing, a preparation method and application thereof.
Background
3D printing is used as a novel precision machining manufacturing technology, and is characterized in that the technology adopts a material increase manufacturing process from inexistence to inexistence in the manufacturing process, and a material decrease manufacturing process from inexistence to inexistence by gradually subtracting redundant materials is adopted in the traditional process. Compared with the traditional manufacturing process, the 3D printing technology of additive manufacturing has higher flexibility and practicability. At present, the common 3D printing technologies include fused deposition ((FDM), stereo light curing (DLP, CLIP, or PolyJet), selective laser sintering (SLA, SLS), and three-dimensional printing (3DP), however, none of these 3D printing technologies can use silica gel type dielectric materials to print precise structures.
Direct Ink Writing (DIW) is a new 3D printing technology, which is widely applied to the fields of electronic devices, structural materials, tissue engineering, soft robots and the like at present, and is capable of well fitting silica gel type dielectric materials to perform corresponding precision processing on products by extruding semisolid ink materials with shear thinning property from a printing nozzle and stacking the ink layers to construct a pre-designed three-dimensional structure.
In the prior art, technologies for researching silica gel printing media are available, for example, CN105643939B and CN107674429A disclose a 3D printing silica gel and a printing method thereof, respectively, however, a single-component silica gel material is adopted, and there is a risk that a storage period is short, and when printing, a printing nozzle is easily blocked due to thickening, gel or coarse particles. CN106313505A and CN107638231A disclose a two-component mixed silica gel 3D printer and a printing method thereof, and the specific technical details of the two-component mixed silica gel are not disclosed, and the temperature of an adopted annular heating plate is as high as 100-400 ℃ during printing, so that the printing nozzle is easily blocked by the high-temperature gel of the silica gel in the printing nozzle due to the high temperature. In addition, the thermosetting silica gel composite materials commonly available in the market generally have the problem of nozzle blockage caused by viscosity increase after slow curing at room temperature.
In summary, no silica gel composite material which can be well adapted to direct-writing 3D printing exists in the market at present, and market popularization and application of the 3D printing technology are further limited.
Disclosure of Invention
The invention aims to provide a photo-thermal dual-curing composite direct-writing 3D printing medium, a preparation method and application thereof.
In order to achieve the above object, in a first embodiment, the present disclosure provides a photo-thermal dual-cured composite direct-writing 3D printing medium, where the viscosity of the composite direct-writing 3D printing medium is 200 to 1000Pa · s, the viscosity change value is less than or equal to 10% after being placed in a dark place for more than 30 days at room temperature, the shore hardness after curing is more than 30A, and the curing method is pre-curing by illumination first, and then fully curing by heating.
The material printed under illumination can have good shape retention, so that the phenomenon of leveling or collapse can be avoided under the condition of thermocuring.
The photo-thermal dual-curing composite direct-writing 3D printing medium is prepared by the following method: s1, mixing polysiloxane containing carbon double bonds, hydrogen-containing polysiloxane, photosensitive resin monomer, tackifier, polymerization inhibitor and inorganic nano filler to obtain a first mixture; s2, heating the first mixture for a first time to obtain a second mixture; s3, cooling the second mixture, mixing the second mixture with a platinum catalyst and a photoinitiator, and mixing under a dark condition to obtain a third mixture; and S4, sequentially carrying out vacuum defoaming and pressure filtration on the third mixture to obtain the composite direct-writing 3D printing medium.
In a second embodiment, the present disclosure provides a method for preparing a photo-thermal dual-cured composite direct-writing 3D printing medium, including the following steps:
s1, mixing polysiloxane containing carbon double bonds, hydrogen-containing polysiloxane, photosensitive resin monomer, tackifier, polymerization inhibitor and inorganic nano filler to obtain a first mixture;
s2, heating the first mixture for a first time to obtain a second mixture;
s3, cooling the second mixture, mixing the second mixture with a platinum catalyst and a photoinitiator, and mixing under a dark condition to obtain a third mixture;
and S4, sequentially carrying out vacuum defoaming and pressure filtration on the third mixture to obtain the composite direct-writing 3D printing medium.
