CN110119038B - Thermal field adjustable terahertz wave optical window and preparation method and application thereof - Google Patents
Thermal field adjustable terahertz wave optical window and preparation method and application thereof Download PDFInfo
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- CN110119038B CN110119038B CN201810117461.5A CN201810117461A CN110119038B CN 110119038 B CN110119038 B CN 110119038B CN 201810117461 A CN201810117461 A CN 201810117461A CN 110119038 B CN110119038 B CN 110119038B
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- 230000003287 optical effect Effects 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 238000005516 engineering process Methods 0.000 claims abstract description 13
- 238000010146 3D printing Methods 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 24
- 238000007639 printing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 230000000737 periodic effect Effects 0.000 claims description 8
- 238000001029 thermal curing Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001723 curing Methods 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 6
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 6
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 5
- 239000002023 wood Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 238000001328 terahertz time-domain spectroscopy Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
-
- 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
-
- 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
- B33Y80/00—Products made by additive manufacturing
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/0009—Materials therefor
- G02F1/009—Thermal properties
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
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- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
The invention discloses a terahertz wave optical window with an adjustable thermal field and a preparation method and application thereof, and belongs to the technical field of 3D printing and terahertz wave application. Directly preparing and molding the slurry with the thermochromic characteristic by a 3D printing die-free direct writing technology to obtain the terahertz wave optical window with the three-dimensional space structure. The terahertz wave optical window can realize selective permeation of terahertz waves with different wavelengths under the regulation and control of a thermal field, solves the defect that the traditional optical window cannot respond to the external environment in real time, and particularly can be used as a heat sensor to realize the functions of early warning and sensing of temperature change.
Description
Technical Field
The invention relates to the technical field of 3D printing and terahertz wave application, in particular to a terahertz wave optical window with an adjustable thermal field and a preparation method and application thereof.
Background
Terahertz waves refer to waves with a frequency of 0.1-10THz (1THz ═ 10)12Hz) having a wavelength in the range of 3mm to 30 μm. In recent years, with the development of ultrafast optics, terahertz technology and applications have made significant progress. The characteristics of high permeability, transient property, low energy, coherence, fingerprint spectrum and the like of the terahertz wave enable the terahertz technology to have great application potential in the fields of wireless communication, biomedical imaging, nondestructive testing, material identification, national defense industry and the like. The terahertz wave optical window is a photoelectric device capable of generating optical response to terahertz waves, can regulate and control the transmission of the terahertz waves, and is one of key devices of the terahertz technology. Once the traditional terahertz wave optical window is formed, the optical characteristics of the traditional terahertz wave optical window cannot be changed. With the complexity of application environment, a terahertz wave optical window with adjustable optical characteristics is urgently needed, and the terahertz wave optical window can respond to the change of the external environment in real time.
The thermochromic material refers to a material in which optical characteristics are changed due to phase change or crystal transformation during heating or cooling. In the phase change process, the dielectric property of the thermochromic material can be greatly changed, so that an electromagnetic wave functional device capable of responding to temperature in real time can be prepared by utilizing the change of the dielectric property. The key issues that this technology has achieved are the choice of thermochromic materials, and the design of hybrid materials with thermochromic properties (since only thermochromic component material systems are often not easily moldable to form specific optical windows). In addition, this type of mixed material system is required to have not only suitable optical characteristics but also few rheological characteristics, wettability and processing formability so as to be three-dimensionally designed to satisfy the response to electromagnetic waves of a specific wavelength band in various practical situations.
In the aspect of preparation of terahertz devices, compared with microwave devices, the terahertz devices are smaller in size, and the traditional processing method is difficult to meet the precision requirement. The 3D printing technology based on the mode-free direct writing forming can realize the preparation of a complex three-dimensional structure with the characteristic dimension ranging from submicron to several millimeters, and provides a new method for the preparation and processing of terahertz devices.
