CN108084624A - A kind of preparation method for having defective Responsive photonic crystals - Google Patents

A kind of preparation method for having defective Responsive photonic crystals Download PDF

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CN108084624A
CN108084624A CN201810013115.2A CN201810013115A CN108084624A CN 108084624 A CN108084624 A CN 108084624A CN 201810013115 A CN201810013115 A CN 201810013115A CN 108084624 A CN108084624 A CN 108084624A
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ipn
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photonic crystals
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CN108084624B (en
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鲁希华
李晓晓
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Donghua University
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Abstract

The invention discloses a kind of preparation methods for having defective Responsive photonic crystals, which is characterized in that adds in deionized water monomer N N-isopropylacrylamides etc. and reacts, then adding in initiator, the reaction was continued, obtains nano-hydrogel PNIPAM；Crosslinking agent is added in, monomeric acrylic etc. is added, obtains nano-hydrogel PNIPAM/PAA；Sequentially add the Fe of various concentration2+Deng obtaining nano-hydrogel IPN/Fe3O4；Monomer N N-isopropylacrylamides etc. are added in, temperature reaction, adding in initiator, the reaction was continued, obtains nano-hydrogel PNIPAM@(IPN/Fe3O4)；By IPN/Fe3O4It is mixed, it is concentrated to give the defective Responsive photonic crystals of tool.The photonic crystal has response to temperature, and when temperature raises, defect disappears, and when being cooled to room temperature, defect occurs.

Description

A kind of preparation method for having defective Responsive photonic crystals
Technical field
The present invention relates to a kind of preparation methods for having defective Responsive photonic crystals, belong to nano-hydrogel photon crystalline substance The preparing technical field of body.
Background technology
Photonic crystal (is a kind of by two kinds or the two or more materials with different refractivity have in certain space The material with periodic structure that sequence arrangement forms.The periodic structure of this uniqueness can generate electromagnetic wave, and " Prague dissipates Penetrate ", so as to be formed " forbidden photon band ".When frequency of light wave falls in forbidden band, light just cannot be propagated.Photon band gap and photon The lattice constant of crystal, structure, the refractive index of material packing ratio and material etc. are related.Therefore we can by change these because Element produces the photon crystal material of variety classes, difference in functionality.Another key character of photonic crystal is the office of photonic crystal Domain property, i.e., when photon crystal material has certain defect (degree of order of photonic crystal is destroyed), part is former in photonic crystal Some periodic arrangements are destroyed, and corresponding forbidden photon band position also occurs to change accordingly.In the photonic crystal, defective form master There are point defect, line defect, planar defect etc., by artificially manufacturing certain defect so as to the propagation for controlling light inside photonic crystal Mode.Have defective photonic crystal and can be applied to fiber waveguide, laser emitter increases or inhibit spontaneous radiation etc..
At present, preparing the method for having defective photonic crystal has mechanical processing method, laser ablation method, electroetching method etc., Although these methods have design flexibility, time-consuming for they, trivial operations, is not suitable for mass producing.Compared to this A little methods, the method for hydrogel particle self assembly possess easy to operate, low manufacture cost and take the characteristics such as short.For example, C.L ó pez etc. are by polymethyl methacrylate (PMMA) polystyrene doped microballoon (PS), being presented tool after colloidal solid self assembly Defective photonic crystal, and pass through the dosage for adjusting PS and the unordered degree of particle size adjustment photonic crystal, so as to regulate and control it The property of forbidden photon band
(Palacios-Lidon E, Juarez B H, Castillo-Martinez E, et al.Optical and Morphological study of disorder in opals [J] .Journal ofApplied Physics, 2005,97 (6)：063502-063502-7.).In addition, Koen Clays are in SiO2The photonic crystal of assembling, by adulterating different-grain diameter SiO2Particle prepares photonic crystal (Kurt Wostyn, Yuxia Zhao, G D S, et with planar defect al.Insertion of a Two-Dimensional Cavity into a Self-Assembled Colloidal Crystal [J] .Langmuir, 2003,19 (10)：4465-4468.).However, this kind of defective photonic crystal of tool is to the external world Non-responsiveness is stimulated, limits its application range.At present, the side of defect is controllably introduced in responsiveness aquagel photonic crystal The rare report of method.
The content of the invention
Problem to be solved by this invention is：A kind of preparation method for having defective Responsive photonic crystals is provided, Have a wide range of application.