In step S1, the polysiloxane, the hydrogenpolysiloxane, the photosensitive resin monomer, the tackifier, the polymerization inhibitor, and the inorganic nanofiller are mixed with each other, which is advantageous in that: photosensitive resin monomers are introduced as auxiliary materials of the silica gel material, so that the shape keeping property of the material is realized through curing of photosensitive resin in the printing process of the material, and then the full curing of the composite material in the heating process ensures the shape keeping of the printed graph.
Because the silica gel material is easy to level, if the photosensitive resin is not added, the printed material can not be ensured, and the good appearance can be ensured before thermocuring. And the addition of photosensitive resin makes the silica gel material itself receive irradiant influence before the thermosetting, has certain hardness after the curing, can guarantee can not appear leveling and even the condition of collapsing before the thermosetting.
In the mixing reaction, the dosage of the polysiloxane, the hydrogenpolysiloxane, the photosensitive resin monomer and the tackifier meets the following conditions: 100: 20-100: 20-50: 10 to 50. In some embodiments, it is preferably 100: 20-80: 10-30: 20 to 40.
The polysiloxane containing carbon double bonds is at least one of vinyl polysiloxane, methyl vinyl polysiloxane and methyl phenyl vinyl polysiloxane. If the polysiloxane containing the carbon double bond is selected from vinyl polysiloxane, wherein vinyl in the vinyl polysiloxane is at the alpha position, the omega position or the middle position of a polysiloxane molecular chain, the viscosity of the vinyl polysiloxane is 50-500 Pa.s, the vinyl content is 0.05-l0 mol%, each molecule of the vinyl polysiloxane contains more than 2 vinyl functional groups connected with silicon atoms, and the molecular weight is (40-100) multiplied by 104。
The tackifier is: HO-Si (CH)3)2O[Si(CH3)2O]nSi(CH3)2-OH, n-3-8, hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), one or more of dimethylsiloxane mixed ring bodies (DMC).
The polymerization inhibitor is alkynol with the carbon number of less than 15, preferably one or more of 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 3-butyn-1-ol and 3, 5-dimethyl-1-hexyn-3-ol, and the mass fraction of the inhibitor added into the dielectric material is 0.1-2%.
The hydrogenpolysiloxane is at least one of methyl hydrogenpolysiloxane, methyl phenyl hydrogenpolysiloxane, methyl hydrogenpolysiloxane and phenyl hydrogenpolysiloxane, wherein the viscosity of the hydrogenpolysiloxane is 50-500 Pa.s, and the hydrogen content is 0.1-1 mol%; the hydrogen-containing polysiloxane contains more than 2 hydrogen atoms connected with silicon atoms in each molecule, and the molecular weight is (40-100) multiplied by 104。
The inorganic nano filler is one or more of silicon dioxide, calcium silicate, calcium carbonate, titanium dioxide, carbon black, graphene and zinc oxide, and the size of the inorganic nano filler is 1-500 nm.
The photosensitive resin monomer is selected from one or more of epoxy acrylic acid, polyurethane acrylic acid, polyester acrylic acid, polyether acrylic acid, hydroxyl acrylate and the like.
In step S2, the first mixture is heated to 50-80 ℃, and the first mixture is stabilized at any temperature of 50-80 ℃ for a first time period, so as to: the viscosity of the material will decrease with increasing temperature and the material fluidity will change at higher temperatures provided that the mixing is more uniform and thorough, for a first period of 30-180 minutes, which may be 40/50/60/70/80/90/100/110 minutes; the first mix was also stable at 60/70 ℃.
In addition, in step S2, the first mix is heated while being stirred at a high speed.
