CN108249912A - A kind of method for preparing three-dimensional nano titania porous structure using direct write molding 3D printing technique - Google Patents
A kind of method for preparing three-dimensional nano titania porous structure using direct write molding 3D printing technique Download PDFInfo
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- CN108249912A CN108249912A CN201810047404.4A CN201810047404A CN108249912A CN 108249912 A CN108249912 A CN 108249912A CN 201810047404 A CN201810047404 A CN 201810047404A CN 108249912 A CN108249912 A CN 108249912A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
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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
- B33Y10/00—Processes of additive manufacturing
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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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
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Abstract
The present invention relates to a kind of methods for preparing three-dimensional nano titania porous structure using direct write molding 3D printing technique, it includes the following steps：(a) F127 dispersion liquids are formed, then adds in nano titanium dioxide powder several times into the F127 dispersion liquids and forms TiO2Slurry；The addition of the nano titanium dioxide powder is successively decreased successively；(b) by the TiO2Slurry is transferred in syringe, and it is made to connect the adapter of gas pressure regulator with one end and is connected；Then the syringe is installed on 3D printer；(c) print routine is write according to required three-dimensional structure in a computer；(d) air pressure for adjusting and testing the gas pressure regulator makes TiO2Slurry squeezes out, then 3D printer is controlled to be printed by print routine by computer；(e) high-temperature calcination is carried out after step (d) products obtained therefrom is dried.Directly printing prepares the three-dimensional nano titania porous structure with abundant nano aperture at room temperature；And it can be adapted for a variety of three-dimensional structures of rapid shaping.
Description
Technical field
The invention belongs to the three-dimensional structure rapid shaping fields of nano material, and it is porous to be related to a kind of three-dimensional nano titania
The preparation method of structure, and in particular to a kind of to prepare three-dimensional nano titania porous structure using direct write molding 3D printing technique
Method.
Background technology
In recent years, 3D printing technique has shown the prospect of being widely applied as a kind of increases material manufacturing technology, it is considered to be
It realizes one of key technology of industrial technology innovation next time, great concern is all caused in academia and industrial quarters.3D is beaten
Print is as a kind of novel, flexible forming technique, suitable for fast, accurately manufacturing 3 D complex structure.Compared to it is traditional into
Type technology, 3D printing technique have many advantages, such as easy to use, high reliability, high performance-price ratio and various material compatibility.This
A little characteristics make 3D printing technique that can not only manufacture small sensor and micro-fluidic device in microelectronics and micro-system, can also manufacture
Greatly to the large-sized structural parts such as the undercarriage in aircraft industry and petroleum pipeline.
It is multidisciplinary that direct write molding 3D printing technique based on slurry combines CAD, chemistry and materialogy etc.
The Moldless molding method using no mold in field, make it possible complexity, fine structure in three dimensions quick manufacture and integrated molding.
Using CAD three-dimensional structure, by the control to slurry rheological property, control slurry is squeezed out from nozzle, layer stackup
Add, quickly prepare various complicated, fine three-dimensional structures.Compared with other forming methods, the direct write molding 3D based on slurry is beaten
The technical characterstic of print includes：First, raw material nano-powder, which is dispersed in liquid phase medium, forms stable, uniform slurry, passes through
The requirement of 3D printing is adapted for the regulation and control of its rheologic behavio(u)r, material forming process is more simple and practicable and safe and harmless；The
Two, it can significantly alleviate malformation and collapse phenomenon caused by drying and sintering using the higher slurry of solid concentration, can avoid
Its physical property to structure damages；Third, by loading multiple print heads, squeezed out in same forming process it is different into
The slurry divided, can freely construct the three-dimensional structure of heterogeneity, it can be achieved that the rapid shaping of multifunctional gradient composite structure.