To solve the above-mentioned problems, the present invention provides a kind of preparation method for having defective Responsive photonic crystals, It is characterised in that it includes following steps：
Step 1)：Monomer n-isopropyl acrylamide (NIPAM), crosslinking agent, emulsifier are added in deionized water, room temperature Nitrogen charging deoxygenation, stirring and dissolving are reacted under nitrogen atmosphere, and then adding in initiator, the reaction was continued, through dialysis, obtains Thermo-sensitive Nano-hydrogel PNIPAM；
Step 2)：The nano-hydrogel PNIPAM that step 1) obtains with deionized water is diluted, adds in crosslinking agent, nitrogen gas It is stirred under atmosphere, sequentially adds monomeric acrylic (AA), initiator, catalyst at room temperature and persistently stir, through dialysis, obtain interpenetrating net The nano-hydrogel PNIPAM/PAA of network IPN structures；
Step 3)：The nano-hydrogel PNIPAM/PAA that step 2) obtains is divided into more parts after nitrogen charging deoxygenation, room temperature Under be sequentially added into the Fe of various concentration2+、NaNO2, ammonium hydroxide, be stirred to react under nitrogen atmosphere, through dialysis, obtain Thermo-sensitive magnetic The nano-hydrogel IPN/Fe of property IPN structures3O4；
Step 4)：The nano-hydrogel IPN/Fe obtained to step 3)3O4Add in monomer n-isopropyl acrylamide, crosslinking Agent, room temperature nitrogen charging deoxygenation are stirred under nitrogen atmosphere, then temperature reaction, and adding in initiator, the reaction was continued, through dialysis, is had There are the magnetic Nano hydrogel PNIPAM@(IPN/Fe of nucleocapsid3O4)；
Step 5)：Contain Fe by what step 3) obtained3O4Measure different nano-hydrogel IPN/Fe3O4It is obtained with step 4) The magnetic Nano hydrogel PNIPAM@(IPN/Fe of nucleocapsid3O4) mixing, 2~8wt% is concentrated into, is stood at room temperature from group Dress, obtains having defective Responsive photonic crystals.
Preferably, the crosslinking agent in the step 1) is N, and N '-bis- (propylene acyl) cystamine (BAC), emulsifier is dodecane Base sodium sulphate (SDS), initiator are ammonium persulfate (APS)；Crosslinking agent in step 2) is N, N '-methylene-bisacrylamide (BIS), initiator is ammonium persulfate (APS), and catalyst is sodium pyrosulfite (Na2S2O5)；The quality of ammonium hydroxide in step 3) is dense It spends for 25~30%；Crosslinking agent in step 4) is N, and N '-methylene-bisacrylamide (BIS), initiator is ammonium persulfate (APS)。
Preferably, monomer n-isopropyl acrylamide in the step 1), crosslinking agent, emulsifier, initiator, catalyst Mass ratio is 100: 1~3: 2~5: 3~6: 3~6；PNIPAM, monomeric acrylic, crosslinking agent, initiator, catalysis in step 2) The mass ratio of agent is 100: 5~20: 5~30: 3~6: 3~6；PNIPAM/PAA, Fe in step 3)2+、NaNO2, ammonium hydroxide dosage Than for 100g：0.007~0.07g：0.001~0.100g：0.01~1mL；IPN/Fe in step 4)3O4, monomer N- isopropyls third Acrylamide, crosslinking agent, the amount ratio of initiator are 100mL: 0.05~0.3g: 0.0025~0.075g: 0.005~0.09g；
Preferably, using magnetic agitation, mixing time is 25~35min for stirring in the step 1)；The temperature of first set reaction It spends for 60~80 DEG C, the reaction time is 30~50min；The time that the reaction was continued is 1~4h.
Preferably, the diluted multiple of deionization is 5~10 times in the step 2)；Stirring uses magnetic agitation；For the first time Mixing time is 15~40min；It is 15~60min to continue mixing time.
Preferably, the time of nitrogen charging is 20~40min in the step 3)；Stirring is using mechanical agitation；Add in Fe2+Afterwards Mixing time is 20~60min；Add in NaNO2Mixing time afterwards is 5~20min；Add in the mixing time after ammonium hydroxide for 1~ 3h。
Preferably, the time of nitrogen charging is 30~50min in the step 4)；Stirring uses magnetic agitation, and mixing time is 20~40min；The temperature of temperature reaction is 50~70 DEG C, and the reaction time is 30~40min；Add in initiator the reaction was continued time For 1~4h.
Preferably, the step 1) -4) in dialysis technological parameter be：It is 8000~14000 to be packed into molecular cut off It is impregnated 3~7 days in deionized water in bag filter, changes 3 water daily.