In step S3, the temperature of the second mixed material is reduced to less than 50 ℃, which has the advantages that: the introduction of the catalyst at a relatively low temperature prevents the material from already beginning to cure during the glue making process. Platinum catalysts have high catalytic activity at higher temperatures, which leads to polymeric curing of the polysiloxane.
And in the step, a platinum catalyst and a photoinitiator are added into the second mixture to serve as catalysts corresponding to the subsequent material light and heat curing.
The platinum catalyst used was: the catalyst is prepared from chloroplatinic acid or at least one complex formed by chloroplatinic acid and alkene, cycloalkane, alcohol, ester, ketone and ether, preferably a Speier platinum catalyst or a Karstedt platinum catalyst with the platinum metal content of 0.1-5%, and the mass fraction of the catalyst added into the medium material is 0.1-0.5%.
The photoinitiator is selected from benzoin and derivatives, benzil, alkyl benzophenones, acyl phosphorus oxide, benzophenone, thioxanthone, diaryl iodine
Salt, triaryl iodide
Salt, alkyl iodide
One or more of salt, cumen ferrocenyl hexafluorophosphate and its analogues in photosensitive tree0.1-20% of the mass of the fat monomer.
Further, the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (819), bis 2, 6-difluoro-3-pyrrolylphenylferrocene (784), 2-hydroxy-2-methyl-1-phenylpropanone, l-hydroxycyclohexylphenylketone, bis 2, 6-difluoro-3-benzenoyl-ferrocene, 4-isobutylphenyl-4' -methylphenyliodide
Hexafluorophosphate, 4- (phenylthio) phenyldiphenylsulfide
One or more of hexafluorophosphates.
The mixing means provided by the scheme adopts one or more of ball milling, grinding or mechanical stirring, and the mixing materials can be uniformly mixed.
In a third embodiment, the scheme provides an application of the composite direct-writing 3D printing medium prepared according to the preparation method, and the composite direct-writing 3D printing medium is applied to direct-writing 3D printing, wherein the printed line width is 1-200 μm, and the composite direct-writing 3D printing medium is suitable for line printing with the aspect ratio larger than 0.5, and the curing method comprises the steps of pre-curing by illumination first and fully curing by reheating.
Compared with the prior art, the technical scheme has the following characteristics and beneficial effects:
1. the viscosity attribute of the composite direct-writing 3D printing medium can be as high as 200-1000 Pa.s, the shape retention of a printed product is strong, the phenomenon of line collapse is not easy to occur in the curing process of the product, the high-precision printing of micron-level lines is further met, the printed line width is 1-200 mu m, and the composite direct-writing 3D printing medium is suitable for line printing with the aspect ratio larger than 0.5. And be different from the traditional medium material and promote the condition of material viscosity through the packing particle of packing micron size granule, the compound viscosity of directly writing formula 3D printing medium itself of this scheme is higher, and then reduces the risk that the jam shower nozzle appears.
2. The composite direct-writing 3D printing medium has good long-time storage stability, can have a viscosity change value of less than or equal to 10% at room temperature for more than 30 days, has a cone penetration of 280 multiplied by 0.1mm at 25 ℃, has a change value of less than or equal to 10% within 30 days, can meet the long-time printing requirement of 3D printing, and has high viscosity and high stability.
3. This scheme introduces photosensitive resin monomer as the auxiliary material of silica gel material at the in-process of preparing compound formula 3D printing medium that directly writes, guarantees that the material passes through photosensitive resin's solidification at the printing in-process, realizes the shape preserving nature of material, and the full solidification of combined material in the heating process afterwards guarantees to print back figure shape preserving, can guarantee the viscosity of material and stability when depositing, combines the dual efficiency of photocuring and high temperature curing simultaneously. The Shore hardness after curing is above 30A, and the curing mode is that the curing is performed by illumination for precuring and then heating for full curing.