Disclosure of Invention
The invention aims to provide a terahertz wave optical window with an adjustable thermal field, and a preparation method and application thereof. Directly preparing and molding the slurry with the thermochromic characteristic by a 3D printing die-free direct writing technology to obtain the terahertz wave optical window with the three-dimensional space structure. The terahertz wave optical window can realize selective permeation of terahertz waves with different wavelengths under the regulation and control of a thermal field, solves the defect that the traditional optical window cannot respond to the external environment in real time, and particularly can be used as a heat sensor to realize the functions of early warning and sensing of temperature change.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a terahertz wave optical window with an adjustable thermal field is characterized by comprising the following steps: according to the method, the slurry with the thermochromic characteristic is directly prepared and molded through a 3D printing die-free direct writing technology, and the terahertz wave optical window with the three-dimensional space structure is obtained. The method specifically comprises the following steps:
(1) preparing slurry: adding a powdery thermochromic material into a parent material, and uniformly mixing to obtain slurry; the content of thermochromic material in the slurry is 5-95 wt.%; the prepared slurry has the property of shear thinning, and can meet the requirements of 3D printing dieless direct-writing forming technology on the rheological property of the slurry.
(2) The structure is as follows: preparing the prepared slurry into an optical window with a three-dimensional periodic structure by adopting a 3D printing die-free direct-writing forming technology;
(3) curing and forming: carrying out thermocuring treatment on the printed optical window with the three-dimensional periodic structure, wherein the thermocuring temperature is 60-100 ℃, and the thermocuring time is 2-10 hours; and obtaining the terahertz wave optical window with the adjustable thermal field after thermal curing treatment.
In the step (1), the color change temperature range of the thermochromic material is within 200 ℃. The thermochromic material is preferably VO2、V1-xWxO2、Sm3Fe5-xAlxO12、La1-xSrxMnO3、CuHgI4、Ag2HgI4、[(CH3)2CHNH2]CuCl3Wherein: x is 0-0.9; or the thermochromic material is tungstate, vanadate or chromate with other thermochromic characteristics.
In the step (1), the matrix material is a material with small terahertz wave absorption, such as PDMS silica gel, glass sealant or resin.
In the step (1), the transmittance of the terahertz wave optical window can be changed by adjusting the content of the thermochromic material in the slurry.
The specific process of the step (2) is as follows: firstly, writing a three-dimensional periodic structure printing program by using a G code; then the slurry is loaded into a barrel; and printing the three-dimensional optical window according to the three-dimensional structure path. When a three-dimensional periodic structure is compiled, the spacing of the dielectric rods is set to be 30-1000 mu m, and the number of layers is set to be more than 4; and selecting a needle head with the diameter of 10-500 mu m from the charging barrel, and printing layer by layer to obtain a preformed terahertz wave optical window. In the process, the three-dimensional optical windows with different structural parameters can be printed to adapt to different working wavelengths by selecting needles with different diameters, designing different printing programs and adjusting printing parameters.
The terahertz wave optical window with the adjustable thermal field is prepared by adopting the method, the optical window responds to the external environment temperature in real time, and the terahertz waves with different wavelengths can be selectively transmitted under the regulation and control of the thermal field. Particularly, the terahertz wave optical window can also be used as a heat sensor to realize the functions of early warning and sensing of temperature change.
The invention has the following advantages and beneficial effects:
1. according to the invention, the accurate forming of the terahertz wave optical window with the adjustable thermal field is realized by adopting the thermochromic material and combining the 3D printing technology. The terahertz wave optical window with a specific working wavelength can be prepared by flexibly designing the structural parameters and adjusting the printing parameters.
2. The terahertz wave optical window prepared by the invention can respond to the external environment temperature in real time, and can realize selective transmission of terahertz waves with different wavelengths under the regulation and control of a thermal field.
Drawings
FIG. 1 is a thermal field tunable terahertz optical window prepared in example 1; wherein: (a) the optical picture is an optical window with the diameter of a dielectric rod being 210 mu m, the interval being 700 mu m and the number of layers being 8; (b) a front Scanning Electron Microscope (SEM) picture of the optical window; (c) a cross-sectional Scanning Electron Microscope (SEM) picture of the optical window.