Therefore, the direct write molding 3D printing technique based on slurry has many merits：First, it can easily change the shape of molding structure
Size, control is accurate and operation is flexible；Second is that can greatly shorten the production cycle without expensive mold in forming process, improve
Efficiency reduces production cost；Third, the requirement to raw material is low, be applicable to Multimetal oxide, organic polymer and
Other composite materials；Fourth, being widely used, the functional material and device of optics, electronic field and biological field can be prepared
Invention content
A kind of utilization direct write the invention aims to overcome the deficiencies in the prior art is provided and is molded 3D printing technique system
The method of standby three-dimensional nano titania porous structure.
In order to achieve the above objectives, the technical solution adopted by the present invention is：It is a kind of to be prepared using direct write molding 3D printing technique
The method of three-dimensional nano titania porous structure, it includes the following steps：
(a) polymer powder is added in into deionized water and forms polymer dispersion liquid, then into the polymer dispersion liquid
Nano-TiO is added in several times2Powder forms TiO2Mass fraction is 30~60% slurry；The nano titanium dioxide powder
Addition is successively decreased successively；The polymer is F-127, polyvinyl alcohol or acrylic resin；
(b) by the TiO2Slurry is transferred in syringe, and it is made to connect the adapter of gas pressure regulator with one end and is connected
It connects；Then the syringe is installed on 3D printer；
(c) print routine is write according to required three-dimensional structure in a computer；
(d) air pressure for adjusting and testing the gas pressure regulator makes TiO2Slurry squeezes out, then 3D is controlled to beat by computer
Print machine is printed by print routine；
(e) high-temperature calcination is carried out after step (d) products obtained therefrom is dried.
Optimally, it is further included：
(f) by 1H, 1H, 2H, 2H- perfluor certain herbaceous plants with big flowers base trimethoxy silanes, which are dissolved in organic solvent, forms mixed solution, then to
The mixed solution, the three-dimensional manometer titanium dioxide are sequentially added in container to be heated.
It further,, will before adding in nano titanium dioxide powder several times into the F127 dispersion liquids in step (a)
The F127 dispersion liquids make its transparent, clarification as refrigeration under conditions of 2~5 DEG C.
Further, it in step (a), after adding in nano titanium dioxide powder into the F127 dispersion liquids, is put
In on planetary mixer under 1000~2000rpm/min rotating speeds stir 1~5min.
Further, in step (b), by the TiO2After slurry is transferred to syringe, is shaken and to stand 10~30 small
When to remove TiO2Bubble in slurry.
Further, it in step (e), spontaneously dries 10~30 hours at room temperature.
Further, in step (e), 600~1200 DEG C are warming up to the heating rate of 3~10 DEG C/min, heat preservation sintering
It is cooled to room temperature again with the rate of 3~10 DEG C/min after 0.5~2 hour.
Further, in step (f), the organic solvent is one kind in toluene and n-hexane, described organic
Solvent and the 1H, 1H, 2H, the volume ratio of 2H- perfluor certain herbaceous plants with big flowers base trimethoxy silanes is 10~100：1.
Further, in step (f), the heat treatment is keeps the temperature 1~5 hour under conditions of 60~100 DEG C
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：The present invention utilizes direct write
The method that 3D printing technique prepares three-dimensional nano titania porous structure is molded, by the way that high concentration TiO is configured2Slurry and it is direct
3D printing is carried out, it is porous so as to directly three-dimensional nano titania of the printing preparation with abundant nano aperture at room temperature
Structure；And can be adapted for a variety of three-dimensional structures of rapid shaping, there is very high design freedom；Also have it is easy to operate,
The advantages that saving raw material and nontoxic, pollution-free material therefor；And prepare three-dimensional nano titania porous structure degradation,
The fields such as catalysis and sensor have wide practical use.
Description of the drawings
Fig. 1 is TiO2 apparent viscosity of slurry-shear rate curve that the present invention is configured；
Fig. 2 is that the nanometer titanium dioxide titanium products with porous structure are made in embodiment 1：(a) print procedure schematic diagram；
(b) macroscopical sample photo；
Fig. 3 is that SEM of the nanometer titanium dioxide titanium products with porous structure in different enlargement ratios is made in embodiment 1
Figure：
Fig. 4 be embodiment 1 in through silicon fluoride treated have porous structure nano-titanium dioxide product surface leaching
Moisten effect photo：(a) chromonic is in the infiltration picture of sample surfaces；(b) the contact angle test chart of sample.