Drawings
Fig. 1 is a schematic view of a print result corresponding to embodiment 1.
Fig. 2 is a three-dimensional structural view of a print line width corresponding to embodiment 1.
Fig. 3 is a schematic view of a print result corresponding to embodiment 2.
Fig. 4 is a three-dimensional structural view of a print line width corresponding to embodiment 2.
Fig. 5 is a schematic view of a print result corresponding to embodiment 3.
Fig. 6 is a three-dimensional structural view of a print line width corresponding to embodiment 3.
Fig. 7 is a schematic view of the print result corresponding to the control group 1.
Fig. 8 is a three-dimensional structural view of the print line width corresponding to the control group 1.
Fig. 9 is a schematic view of the print result corresponding to the control group 2.
Fig. 10 is a three-dimensional structural view of the print line width corresponding to the control group 2.
Fig. 11 is a schematic diagram of the print result corresponding to the control group 4.
Fig. 12 is a three-dimensional structural view of the print line width corresponding to the comparison group 4.
Fig. 13 is a schematic flow chart of a method for manufacturing the photothermal dual cured composite direct-write 3D printing medium according to the present embodiment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
It is understood that the terms "a" and "an" should be interpreted as meaning that a number of one element or element is one in one embodiment, while a number of other elements is one in another embodiment, and the terms "a" and "an" should not be interpreted as limiting the number.
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. It is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. The test methods in the following examples, in which specific conditions are not specified, are generally carried out according to conventional methods or according to conditions recommended by the respective manufacturers.
The first embodiment is as follows: preparation of composite direct-write 3D printing medium (viscosity 200Pa · s):
(1) 80g of a polymer having a viscosity of 50 pas, a vinyl content of 0.05mo 1% and a molecular weight of 40X 10460g of a vinylpolysiloxane having a viscosity of 50 pas, a hydrogen content of 0.1mo 1%, a molecular weight of 40X 104The hydrogen-containing polysiloxane, 20g of acrylic epoxy resin, 20g of hexamethylcyclotrisiloxane (D3), 0.2g of 1-ethynyl-1-cyclohexanol and 20g of 20-30 nm hydrophobic fumed silica are added into a stirring kettle and uniformly mixed,
(2) heating to 70 ℃, reacting for 30min,
(3) reducing the temperature to 30 ℃, adding 0.2g Karstedt platinum catalyst and 0.02g TPO under the dark condition, uniformly mixing, and stirring for 2 hours at normal temperature under the vacuum degree of less than 0.1 MPa;
(4) and (4) moving out to a three-roller machine, grinding to the size of less than 5 mu m, and finally performing pressure filtration to obtain the composite direct-writing 3D printing medium with the viscosity of 200Pa & s.
And (3) performance testing:
the viscosity of the composite direct-write 3D printing medium was measured by a viscometer and was 200Pa · s. The cone penetration was measured for 30 days using a cone penetration meter (25 ℃,0.1mm) and the values were 279 (initial value) and 277 (value after 30 days), respectively, and the material showed good storage stability.
Application test: as shown in fig. 1 and fig. 2, in this embodiment, a ceramic needle with an inner diameter of 10 μm is used, and a line width with a good aspect ratio can still be printed at a printing speed of 70mm/s, where the specific values are: the height is 8 μm, the width is 12 μm, and the hardness of the cured material is 45 by a Shore A durometer test.