FIG. 2 is a photonic band gap diagram of an optical window of a thermal field tunable terahertz wave prepared in example 1, wherein the optical window has a diameter of 210 μm, a pitch of 700 μm and 8 layers at 25 ℃ and 75 ℃.
FIG. 3 is a photonic band gap diagram of an optical window of a thermal field tunable terahertz wave prepared in example 2, wherein the optical window has a diameter of 210 μm, a pitch of 600 μm and 8 layers at 25 ℃ and 75 ℃.
FIG. 4 is a photonic band gap diagram of a thermal field tunable terahertz wave optical window with a diameter of 210 μm, a pitch of 600 μm and 4 layers prepared in example 3 at 25 ℃ and 75 ℃.
Detailed Description
The present invention will be further described with reference to specific examples.
Example 1
1. Weighing 4g of vanadium dioxide powder, adding the vanadium dioxide powder into 4g of Dow Corning SE1700 silica gel, mechanically stirring uniformly to obtain slurry with the vanadium dioxide content of 50 wt.%, and filling the slurry into a 10mL charging barrel to be printed.
2. Writing a 3D printing program of a wood stack structure, setting the space of media rods to be 700 mu m, setting the number of layers to be 8, selecting a needle head with the diameter of 210 mu m, setting the extrusion pressure to be 60psi, and printing at the printing speed of 10mm/s, and printing layer by layer to obtain a preformed terahertz wave optical window.
3. And carrying out heat curing treatment on the preformed optical window for 2 hours at 80 ℃ to obtain the terahertz wave optical window with the adjustable thermal field, wherein the diameter of the dielectric rod is 210 micrometers, the interval is 700 micrometers, and the number of layers is 8. The structure of the optical window is a three-dimensional wood pile structure, and an optical picture and a scanning electron microscope picture of the optical window are shown in figure 1.
4. The terahertz time-domain spectroscopy test is carried out on the optical window at 25 ℃ and 75 ℃ respectively, and a photonic band gap diagram of the optical window is obtained after the rapid Fourier transform, as shown in figure 2.
The optical window has a bandgap position at 25 deg.C at room temperature of 0.295THz and a bandgap depth of-23 dB, and when the temperature is raised to 75 deg.C, the bandgap position is shifted to low frequency of 0.270THz and the bandgap depth is-27 dB.
Example 2
1. A slurry with a vanadium dioxide content of 50 wt.% was formulated as in step 1 of example 1 and charged into a 10mL cartridge to be printed.
2. Writing a 3D printing program of a wood stack structure, setting the space of media rods to be 600 mu m, setting the number of layers to be 8, selecting a needle head with the diameter of 210 mu m, setting the extrusion pressure to be 60psi, and printing at the printing speed of 10mm/s, and printing layer by layer to obtain a preformed terahertz wave optical window.
3. And carrying out heat curing treatment on the preformed optical window for 2 hours at 80 ℃ to obtain the terahertz wave optical window with the adjustable thermal field, wherein the diameter of the dielectric rod is 210 micrometers, the interval is 600 micrometers, and the number of layers is 8.
4. The terahertz time-domain spectroscopy test is carried out on the optical window at 25 ℃ and 75 ℃ respectively, and a photonic band gap diagram of the optical window is obtained after the rapid Fourier transform, as shown in figure 3.
The optical window has a bandgap position of 0.325THz and a bandgap depth of-25.0 dB at room temperature of 25 deg.C, and moves to a low frequency of 0.300THz and a bandgap depth of-27.0 dB when the temperature is raised to 75 deg.C.
Example 3
1. A slurry with a vanadium dioxide content of 50 wt.% was formulated as in step 1 of example 1 and charged into a 10mL cartridge to be printed.
2. Writing a 3D printing program of a wood stack structure, setting the space of media rods to be 600 mu m, setting the number of layers to be 4, selecting a needle head with the diameter of 210 mu m, setting the extrusion pressure to be 60psi, and printing at the printing speed of 10mm/s, and printing layer by layer to obtain a preformed terahertz wave optical window.