Preferably, nano-hydrogel IPN/Fe in the step 5)3O4With magnetic Nano hydrogel PNIPAM@(IPN/ Fe3O4) mass percent be 0%~5%；The temperature of concentration is 40~70 DEG C.
The present invention by responsiveness aquagel introduce with body granules grain size, refractive index, the different emulsion particle of structure, By colloidal solid self assembly, the photonic crystal with point defect is prepared.The photonic crystal has response to temperature, in temperature During rise, defect disappears, and when being cooled to room temperature, defect occurs.
Compared with prior art, the beneficial effects of the present invention are：
(1) method that the present invention uses is simple for process, and raw material is easy to get, environmentally protective；
(2) prepared by the present invention has defective Responsive photonic crystals, and forbidden photon band position can be by adulterating latex The properties such as grain concentration, grain size, refractive index are adjusted；
(3) present invention prepares the hydrogel particle after doping, by heating-falling temperature technique, can Rapid self assembly into The photonic crystal of defect, and defect disappears at high temperature, and defect occurs during cooling.
Description of the drawings
Fig. 1 is the optics picture of the defective Responsive photonic crystals of tool obtained of embodiment 1；
Fig. 2 is that responsiveness aquagel made from embodiment 1 is hydrated grain-size graph；
Fig. 3 is pair of the reflectance spectrum figure obtained for having defective Responsive photonic crystals and each intermediate of embodiment 1 Than figure；
Fig. 4 is the reflectance spectrum figure of the defective Responsive photonic crystals of tool obtained of embodiment 2；
Fig. 5 be the defective Responsive photonic crystals of tool obtained of embodiment 2 40 DEG C with 25 DEG C when reflectance spectrum figure.
Specific embodiment
To be clearer and more comprehensible the present invention, hereby with preferred embodiment, and attached drawing is coordinated to be described in detail below.
Embodiment 1
A kind of preparation method for having defective Responsive photonic crystals：
(1) by 1.9825g monomer n-isopropyl acrylamide NIPAM, 0.0321g crosslinking agent B AC, 0.1008g emulsifiers SDS is dissolved in 250mL deionized waters, and blasts N at room temperature2Deoxygenation, magnetic agitation 30min, in a nitrogen atmosphere 70 DEG C it is anti- 30min is answered, then 0.0815g initiator As PS is dissolved in 10mL deionized waters, adds in above-mentioned solution, keeps nitrogen atmosphere, after Then continuous reaction 4h is soaked in deionized water with the bag filter that molecular cut off is 8000~14000 and dialysed 7 days, changed daily Water three times, removal remain electrolyte in reaction raw materials and reaction system, obtain temperature-sensitive nano hydrogel PNIPAM.
(2) PNIPAM that 60mL steps (1) obtain is diluted to 440mL with deionized water, adds in 0.5954g crosslinking agents BIS, magnetic agitation 30min under nitrogen atmosphere add in 3g monomeric acrylic AA magnetic agitation 20min, then by 0.2g initiators APS, 0.2g catalyst n a2S2O5It is dissolved in respectively in 5mL deionized waters, sequentially adds above-mentioned solution, keep nitrogen atmosphere, continue 30min is reacted, is then soaked in deionized water and dialysed 7 days with the bag filter that molecular cut off is 8000~14000, changed daily Water three times, removal remain electrolyte in reaction raw materials and reaction system, obtain interpenetrating networks IPN structure nano hydrogels PNIPAM/PAA。
(3) the IPN structure nano hydrogels PNIPAM/PAA that 300g steps (2) obtain is taken to be equally divided into 2 parts, every part 150mL, N2Deoxygenation 30min is separately added into 0.0125g, 0.0432g Fe at room temperature2+, N2The lower mechanical agitation 40min of protection, so 0.01g NaNO are added in afterwards2, the ammonium hydroxide that 0.05mL concentration is 25wt% is added in after 5min, keeps nitrogen atmosphere sustained response 1h, Then it is soaked in deionized water and is dialysed 7 days with the bag filter that molecular cut off is 8000~14000, is changed water three times daily, go Except electrolyte in residual reaction raw materials and reaction system, inierpeneirating network structure magnetic Nano hydrogel IPN/Fe is obtained3O4It orders respectively Entitled M1, M2.