Example two: preparation of composite direct-write 3D printing medium (viscosity 500Pa · s):
(1) 80g of a polymer having a viscosity of 100 pas, a vinyl content of 5mo 1% and a molecular weight of 70X 10460g of methylvinylpolysiloxane having a viscosity of 100 pas, a hydrogen content of 0.5mo 1%, a molecular weight of 70X 104Of a hydrogen-containing polysiloxane, 10g of a hydroxy hexyl methacrylate, HO-Si (CH)3)2O[Si(CH3)2O]3Si(CH3)2OH30g, propargyl alcohol 1g and titanium dioxide 20 g-100 nm are added into a stirring kettle and mixed evenly,
(2) heating to 80 ℃, and reacting for 100 min;
(3) reducing the temperature to 30 ℃, adding 0.5g of Karstedt platinum catalyst and 0.5g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819) under the dark condition, uniformly mixing, and stirring for 2 hours at normal temperature under the vacuum degree of less than 0.1 MPa;
(4) and (4) moving out to a three-roller machine, grinding to a size of less than 10 mu m, and finally performing pressure filtration to obtain the composite direct-writing 3D printing medium with the viscosity of 500Pa & s.
And (3) performance testing:
the viscosity of the composite direct-write 3D printing medium was measured by a viscometer and was 500Pa · s. The cone penetration was measured for 30 days using a cone penetration meter (25 ℃,0.1mm) and was 167 (initial value) and 165 (value after 30 days), respectively, and the material showed good storage stability.
Application test: as shown in fig. 3 and 4, the present embodiment uses a ceramic needle with an inner diameter of 50 μm, and can still print a line width with a good aspect ratio at a printing speed of 70mm/s, where the specific values are: the height is 45 μm, the width is 35 μm, and the hardness of the cured material is 63 by using a Shore A durometer.
Example three: preparation of composite direct-write 3D printing medium (viscosity 1000Pa · s):
(1) 100g of a polymer having a viscosity of 100 pas, a vinyl content of 10mo 1% and a molecular weight of 70X 10420g of a methylphenylvinylpolysiloxane having a viscosity of 100 pas, a hydrogen content of 1mo 1% and a molecular weight of 100X 104Adding hydrogen-containing polysiloxane, 10g of polyurethane acrylic acid, 40g of dimethyl siloxane mixed ring body (DMC), 4g of 3-butyne-1-ol and 40g of carbon black with the particle size of 10-20 nm into a stirring kettle, uniformly mixing,
(2) heating to 80 ℃, and reacting for 100 min;
(3) reducing the temperature to 30 ℃, adding 1g of Karstedt platinum catalyst and 2g of bis (2, 6-difluoro-3-pyrrolyl) phenyl ferrocene (784) under the dark condition, uniformly mixing, and stirring for 2 hours at normal temperature under the vacuum degree of less than 0.1 MPa;
(4) and (4) moving the mixture out of the three-roller mill, grinding the mixture to a size of less than 10 mu m, and finally performing pressure filtration to obtain the composite material with the viscosity of 1000Pa & s.
And (3) performance testing:
the viscosity of the composite direct-write 3D printing medium was measured by a viscometer and was 1000Pa · s. The cone penetration was measured for 30 days using a cone penetration meter (25 ℃,0.1mm) and was 119 (initial value) and 121 (after 30 days), respectively, and the material showed good storage stability.
Application test: as shown in fig. 5 and fig. 6, the present embodiment uses a ceramic needle with an inner diameter of 100 μm, and can still print a line width with a good aspect ratio at a printing speed of 50mm/s, where the specific values are: the height is 95 μm, the width is 102 μm, and the hardness of the cured material is 90 by using a Shore A durometer.