Specific embodiment
The method that the present invention prepares three-dimensional nano titania porous structure using direct write molding 3D printing technique, it includes
Following steps：(a) polymer powder is added in into deionized water and forms polymer dispersion liquid, then into the polymer dispersion liquid
Nano-TiO is added in several times2Powder forms TiO2Mass fraction is 30~60% slurry；The nano titanium dioxide powder
Addition is successively decreased successively；The polymer is F-127, polyvinyl alcohol or acrylic resin；(b) by the TiO2Slurry is transferred to
In syringe, and it is made to connect the adapter of gas pressure regulator with one end and is connected；The syringe is then installed to 3D printer
On；(c) print routine is write according to required three-dimensional structure in a computer；(d) adjust and test the gas of the gas pressure regulator
Pressure makes TiO2Slurry squeezes out, then 3D printer is controlled to be printed by print routine by computer；It (e) will be obtained by step (d)
High-temperature calcination is carried out after product drying.By the way that high concentration TiO is configured2Slurry and directly carry out 3D printing, so as to
Directly printing prepares the three-dimensional nano titania porous structure with abundant nano aperture without caving at room temperature；It and can be with
Suitable for three-dimensional structure as rapid shaping multiple types, there is very high design freedom；Also there is easy to operate, saving original
The advantages that material and material therefor are nontoxic, pollution-free；And prepare three-dimensional nano titania porous structure degradation, catalysis and
The fields such as sensor have wide practical use.
The above-mentioned method for preparing three-dimensional nano titania porous structure using direct write molding 3D printing technique, it is also wrapped
It includes：(f) by 1H, 1H, 2H, 2H- perfluor certain herbaceous plants with big flowers base trimethoxy silanes, which are dissolved in organic solvent, forms mixed solution, then into container
The mixed solution, the three-dimensional manometer titanium dioxide are sequentially added to be heated；By silicon fluoride, treated three
Nano titania porous structure surface contact angle is tieed up up to being 140 °, it is achieved thereby that three-dimensional nano titania structure is super thin
The ability of water surface is laid a good foundation to prepare super-drainage structure using 3D printing method；The realization of ultra-hydrophobicity not only relies on
In the more hollow structures of nanometer, it is also desirable to carry out silane surface processing.In step (a), added in several times into the F127 dispersion liquids
Before nano titanium dioxide powder, the F127 dispersion liquids are made into its transparent, clarification as refrigeration under conditions of 2~5 DEG C；To described
After adding in nano titanium dioxide powder in F127 dispersion liquids, place it on planetary mixer and turn in 1000~2000rpm/min
1~5min of the lower stirring of speed；In step (b), by the TiO2After slurry is transferred to syringe, is shaken and stand 10~30 hours
To remove TiO2Bubble in slurry；The above-mentioned dispersibility for being conducive to improve nano-titanium dioxide is to ensure final TiO2Slurry
Nano titanium dioxide powder with high-content and stabilization.In step (e), usually spontaneously dry 10~30 hours at room temperature.
In step (e), 600~1200 DEG C are warming up to the heating rate of 3~10 DEG C/min, heat preservation sintering is after 0.5~2 hour again with 3
The rate of~10 DEG C/min is cooled to room temperature.In step (f), the organic solvent is one kind in toluene and n-hexane,
The organic solvent and the 1H, 1H, 2H, the volume ratio of 2H- perfluor certain herbaceous plants with big flowers base trimethoxy silanes is 10~100：1, with optimization
Hydrophobic effect；In step (f), the heat treatment is keeps the temperature 1~5 hour under conditions of 60~100 DEG C.
The present invention is further described below in conjunction with embodiment.
