CN106632777A - A method for a thermochromic bionic intelligent nanometer composite material - Google Patents
A method for a thermochromic bionic intelligent nanometer composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 107
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000002114 nanocomposite Substances 0.000 claims description 21
- 238000003828 vacuum filtration Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000002845 discoloration Methods 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 239000003643 water by type Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000001338 self-assembly Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 2
- 239000003471 mutagenic agent Substances 0.000 claims description 2
- 231100000707 mutagenic chemical Toxicity 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 9
- 239000011257 shell material Substances 0.000 abstract description 4
- 230000007123 defense Effects 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 3
- ZPUDRBWHCWYMQS-UHFFFAOYSA-N pentacosa-10,12-diynoic acid Chemical compound CCCCCCCCCCCCC#CC#CCCCCCCCCC(O)=O ZPUDRBWHCWYMQS-UHFFFAOYSA-N 0.000 abstract 1
- 238000006073 displacement reaction Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 9
- 238000002411 thermogravimetry Methods 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 238000007592 spray painting technique Methods 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000002079 double walled nanotube Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920000015 polydiacetylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F138/00—Homopolymers of compounds having one or more carbon-to-carbon triple bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Cosmetics (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A method for a thermochromic bionic intelligent nanometer composite material is disclosed. In recent years, shell-simulated layered materials are research hotspots. Artificial shell materials having excellent mechanical properties can be obtained through selecting base materials and through interface designing. Montmorillonite is adopted as a base material and is composited with 10,12-pentacosadiynoic acid (PCDA) to obtain a thermochromic intelligent bionic layered montmorillonite composite material. The composite material has reversible color changes from purple to orange under a heating condition, and also has high tensile strength. The intelligent artificial shell material has a potential application prospect in the fields of sensing detection, the national defense industry, aviation and spaceflight, and other fields.
Description
Technical field
The present invention relates to a kind of method of thermochromism bionic intelligence nano composite material, belongs to nano composite material preparation
Field.
Background technology
Through the evolution of 1 years, abalone shells had the excellent mechanical performance of tough integration, used as bionical " gold
Standard " improves new Research Thinking for novel nanocomposite materials.Substantial amounts of research shows, the excellent mechanical performance of abalone shells
It is mainly derived from：1) biological organic matter being made up of aragonite calcium carbonate nanoscale twins and chitin and protein is staggeredly constructed layer by layer
" fragment of brick-cement " structure, 2) there are different interface interactions between inorganic sheet and organic matter.Based on this inspiration, in a large number
Research work focus has been placed in bionic laminar nano composite material.The elementary material of general choice at present has montmorillonite
(Science2007,318,80, Angew.Chem.Int.Ed.2010,49,10127), hydrotalcite
(Angew.Chem.Int.Ed.2010,49,2140), CNT (Adv.Mater.2012,24,1838), alundum (Al2O3)
(Science 2008,319,1069), Graphene (Soc.Rev.2016,45,2378, Adv.Mater.2016,
Adv.Mater.2008,20,3557, Adv.Mater.2016,28,1501, Angew.Chem.Int.Ed.2013,52,3750)
Deng.Studart et al. is prepared for alundum (Al2O3)/chitosan nano composite material, and (Science 2008,319,1069), its is tough
Property reach 75MJ/m3；Cheng et al. is prepared for flat double-walled carbon nano-tube/epoxy resin nano composites
(Adv.Mater.2012,24,1838), play intensity and are up to 1600MPa；Tsukruk et al. is prepared for Graphene/cellulose nanometer
(Adv.Mater.2016,28,1501), its Young's modulus reaches 169GPa to brilliant nanometer.Although nano combined material mentioned above
Expect all to show excellent mechanical property, but intelligent bionic nano composite material, and particularly can stimulate to external world is carried out
What is responded is not also reported.