Control group 1: the procedure is as in example 1, the acrylic epoxy resin in step (1) and the photoinitiator TPO in step (3) are removed:
(1) 80g of a polymer having a viscosity of 50 pas, a vinyl content of 0.05mo 1% and a molecular weight of 40X 10460g of a vinylpolysiloxane having a viscosity of 50 pas, a hydrogen content of 0.1mo 1%, a molecular weight of 40X 104The hydrogen-containing polysiloxane, 20g of hexamethylcyclotrisiloxane (D3), 0.2g of 1-ethynyl-1-cyclohexanol and 20g of hydrophobic fumed silica with the particle size of 20-30 nm are added into a stirring kettle and uniformly mixed,
(2) heating to 70 ℃, reacting for 30min,
(3) reducing the temperature to 30 ℃, adding 0.2g Karstedt platinum catalyst under the dark condition, mixing uniformly, and stirring for 2 hours at normal temperature under the vacuum degree of less than 0.1 MPa;
(4) moving out to a three-roller machine to grind to the size of less than 5 mu m, and finally performing pressure filtration to obtain the composite direct-writing 3D printing medium with the viscosity of 200 Pa.s
Final material properties:
material viscosity: 220 Pa.s, cone penetration of 30 days measured with a cone penetration meter (25 ℃,0.1mm) and the values were 277 (initial value) and 282 (value after 30 days), respectively, and the material showed good storage stability. As shown in FIGS. 7 and 8, in the comparative example, the printing line shape retention was poor at a printing speed of 70mm/s using a ceramic tip having an inner diameter of 10 μm, and the specific values were: the height is 6 μm, the width is 15 μm, and the hardness of the cured material is 53 by using a Shore A durometer.
The comparison between the control 1 and the example 1 shows that: if no light-cured resin exists, the shape of the printed lines is poor, and the aspect ratio of the finally obtained material is less than 0.5.
Control group 2:
the procedure of example 1 was followed to remove the photoinitiator TPO of step (3).
Final material properties:
material viscosity: 250 Pa.s, and a cone penetration degree of 262 (initial value) and 265 (after 30 days) measured by a cone penetration meter (25 ℃,0.1mm), the hardness of the material gradually increased after standing for a long time, and the storage stability was poor. As shown in FIGS. 9 to 10, in the comparative example, the printing line shape retention was poor at a printing speed of 70mm/s using a ceramic tip having an inner diameter of 10 μm, and the specific values were: the height is 5 μm, the width is 13 μm, and the hardness of the cured material is 33 by using a Shore A durometer.
The comparison between the control group 2 and the example 1 shows that: the curing of the photosensitive resin cannot be realized without adding a photoinitiator, and the shape retention of the material is poor.
Control group 3:
the final material properties of the polymerization inhibitor 1-ethynyl-1-cyclohexanol of step (2) were removed as in the procedure of example 1:
material viscosity: 260 Pa.s, and a cone penetration degree tester (25 ℃,0.1mm) is adopted to test the cone penetration degree for 30 days, the values are 241 (initial values), the hardness reaches 146 after 30min, and the storage stability of the material is poor. The hardness of the cured material was 45 as measured by a shore a durometer.
Control group 4
The procedure of example 1 was followed to remove the adhesion promoter hexamethylcyclotrisiloxane (D3) of step (1).
Material viscosity: 100 pas, and the values were 348 (initial value) and 305 (value after 30 days) respectively, as measured by a cone penetration meter (25 ℃,0.1mm), and the hardness gradually increased with the material left for a long time, and the storage stability was poor. As shown in fig. 11 and 12, the present scheme adopts a ceramic needle with an inner diameter of 10 μm, and the printed linear shape retention is poor when the printing speed is 70mm/s, and the specific values are as follows: 4 μm in height and 15 μm in width, and the hardness of the cured material is 12 measured by a Shore A durometer
Summary the performance tests of the composite direct write 3D printing media of the above examples and control are as follows:
it can also be clearly seen from the table that the composite direct-write 3D printing media of examples 1 to 3 provided by the present solution perform well, and the preparation method provided by the present solution is particularly unique in beneficial effects.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products in various forms can be obtained by anyone in the light of the present invention, but any changes in the shape or structure thereof, which have the same or similar technical solutions as those of the present application, fall within the protection scope of the present invention.
Claims (12)
1. The photo-thermal dual-curing composite direct-writing 3D printing medium is characterized in that the viscosity of the composite direct-writing 3D printing medium is 200-1000 Pa.s, the viscosity change value is less than or equal to 10% after the medium is placed in a dark place for more than 30 days at room temperature, the Shore hardness after curing is more than 30A, and the curing mode is that the medium is pre-cured by illumination firstly and then fully cured by heating.