Embodiment 1
The present embodiment provides a kind of three-dimensional nano titania porous structure is prepared using direct write molding 3D printing technique
Method, it includes the following steps：
(a) deionized water of 120ml is added in beaker, is persistently stirred at 20 DEG C and is slowly added to F127 powder
(Pluronic, CMC:900~1000ppm, SIGMA), prepare the F127 dispersion liquids that mass fraction is 40wt%；Disperse to F127
Nano titanium dioxide powder (total 200g, average grain diameter 21nm, Degussa) is added in liquid in three times；Nanometer two is added in every time
After titanium oxide need on planetary mixer under 1000~2000rpm/min rotating speeds 1~5min of stir about；With slurry viscosity
Raising, the nano titanium dioxide powder amount of addition constantly successively decrease and (are followed successively by 120g, 60g, 20g), equal to be conducive to obtain mixing
Even slurry；It is final to be configured to the TiO that mass fraction is 50wt%2Slurry.The results are shown in Figure 1 for rheometer test, the slurry
Apparent viscosity increase and linear reduction with shear rate, there is shear shinning property, be suitble to do direct write molding 3D printing slurry.
(b) by TiO2Slurry is transferred in syringe (the special syringe of 3cc), is shaken and is stood 24 hours further removal slurries
Bubble in material；The adapter for then syringe being made to connect gas pressure regulator with one end is connected；Then the syringe is installed to
It (needs to select appropriately sized syringe needle, and for syringe to be fixed on the fixed transverse rod of 3D printer mechanical arm) on 3D printer；
(c) print routine is write according to required three-dimensional structure in a computer (step can be in the advance of step (a)
Row needs design to want molding three-dimensional structure, and write print routine according to existing computer literacy；Or using existing
Three-dimensional structure print routine)；
(d) it adjusts and the air pressure of measuring air pressure controller makes TiO2Slurry, which squeezes out, (realizes that slurry is smoothly squeezed from syringe needle
Go out), then 3D printer is controlled to be printed by print routine to obtain product (such as Fig. 2 (a) of corresponding three-dimensional structure by computer
With Fig. 2 (b) Suo Shi)；As it can be seen that realize prepare centimetres, have three dimensional network structure, porous structure nanometer titanium dioxide
Titanium, so that the size and three-dimensional structure of the structure based on direct write molding 3D printing technique preparation can be adjusted easily.
(e) step (d) products obtained therefrom is placed in and spontaneously dried 24 hours at room temperature, be then transferred into Muffle furnace and carry out heat
The three-dimensional nano titania with porous structure is made in processing.Heat treatment parameter is as follows：With the heating rate liter of 5 DEG C/min
To 900 DEG C, then heat preservation sintering 0.5~2 hour is cooled to room temperature temperature with 5 DEG C/min rate of temperature fall.It is micro- for characterization sample surfaces
Pattern, size and the distribution of hole are tested using scanning electron microscope (SEM) using the three-dimensional manometer titanium dioxide prepared
Surface microscopic topographic, as shown in Fig. 3 (a)-Fig. 3 (c).It can be seen that after thermally treated, using the three-dimensional dioxy of this technique preparation
The titania nanoparticles for changing titanium nano-porous structure surface have mutually been sintered concurrent first portion fusion phenomenon, while more uniform
Be dispersed with abundant micron, nano aperture structure.
(f) 1H, 1H, 2H of 30~100 μ L, 2H- perfluor certain herbaceous plants with big flowers base trimethoxy silanes, ultrasound are added in into 1~3ml toluene
It is placed in after five minutes in vacuum ware, then three-dimensional nano titania product obtained in step (e) is put into vacuum ware；By vacuum
Ware is placed in 80 DEG C of baking oven and handles 3 hours.