Intelligent thermochromic material can visualize temperature change, so in the fields such as many field sensors tool
Have broad application prospects.Polybutadiene alkynes material is a kind of conjugated polymer, is widely used in thermochromic material.Since poly-
Diacetylene material was prepared first in 1969, through the research of decades, the intelligent color-changing based on polybutadiene alkynes material
Material achieves progress in every field.Lee and Kim et al. report one kind can be to the hot dual sound of humidity
The polybutadiene alkynes material answered, by the preparation of simple inkjet printing, can be used as the mapping substrate to finger pore
(Nat.Commun.2014,5,3736).Peng et al. reports carbon nano-tube/poly diacetylene composite fibre, with reversible electricity
Cause discoloration, can apply to the fields such as sensor, brake (Nat.Nanotechnol.2009,4,738).The poly- fourth of tradition
Diine material is typically chosen in matrix and is deposited, be obtained thermochromic thin film (Adv.Funct.Mater.2016,26,
498th, Adv.Funct.Mater.2016,26,1769, J.Am.Chem.Soc.2005,127,12782, Nature 2001,
410,913 etc.), thus be difficult to obtain the self-supporting film material with excellent mechanical performance.
In sum, current thermochromic material is difficult to the raising of mechanical property, therefore by the strategy of bionical preparation
The thermochromism nano composite material with excellent mechanical performance has been obtained.
The content of the invention
The technology solve problem of the present invention：Overcome existing technical deficiency, there is provided a kind of thermochromism bionic intelligence is received
The method of nano composite material.Using the thinking of bionical preparation, from montmorillonite as elementary material, with the carbon two of 10,12- 25
Acetylenic acid (PCDA) is compound can to obtain thermochromism intelligent bionic stratiform montmorillonite composite material.The material not only can be in heating
Under the conditions of occur from purple to orange reversible color change, also with higher tensile strength.This intelligent artificial shell material
Material has potential application prospect in fields such as sensing detection, national defense industry, Aero-Space.
The present invention is achieved through the following technical solutions：A kind of side of thermochromism bionic intelligence nano composite material
Method, by the method for solution blending, obtains montmorillonite/PCDA mixed solutions, and obtains with thermochromism after ultraviolet irradiation
The purple solution of performance.A series of illiteracy that the method for self assembly has obtained different montmorillonite contents is induced to take off using vacuum filtration
Soil-PCDA stratiform montmorillonite composite materials.By impregnating APTES, strengthened montmorillonite-PCDA-APTES thermics have been obtained
Intelligent color-changing bionic laminar montmorillonite composite material.
Implement step as follows：
(1) montmorillonite solution is obtained using the method for stirring, centrifugation；The carbon diacetylenic acids (PCDA) of 10,12- 25 are dissolved in
NaOH solution in, heating a moment, obtain PCDA solution；
(2) montmorillonite solution and PCDA solution are placed in into illumination under uviol lamp with certain proportion mixing, obtain purple
Thermochromism montmorillonite-PCDA solution；
(3) the thermochromism montmorillonite-PCDA solution obtained by step (2) is carried out into vacuum filtration, is lured using vacuum filtration
Leading self-assembling method carries out induction self assembly, obtains montmorillonite-PCDA laminar composites；
(4) ratio of montmorillonite solution and PCDA solution in step (2) is changed, repeat step (2) (3), regulation and control montmorillonite-
The content of montmorillonite in PCDA laminar composites, in determining the optimal montmorillonite-PCDA laminar composites of mechanical property
Montmorillonite content；
(5) by the optimal montmorillonite-PCDA laminar composites of the mechanical property of gained in step (4) in 3- aminopropyls three
Dipping in Ethoxysilane (APTES), obtains strengthened montmorillonite-PCDA-APTES thermochromism intelligent bionics stratiform and covers
De- soil composite material.Different dip times are set, regulate and control the content of APTES, determine the optimum montmorillonite-PCDA- of mechanical property
The content of the APTES in APTES thermochromism intelligent bionic stratiform montmorillonite composite materials.