2. The photothermal dual cured composite direct write 3D printing medium according to claim 1, prepared by the following method:
s1, mixing polysiloxane containing carbon double bonds, hydrogen-containing polysiloxane, photosensitive resin monomer, tackifier, polymerization inhibitor and inorganic nano filler to obtain a first mixture;
s2, heating the first mixture for a first time to obtain a second mixture;
s3, cooling the second mixture, mixing the second mixture with a platinum catalyst and a photoinitiator, and mixing under a dark condition to obtain a third mixture;
and S4, sequentially carrying out vacuum defoaming and pressure filtration on the third mixture to obtain the composite direct-writing 3D printing medium.
3. A preparation method of a photo-thermal dual-curing composite direct-writing 3D printing medium is characterized by comprising the following steps:
s1, mixing polysiloxane containing carbon double bonds, hydrogen-containing polysiloxane, photosensitive resin monomer, tackifier, polymerization inhibitor and inorganic nano filler to obtain a first mixture;
s2, heating the first mixture for a first time to obtain a second mixture;
s3, cooling the second mixture, mixing the second mixture with a platinum catalyst and a photoinitiator, and mixing under a dark condition to obtain a third mixture;
and S4, sequentially carrying out vacuum defoaming and pressure filtration on the third mixture to obtain the composite direct-writing 3D printing medium.
4. The method for preparing a photothermal dual cured composite direct write 3D printing medium according to claim 3, wherein the carbon double bond-containing polysiloxane is at least one of vinyl polysiloxane, methyl vinyl polysiloxane, and methylphenyl vinyl polysiloxane.
5. The method for preparing a photothermal dual cured composite direct write 3D printing medium according to claim 3, wherein the hydrogenpolysiloxane is at least one of methyl hydrogenpolysiloxane, methylphenyl hydrogenpolysiloxane, methyl hydrogenpolysiloxane, and phenyl hydrogenpolysiloxane.
6. The method of preparing a photothermal dual cured composite direct write 3D printing medium according to claim 3, wherein the platinum catalyst is: chloroplatinic acid or at least one complex of chloroplatinic acid and alkene, cycloalkane, alcohol, ester, ketone and ether.
7. The method of preparing a photothermal dual cured composite direct write 3D printing medium according to claim 3, wherein the adhesion promoter is: HO-Si (CH)3)2O[Si(CH3)2O]nSi(CH3)2-OH, n-3-8, hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), one or more of dimethylsiloxane mixed ring bodies (DMC).
8. The method of preparing a photothermal dual cured composite direct write 3D printing medium according to claim 3, wherein the polymerization inhibitor is an alkynol with a carbon number < 15.
9. The method for preparing a photothermal dual cured composite direct write 3D printing medium according to claim 3, wherein the photosensitive resin monomer is selected from one or more of epoxy acrylic, urethane acrylic, polyester acrylic, polyether acrylic, hydroxy acrylate, and the like.
10. The method for preparing the photothermal dual cured composite direct write 3D printing medium according to claim 3, wherein the inorganic nanofiller is one or more of silica, calcium silicate, calcium carbonate, titanium dioxide, carbon black, graphene, and zinc oxide.
11. The method for preparing a photothermal dual cured composite direct write 3D printing medium according to claim 3, wherein the temperature of the first mix material is raised to 50-80 ℃ in step S2, and the temperature of the second mix material is lowered to below 50 ℃ in step S3.
12. The application of the composite direct-writing 3D printing medium is characterized in that the photothermal dual-curing composite direct-writing 3D printing medium according to any one of claims 1 to 2 is applied to direct-writing 3D printing, the printed line width is 1-200 microns, and the printing medium is suitable for line printing with the aspect ratio larger than 0.5.
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