Surface silicon fluoride processing is carried out by the three-dimensional titanium dioxide to 3D printing, using the abundant micron in its surface, is received
Rice pore space structure, makes which give good surface super hydrophobic characteristics.As shown in Fig. 4 (a), it is added dropwise after silicon fluoride hydrophobic treatment
The chromonic on three-dimensional titania structure surface do not penetrate into grid, three-dimensional grid table is still attached in the form of drop
Face.Surface contact angle test result shows, silicon fluoride treated three-dimensional nano titania porous structure surface contact angle is about
For 140 ° (such as Fig. 4 (b)) Suo Shi.It can be seen that the surface micro-nano structure feature of the three-dimensional nano titania porous structure of preparation, makes
It has the ability of structure super hydrophobic surface, lays a good foundation to prepare super-drainage structure using 3D printing method.
Embodiment 2
The present embodiment provides a kind of three-dimensional nano titania porous structure is prepared using direct write molding 3D printing technique
Method, it is basically identical with the step in embodiment 1, unlike：The TiO formed is configured2The mass fraction of slurry is
30wt%.
Embodiment 3
The present embodiment provides a kind of three-dimensional nano titania porous structure is prepared using direct write molding 3D printing technique
Method, it is basically identical with the step in embodiment 1, unlike：The TiO formed is configured2The mass fraction of slurry is
60wt%.
Embodiment 4
The present embodiment provides a kind of three-dimensional nano titania porous structure is prepared using direct write molding 3D printing technique
Method, it is basically identical with the step in embodiment 1, unlike：It, which does not include, step (f), and product is hydrophilic, is not had
There is superhydrophobic characteristic.
Comparative example 1
The present embodiment provides a kind of three-dimensional nano titania porous structure is prepared using direct write molding 3D printing technique
Method, it is basically identical with the step in embodiment 1, unlike：In step (a), disposably added in into F127 dispersion liquids
Nano titanium dioxide powder cannot get the uniform sizing material that mass fraction is up to 50wt% in this way.
Comparative example 2
The present embodiment provides a kind of methods of titanium dioxide nanostructure, it is basically identical with the step in embodiment 1, no
Be：The titanium dioxide layer of plane is prepared in step (d) using spraying technology, product does not have super-hydrophobic spy yet
Property.
Comparative example 3
The present embodiment provides a kind of three-dimensional nano titania porous structure is prepared using direct write molding 3D printing technique
Method, it is basically identical with the step in embodiment 1, unlike：The TiO formed is configured2The mass fraction of slurry is only
20wt%.
Although can form three-dimensional nano titania porous structure in comparative example 3, viscosity is relatively low and causes certainly
Support performance is slightly worse so that sedimentation, bonding phenomenon occurs in the three-dimensional structure of printing, and printing precision reduces；It is obtained in embodiment 1
Slurry print performance is best；The slurry obtained in embodiment 3 causes to be susceptible to plug phenomenon during printing since viscosity is higher,
Cause printing fluency poor.In addition, polymer selects the performance of F-127 best, and polyvinyl alcohol or acrylic resin are only capable of
Realize aforesaid operations, final products performance is general.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of method for preparing three-dimensional nano titania porous structure using direct write molding 3D printing technique, feature exist
In it includes the following steps：
(a) polymer powder is added in into deionized water and forms polymer dispersion liquid, then into the polymer dispersion liquid it is point more
Secondary addition nano-TiO2Powder forms TiO2Mass fraction is 30~60% slurry；The addition of the nano titanium dioxide powder
Amount is successively decreased successively；The polymer is F-127, polyvinyl alcohol or acrylic resin；
(b) by the TiO2Slurry is transferred in syringe, and it is made to connect the adapter of gas pressure regulator with one end and is connected；With
The syringe is installed on 3D printer afterwards；
(c) print routine is write according to required three-dimensional structure in a computer；
(d) air pressure for adjusting and testing the gas pressure regulator makes TiO2Slurry squeezes out, then 3D printer is controlled to press by computer
Print routine is printed；
(e) high-temperature calcination is carried out after step (d) products obtained therefrom is dried.
2. the side of three-dimensional nano titania porous structure is prepared using direct write molding 3D printing technique according to claim 1
Method, which is characterized in that it is further included：
(f) by 1H, 1H, 2H, 2H- perfluor certain herbaceous plants with big flowers base trimethoxy silanes, which are dissolved in organic solvent, forms mixed solution, then to container
In sequentially add the mixed solution, the three-dimensional manometer titanium dioxide to be heated.