In the step (1), the process for obtaining montmorillonite solution using the method for stirring, centrifugation is as follows：1.5-3g is covered
De- soil is dissolved in 250-500mL deionized waters, after stirring 7-10 days, is taken suspension and is centrifuged several times, and rotating speed is 2800-3000
Rpm, take supernatant and obtain montmorillonite solution.
In the step (1), the 1-2mL 0.5mol/ that 10-20mg 10, the carbon diacetylenic acids (PCDA) of 12- 25 are dissolved in
In L NaOH solutions, 70-80 DEG C of heating 5-10min obtains PCDA solution.
In the step (1), the concentration of montmorillonite solution is 2.7mg/mL to 3.2mg/mL.
In the step (2), montmorillonite solution and PCDA solution are accounted for into illiteracy with certain proportion mixing, the i.e. quality of PCDA de-
The 40% of both soil and PCDA gross mass, 70-80 DEG C of heating 5-10min is needed, after being well mixed, room temperature is sufficiently cooled to, and
Stand 15-30min.
In the step (2), illumination 5min to 10min under uviol lamp is placed in so that PCDA molecules occur polymerisation, obtain
To the thermochromism montmorillonite-PCDA solution of purple.
In the step (3), adopt vacuum filtration induction self-assembling method implement process for：To uniformly cover first
De- soil-PCDA mixed solutions are added in vacuum filtration bottle；Start vavuum pump, carry out vacuum filtration；With the carrying out of suction filtration, cover de-
Native nanoscale twins are slowly self-assembled into layer structure under flow action, treat that suction filtration is completed, that is, obtain montmorillonite-PCDA stratiforms and answer
Condensation material.
The thickness range of montmorillonite-PCDA laminar composites prepared by the step (3) is 5-20 microns.
In the step (4), the content for regulating and controlling montmorillonite is respectively 60%, 70%, 80%, 90%, 95%, that is, add
The quality of PCDA accounts for the 40% of both montmorillonite and PCDA gross mass, and 30%, 20%, 10%, 5%, different cover de- by characterizing
The mechanical property of the montmorillonite-PCDA laminar composites of native content, determines the montmorillonite mass fraction of optimum performance.
In the step (5). the dip time of regulation and control APTES is respectively 10min, 30min, 60min, 120min；Pass through
Characterize the mechanics of the montmorillonite-PCDA-APTES thermochromism intelligent bionic stratiform montmorillonite composite materials of difference APTES contents
Performance, determines the APTES mass fractions of optimum performance.
The principle of the present invention：Through the evolution of hundreds of millions of years, the abalone shells of nature, orderly micro-nano many of stratiform are defined
Level structure and compound interface, impart the excellent intensity of abalone shells and toughness, and mechanical stretch intensity reaches 80-170MPa, toughness
Up to 1.8KJm-3.This " fragment of brick "-" cement " structure is with layer by the calcium carbonate lamella and protein of 200-900 nanometer thickness
What layer was alternately realized.In the micro-nano multistage layer structure of abalone shells, the volume content of inorganic carbonate calcium is up to 95%, while having
Machine protein is strengthening phase interlayer formation nanometer Reinforced structure.
By abalone shells organic and inorganic, layer by layer micro-nano package assembly is inspired, and the present invention is bionical with PCDA using montmorillonite
The composite of layer structure is constructed, compared with the existing technology for preparing graphene oxide composite material, the characteristics of of the invention
It is：(1) in the presence of ultraviolet lighting there is polymerisation in PCDA, and the polymer has thermochromic properties, can be with temperature
Change and reversible color change occurs；(2) using APTES covalent cross-linking montmorillonite layers, montmorillonite interlaminar strength is enhanced, is made
The intensity of composite film material is increased dramatically, tensile strength up to 80.1 to 101.8MPa, fracture toughness up to 0.33 to
0.65MJm-3；(3) the method develops a kind of montmorillonite-PCDA mixed solutions of thermochromism, with preferable operability, can
So as to being prepared thermochromism intelligent bionic stratiform montmorillonite composite material on a large scale.Such as can be by the method for spray-painting
The thermochromism intelligent bionic stratiform montmorillonite composite material of patterning is prepared in various substrates, it may have reversible thermotropic
Chromatic effect.