3. And carrying out heat curing treatment on the preformed optical window for 2 hours at 80 ℃ to obtain the terahertz wave optical window with the adjustable thermal field, wherein the diameter of the dielectric rod is 210 micrometers, the interval is 600 micrometers, and the number of layers is 4.
4. The terahertz time-domain spectroscopy test is carried out on the optical window at 25 ℃ and 75 ℃ respectively, and a photonic band gap diagram of the optical window is obtained after the rapid Fourier transform, as shown in figure 4.
The optical window has a bandgap location of 0.325THz and a bandgap depth of-13.3 dB at room temperature of 25 deg.C, and moves to a low frequency of 0.300THz and a bandgap depth of-15.0 dB when the temperature is raised to 75 deg.C.
The above examples are only for reference, and the method for preparing the thermal field adjustable terahertz wave optical window through 3D printing, which is similar to or extends from the idea of the present patent, is within the protection scope of the present patent.
Claims (4)
1. A preparation method of a terahertz wave optical window with an adjustable thermal field is characterized by comprising the following steps: firstly, preparing slurry with a thermochromic characteristic, and then preparing the terahertz wave optical window with the adjustable thermal field by the slurry through a 3D printing die-free direct-writing forming technology; the method specifically comprises the following steps:
(1) preparing slurry: adding a powdery thermochromic material into a parent material, and uniformly mixing to obtain slurry; the content of thermochromic material in the slurry is 5-95 wt.%;
(2) the structure is as follows: the prepared slurry is prepared into an optical window with a three-dimensional periodic structure by adopting a 3D printing die-free direct-writing forming technology, and the specific process comprises the following steps: firstly, writing a three-dimensional periodic structure printing program by using a G code; then the slurry is loaded into a barrel; printing the three-dimensional optical window according to the three-dimensional structure path; when the three-dimensional periodic structure is compiled, the spacing of the dielectric rods is set to be 30-1000 mu m, and the number of layers is set to be more than 4; selecting a needle head with the diameter of 10-500 mu m from the charging barrel, and printing layer by layer to obtain a preformed terahertz wave optical window;
(3) curing and forming: carrying out thermocuring treatment on the printed optical window with the three-dimensional periodic structure, wherein the thermocuring temperature is 60-100 ℃, and the thermocuring time is 2-10 hours; obtaining the terahertz wave optical window with the adjustable thermal field after thermal curing treatment;
in the step (1), the color change temperature range of the thermochromic material is within 200 ℃, and the parent material is PDMS silica gel, glass sealant or resin; the thermochromic material is V1-xWxO2、Sm3Fe5-xAlxO12、La1-xSrxMnO3、CuHgI4、Ag2HgI4、[(CH3)2CHNH2]CuCl3Or other tungstate, vanadate or chromate salts having thermochromic properties; wherein: x is 0-0.9;
in the step (1), the transmittance of the terahertz wave optical window can be changed by adjusting the content of the thermochromic material in the slurry.
2. The method for preparing the terahertz wave optical window with the adjustable thermal field according to claim 1, which is characterized in that: by selecting needles with different diameters, designing different printing programs and adjusting printing parameters, three-dimensional optical windows with different structural parameters can be printed to adapt to different working wavelengths.
3. A terahertz wave optical window with adjustable thermal field prepared by the method of claim 1, which is characterized in that: the terahertz wave optical window can realize selective transmission of terahertz waves with different wavelengths under the regulation and control of the thermal field.
4. The application of the optical window of terahertz waves with adjustable thermal field according to claim 3, is characterized in that: the terahertz wave optical window is used as a heat sensor to realize the functions of early warning and sensing of temperature change.
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| CN105500719A (en) * | 2016-01-28 | 2016-04-20 | 北京交通大学 | Method for manufacturing terahertz waveguide preform by means of 3D printing technology |
| CN106046717A (en) * | 2016-07-29 | 2016-10-26 | 佛山市高明区诚睿基科技有限公司 | Thermochromic PBS composite wire for 3D printing |
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