3. according to claim 1 or claim 2 prepare three-dimensional nano titania porous structure using direct write molding 3D printing technique
Method, it is characterised in that：It, will before adding in nano titanium dioxide powder several times into the F127 dispersion liquids in step (a)
The F127 dispersion liquids make its transparent, clarification as refrigeration under conditions of 2~5 DEG C.
4. the side of three-dimensional nano titania porous structure is prepared using direct write molding 3D printing technique according to claim 3
Method, it is characterised in that：In step (a), after adding in nano titanium dioxide powder into the F127 dispersion liquids, planet is placed it in
1~5min is stirred on blender under 1000~2000rpm/min rotating speeds.
5. according to claim 1 or claim 2 prepare three-dimensional nano titania porous structure using direct write molding 3D printing technique
Method, it is characterised in that：In step (b), by the TiO2After slurry is transferred to syringe, is shaken and to stand 10~30 small
When to remove TiO2Bubble in slurry.
6. according to claim 1 or claim 2 prepare three-dimensional nano titania porous structure using direct write molding 3D printing technique
Method, it is characterised in that：In step (e), spontaneously dry 10~30 hours at room temperature.
7. according to claim 1 or claim 2 prepare three-dimensional nano titania porous structure using direct write molding 3D printing technique
Method, it is characterised in that：In step (e), 600~1200 DEG C are warming up to the heating rate of 3~10 DEG C/min, heat preservation sintering
It is cooled to room temperature again with the rate of 3~10 DEG C/min after 0.5~2 hour.
8. the side of three-dimensional nano titania porous structure is prepared using direct write molding 3D printing technique according to claim 2
Method, it is characterised in that：In step (f), the organic solvent is one kind in toluene and n-hexane, the organic solvent with
The 1H, 1H, 2H, the volume ratio of 2H- perfluor certain herbaceous plants with big flowers base trimethoxy silanes is 10~100：1.
9. three-dimensional nano titania porous structure is prepared using direct write molding 3D printing technique according to claim 2 or 8 is described
Method, it is characterised in that：In step (f), the heat treatment is keeps the temperature 1~5 hour under conditions of 60~100 DEG C.
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| CN109111223A (en) * | 2018-09-18 | 2019-01-01 | 中国科学院宁波材料技术与工程研究所 | 3D direct write printing titanium dioxide ceramic composition, slurry, preparation method and application |
| CN109499561A (en) * | 2018-12-18 | 2019-03-22 | 华中科技大学 | A kind of method of increasing material manufacturing three-dimensional photocatalysis material of titanium dioxide |
| CN109878071A (en) * | 2019-03-01 | 2019-06-14 | 西安交通大学 | A method of ionic pressure sensor array is prepared based on 3D printing |
| CN110871068A (en) * | 2019-12-13 | 2020-03-10 | 苏州大学 | TiO 22Synthesis method of porous frame/Pd nanoparticle composite catalyst, composite catalyst and application thereof |
| CN111569870A (en) * | 2020-06-12 | 2020-08-25 | 苏州大学 | Preparation method of optical composite catalyst, optical composite catalyst and application thereof |
| CN113307620A (en) * | 2021-06-17 | 2021-08-27 | 西华大学 | Titanium dioxide ceramic slurry for direct-writing forming 3D printing and preparation method thereof |
| CN113526975A (en) * | 2020-04-16 | 2021-10-22 | 中国石油天然气股份有限公司 | Alumina carrier material with gradient structure and 3D printing forming method thereof |
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| CN109499561A (en) * | 2018-12-18 | 2019-03-22 | 华中科技大学 | A kind of method of increasing material manufacturing three-dimensional photocatalysis material of titanium dioxide |
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| CN111569870A (en) * | 2020-06-12 | 2020-08-25 | 苏州大学 | Preparation method of optical composite catalyst, optical composite catalyst and application thereof |
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