Description of the drawings
Fig. 1 is the preparation technology schematic diagram of the thermochromism intelligent bionic stratiform montmorillonite composite material of the present invention；
The force-displacement curve of Fig. 2 thermochromism intelligent bionic stratiform montmorillonite composite materials, infrared spectrum and its tear type
Looks：A) force-displacement curve of pure montmorillonite, the force-displacement curve of montmorillonite-PCDA laminar composites, montmorillonite-PCDA-
The force-displacement curve of APTES thermochromism intelligent bionic stratiform montmorillonite composite materials；B) montmorillonite-PCDA lamellar composites material
The tensile strength and fracture toughness of material gradually increases with the rising of montmorillonite content；C) montmorillonite-PCDA-APTES thermotropics
The tensile toughness and fracture toughness of color intelligent bionic stratiform montmorillonite composite material gradually increases with the rising of montmorillonite content；
D) force-displacement curve of pure montmorillonite, the force-displacement curve of montmorillonite-PCDA laminar composites, montmorillonite-PCDA-
APTES thermochromism intelligent bionic stratiform montmorillonite composite materials, the infrared spectrum of pure PCDA；E) montmorillonite-PCDA-APTES
The fracture pattern of thermochromism intelligent bionic stratiform montmorillonite composite material；
The discoloration of Fig. 3 montmorillonite-PCDA-APTES thermochromism intelligent bionic stratiform montmorillonite composite materials：A) not
Under synthermal, thermochromism intelligent bionic stratiform montmorillonite composite material is shown from purple to orange different colours；B) it is different
At a temperature of, the ultraviolet-visible spectrum of thermochromism intelligent bionic stratiform montmorillonite composite material；C) under different temperatures, thermotropic
Colorimetric response value (CR) of color intelligent bionic stratiform montmorillonite composite material；D) 20 DEG C, 50 DEG C and it is cooled to 20 DEG C of heat
The ultraviolet-visible spectrum of mutagens color intelligent bionic stratiform montmorillonite composite material；E) the CR values of 8 discoloration circulations, circulating temperature
For 20 DEG C to 50 DEG C.F) the mechanism figure of discoloration；
The preparation process of Fig. 4 spray-paintings and displaying.A) process schematic of spray-painting；B) prepare on A4 paper；c)
Prepare on the glass sheet；D) prepare on stainless steel；E) prepare on plastics dixie cup.All coatings all have reversible thermic
Discoloration.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment is discussed in detail the present invention.But below example is only limitted to explain this
Bright, protection scope of the present invention should include the full content of claim, and the narration for passing through following examples, this area
Technical staff can be the full content for fully achieving the claims in the present invention.
As shown in figure 1, the method for the present invention is embodied as：First, montmorillonite solution is obtained using the method for stirring, centrifugation；
In the NaOH solution that the carbon diacetylenic acids (PCDA) of 10,12- 25 are dissolved in, in heating a moment, PCDA solution is obtained；Montmorillonite is molten
Liquid and PCDA solution are placed in illumination under uviol lamp with certain proportion mixing, and the thermochromism montmorillonite-PCDA for obtaining purple is molten
Liquid；Thermochromism montmorillonite-PCDA solution obtained above is carried out into vacuum filtration, self-assembling method is induced using vacuum filtration
Induction self assembly is carried out, montmorillonite-PCDA laminar composites are obtained.By above-mentioned montmorillonite-PCDA laminar composites in 3-
Dipping in aminopropyl triethoxysilane (APTES), obtains strengthened montmorillonite-PCDA-APTES thermochromisms intelligently imitative
Generating layer shape montmorillonite composite material.Montmorillonite-PCDA-APTES thermochromisms intelligent bionic stratiform the montmorillonite composite material
Thickness range be 5-20 microns.