(4) the M2 nano-hydrogels IPN/Fe that step (3) obtains is taken3O4, add in 0.2105g monomers NIPAM, 0.0203g and hand over Join agent BIS, room temperature nitrogen charging deoxygenation 40min, magnetic agitation 30min, temperature rises to 50 DEG C of reaction 30min, then draws 0.0214g Hair agent APS is dissolved in 2mL deionized waters, adds in above-mentioned solution, keeps nitrogen atmosphere, the reaction was continued 4h, then with retention molecule The bag filter measured as 8000~14000 is soaked in deionized water and dialyses 7 days, changes water three times, removal residual reaction raw materials daily And electrolyte in reaction system, it obtains with core-shell structure magnetic nano-hydrogel PNIPAM@(IPN/Fe3O4), it is named as PM2.
(5) in 50g M2,1.25wt%M1 is added in, is uniformly mixed, is named as M1：M21.25%；In 50g M2, add Enter 1.25wt%PM2, be uniformly mixed, be named as PM2：M21.25%；Above-mentioned mixed liquor is placed in baking oven, is concentrated at 50 DEG C 3.5wt%, taking-up are stood at room temperature, are carried out self assembly, are obtained having defective Responsive photonic crystals.
The present embodiment defective Responsive photonic crystals M1 of tool obtained：M21.25% shows noticeable color Coloured silk, as shown in Figure 1.
Responsiveness aquagel hydration grain size is as shown in Figure 2 made from the present embodiment.
The reflectance spectrum figure of Responsive photonic crystals made from the present embodiment is as shown in Figure 3, it is known that in Bragg diffraction peak The defects of appearance position and the intensity of defect influenced by the latex particle size and structure that adulterate.
Embodiment 2
A kind of preparation method for having defective Responsive photonic crystals：
(1) by 1.8754g monomer n-isopropyl acrylamide NIPAM, 0.0314g crosslinking agent B AC, 0.1056g emulsifiers SDS is dissolved in 250mL deionized waters, and blasts N at room temperature2Deoxygenation, magnetic agitation 30min, in a nitrogen atmosphere 70 DEG C it is anti- 30min is answered, then 0.0812g initiator As PS is dissolved in 10mL deionized waters, adds in above-mentioned solution, keeps nitrogen atmosphere, after Then continuous reaction 4h is soaked in deionized water with the bag filter that molecular cut off is 8000~14000 and dialysed 7 days, changed daily Water three times, removal remain electrolyte in reaction raw materials and reaction system, obtain temperature-sensitive nano hydrogel PNIPAM.
(2) PNIPAM that 60mL steps (1) obtain deionized waters are diluted into 440mL, add in 0.6012g crosslinking agent B IS, Magnetic agitation 30min under nitrogen atmosphere, add in 3g monomeric acrylic AA magnetic agitation 20min, then by 0.2g initiator As PS, 0.2g catalyst ns a2S2O5It is dissolved in respectively in 5mL deionized waters, sequentially adds above-mentioned solution, keep nitrogen atmosphere, sustained response Then 30min is soaked in deionized water with the bag filter that molecular cut off is 8000~14000 and dialysed 7 days, changed daily three times Water, removal remain electrolyte in reaction raw materials and reaction system, obtain interpenetrating networks IPN structure nano hydrogels PNIPAM/ PAA。
(3) the IPN structure nano hydrogels PNIPAM/PAA that 300g steps (2) obtain is taken to be equally divided into 2 parts, every part 150mL, N2Deoxygenation 30min is separately added into 0.0857g Fe at room temperature2+, N2The lower mechanical agitation 40min of protection, then adds in 0.01g NaNO2, the ammonium hydroxide that 0.1mL concentration is 25wt% is added in after 5min, keeps nitrogen atmosphere sustained response 1h, then with cutting The bag filter that molecular weight is stayed to be 8000~14000, which is soaked in deionized water, dialyses 7 days, changes water three times daily, and removal residual is anti- Electrolyte in raw material and reaction system is answered, obtains inierpeneirating network structure magnetic Nano hydrogel IPN/Fe3O4It is respectively designated as M3.
(4) the M3 nano-hydrogels IPN/Fe that step (3) obtains is taken3O4, add in 0.2007g monomers NIPAM, 0.0205g and hand over Join agent BIS, room temperature nitrogen charging deoxygenation 40min, magnetic agitation 30min, temperature rises to 50 DEG C of reaction 30min, then draws 0.0201g Hair agent APS is dissolved in 2mL deionized waters, adds in above-mentioned solution, keeps nitrogen atmosphere, the reaction was continued 4h, then with retention molecule The bag filter measured as 8000~14000 is soaked in deionized water and dialyses 7 days, changes water three times, removal residual reaction raw materials daily And electrolyte in reaction system, it obtains with core-shell structure magnetic nano-hydrogel PNIPAM@(IPN/Fe3O4), it is named as PM3.
(5) 50g M3 are taken, add in 1.25wt%PM3, is uniformly mixed, is named as PM3：M31.25% takes 50g M3, adds in 2.5wt%PM3 is uniformly mixed, is named as PM3：M32.5%；Above-mentioned mixed liquor is placed in baking oven, is concentrated at 50 DEG C 3.5wt%, taking-up are stood at room temperature, are carried out self assembly, are obtained having defective Responsive photonic crystals.
The reflectance spectrum figure of the present embodiment defective Responsive photonic crystals of tool obtained is as shown in Figure 4, it is known that Bradley The position of defect can be adjusted by the concentration of the emulsion particle adulterated in lattice diffraction maximum.
The present embodiment defective Responsive photonic crystals of tool obtained 40 DEG C with 25 DEG C when reflectance spectrum figure such as Fig. 5 It is shown, it is known that photonic crystal has temperature sensibility, high temperature defect erasing, and cold temperature deficiency shows.

Claims (9)

1. a kind of preparation method for having defective Responsive photonic crystals, which is characterized in that comprise the following steps：
Step 1)：Monomer n-isopropyl acrylamide, crosslinking agent, emulsifier are added in deionized water, room temperature nitrogen charging deoxygenation stirs Dissolving is mixed, is reacted under nitrogen atmosphere, then adding in initiator, the reaction was continued, through dialysis, obtains the nanometer water-setting of Thermo-sensitive Glue PNIPAM；
Step 2)：The nano-hydrogel PNIPAM that step 1) obtains is diluted with deionized water, addition crosslinking agent, under nitrogen atmosphere Stirring, sequentially adds monomeric acrylic, initiator, catalyst and persistently stirs at room temperature, through dialysis, obtains interpenetrating networks IPN knots The nano-hydrogel PNIPAM/PAA of structure；
Step 3)：The nano-hydrogel PNIPAM/PAA that step 2) obtains after nitrogen charging deoxygenation is divided into more parts, is divided at room temperature The Fe of various concentration is not sequentially added2+、NaNO2, ammonium hydroxide, be stirred to react under nitrogen atmosphere, through dialysis, obtain Thermo-sensitive magnetism The nano-hydrogel IPN/Fe of IPN structures3O4；
Step 4)：The nano-hydrogel IPN/Fe obtained to step 3)3O4Add in monomer n-isopropyl acrylamide, crosslinking agent, room Warm nitrogen charging deoxygenation is stirred under nitrogen atmosphere, then temperature reaction, and adding in initiator, the reaction was continued, through dialysis, obtains with nucleocapsid The magnetic Nano hydrogel PNIPAM@(IPN/Fe of structure3O4)；
Step 5)：Contain Fe by what step 3) obtained3O4Measure different nano-hydrogel IPN/Fe3O4The nucleocapsid knot obtained with step 4) The magnetic Nano hydrogel PNIPAM@(IPN/Fe of structure3O4) mixing, 2~8wt% is concentrated into, stands self assembly at room temperature, is obtained Have defective Responsive photonic crystals.
2. has the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step 1) crosslinking agent in is N, and N '-bis- (propylene acyl) cystamine, emulsifier is lauryl sodium sulfate, and initiator is ammonium persulfate；Step It is rapid 2) in crosslinking agent for N, N '-methylene-bisacrylamide, initiator is ammonium persulfate, and catalyst is sodium pyrosulfite；Step It is rapid 3) in ammonium hydroxide mass concentration be 25~30%；Crosslinking agent in step 4) is N, N '-methylene-bisacrylamide, is triggered Agent is ammonium persulfate.
3. has the preparation method of defective Responsive photonic crystals as claimed in claim 1 or 2, which is characterized in that described Monomer n-isopropyl acrylamide, crosslinking agent, emulsifier, initiator, the mass ratio of catalyst are 100: 1~3: 2 in step 1) ~5: 3~6: 3~6；PNIPAM in step 2), monomeric acrylic, crosslinking agent, initiator, the mass ratio of catalyst for 100: 5~ 20: 5~30: 3~6: 3~6；PNIPAM/PAA, Fe in step 3)2+、NaNO2, ammonium hydroxide amount ratio for 100g: 0.007~ 0.07g: 0.001~0.100g: 0.01~1mL；IPN/Fe in step 4)3O4, monomer n-isopropyl acrylamide, crosslinking agent, draw The amount ratio for sending out agent is 100mL: 0.05~0.3g: 0.0025~0.075g: 0.005~0.09g.
4. has the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step 1) using magnetic agitation, mixing time is 25~35min for stirring in；The temperature of first set reaction is 60~80 DEG C, and the reaction time is 30~50min；The time that the reaction was continued is 1~4h.
5. has the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step 2) the diluted multiple of deionization is 5~10 times in；Stirring uses magnetic agitation；First mixing time is 15~40min；Continue Mixing time is 15~60min.
6. has the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step 3) time of nitrogen charging is 20~40min in；Stirring is using mechanical agitation；Add in Fe2+Mixing time afterwards is 20~60min；Add Enter NaNO2Mixing time afterwards is 5~20min；The mixing time added in after ammonium hydroxide is 1~3h.
7. has the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step 4) time of nitrogen charging is 30~50min in；Using magnetic agitation, mixing time is 20~40min for stirring；The temperature of temperature reaction For 50~70 DEG C, the reaction time is 30~40min；It is 1~4h to add in initiator the reaction was continued time.
8. has the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step 1) technological parameter of dialysis is in -4)：It is fitted into the bag filter that molecular cut off is 8000~14000 and is impregnated in deionized water 3~7 days, 3 water were changed daily.
9. has the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step 5) nano-hydrogel IPN/Fe in3O4With magnetic Nano hydrogel PNIPAM@(IPN/Fe3O4) mass percent for 0%~ 5%；The temperature of concentration is 40~70 DEG C.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110296769A (en) * 2019-07-17 2019-10-01 上海晨感智能科技有限公司 A kind of fibre optic temperature sensor and measuring system and signal processing method
CN112521634A (en) * 2020-12-23 2021-03-19 安徽美科迪智能微胶囊科技有限公司 Preparation and immobilization method of temperature-responsive nano hydrogel photonic crystal
CN113959582A (en) * 2021-10-27 2022-01-21 南京信息工程大学 Temperature sensing measurement method of mirror image type one-dimensional photonic crystal model

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103436965A (en) * 2013-07-13 2013-12-11 吉林大学 Preparation method of polymer photonic crystals with adjustable photonic band gap and presenting patterned color display
CN104845006A (en) * 2015-05-11 2015-08-19 东华大学 Magnetic acrylamide hydrogel and preparation method thereof
CN106750381A (en) * 2016-12-06 2017-05-31 东华大学 A kind of preparation method of the load ferriferrous oxide nano hydrogel based on inierpeneirating network structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103436965A (en) * 2013-07-13 2013-12-11 吉林大学 Preparation method of polymer photonic crystals with adjustable photonic band gap and presenting patterned color display
CN104845006A (en) * 2015-05-11 2015-08-19 东华大学 Magnetic acrylamide hydrogel and preparation method thereof
CN106750381A (en) * 2016-12-06 2017-05-31 东华大学 A kind of preparation method of the load ferriferrous oxide nano hydrogel based on inierpeneirating network structure

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DI STASIO, F. ETC.: ""Tuning optical properties of opal photonic crystals by structural defects engineering"", 《JOURNAL OF THE EUROPEAN OPTICAL SOCIETY-RAPID PUBLICATIONS》 *
方凯等: ""磁性胶体粒子聚合物壳层的调控及其对光子晶体性能的影响"", 《武汉理工大学学报》 *
马天泽等: ""多重响应的单分散聚_N_异丙基丙_省略_烯酸_纳米水凝胶的制备及性能表征"", 《功能高分子学报》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110296769A (en) * 2019-07-17 2019-10-01 上海晨感智能科技有限公司 A kind of fibre optic temperature sensor and measuring system and signal processing method
CN112521634A (en) * 2020-12-23 2021-03-19 安徽美科迪智能微胶囊科技有限公司 Preparation and immobilization method of temperature-responsive nano hydrogel photonic crystal
CN112521634B (en) * 2020-12-23 2023-08-29 安徽美科迪智能微胶囊科技有限公司 Preparation and immobilization methods of temperature-responsive nano hydrogel photonic crystal
CN113959582A (en) * 2021-10-27 2022-01-21 南京信息工程大学 Temperature sensing measurement method of mirror image type one-dimensional photonic crystal model
CN113959582B (en) * 2021-10-27 2023-05-16 南京信息工程大学 Temperature sensing measurement method of mirror image type one-dimensional photonic crystal model

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