As shown in Fig. 2 force-displacement curve, the infrared spectrum of Fig. 2 thermochromism intelligent bionic stratiform montmorillonite composite materials
And its fracture pattern：A) force-displacement curve of pure montmorillonite, the force-displacement curve of montmorillonite-PCDA laminar composites, illiteracy
The force-displacement curve of de- soil-PCDA-APTES thermochromisms intelligent bionic stratiform montmorillonite composite material；B) montmorillonite-PCDA
The tensile strength and fracture toughness of laminar composite gradually increases with the rising of montmorillonite content；C) montmorillonite-PCDA-
The tensile toughness and fracture toughness of APTES thermochromism intelligent bionic stratiform montmorillonite composite materials with montmorillonite content rising
And gradually increase；D) force-displacement curve of pure montmorillonite, the force-displacement curve of montmorillonite-PCDA laminar composites, illiteracy are de-
Soil-PCDA-APTES thermochromism intelligent bionic stratiform montmorillonite composite materials, the infrared spectrum of pure PCDA.The spectrogram explanation
There is hydrogen bond action between PCDA molecules and montmorillonite, APTES has played covalent cross-linking effect, and condensation reaction occurs, form covalent
Silicon oxygen bond；E) the fracture pattern of montmorillonite-PCDA-APTES thermochromisms intelligent bionic stratiform montmorillonite composite material.
As shown in figure 3, the discolouration of montmorillonite-PCDA-APTES thermochromism intelligent bionic stratiform montmorillonite composite materials
Energy：A) under different temperatures, thermochromism intelligent bionic stratiform montmorillonite composite material is shown from purple to orange different colours；
B) under different temperatures, the ultraviolet-visible spectrum of thermochromism intelligent bionic stratiform montmorillonite composite material, its spectrogram shows, with
Temperature rising, the peak intensity of absworption peak strengthens at 530nm, the peak intensity of absworption peak weakens at 620nm, material shows
Illustrate from purple to orange color change；C) under different temperatures, thermochromism intelligent bionic stratiform montmorillonite composite material
Colorimetric response value (CR).CR=(PB0-PBf)/PB0× 100%, wherein PB represents the ratio shared by blue phase：PB=
A620nm/(A620nm+A530nm), subscript 0 and f represent the original state and final state of colourshifting process.；D) 20 DEG C, 50 DEG C and cold
But to the ultraviolet-visible spectrum of 20 DEG C of thermochromism intelligent bionic stratiform montmorillonite composite material.It can be seen that after cooling, it is purple
Outward-visible spectrum with do not heat before overlap, illustrate discoloration when it is reversible.E) the CR values of 8 discoloration circulations, circulating temperature is 20 DEG C
To 50 DEG C.F) the mechanism figure of discoloration.Temperature is raised, the warm-up movement aggravation of PCDA molecules, the free degree increase of side chain motion, disturbance
The conjugated structure of main chain, the change that color occurs.
As shown in figure 4, the preparation process of spray-painting and displaying.A) process schematic of spray-painting；B) on A4 paper
Prepare；C) prepare on the glass sheet；D) prepare on stainless steel；E) prepare on plastics dixie cup.All coatings all have can
Inverse thermochromic properties.
Embodiment 1
1.5g montmorillonite powder is weighed, in being dissolved in 250mL deionized waters, is persistently stirred 7 days.Will be resulting white suspended
Liquid is centrifuged twice, and rotating speed 2800rpm takes supernatant liquor, obtains montmorillonite solution, and demarcation concentration is 3.20mg/mL.
The PCDA of 10mg is weighed, in being dissolved in the NaOH solution of the 0.5mol/L of 1mL, 70 DEG C of heating 5min obtain pink colour glue
Shape solution.Above-mentioned 5.9mL montmorillonites solution is taken, is mixed with the PCDA hot solutions of 0.1mL, 70 DEG C of heating stirrings 5min stand
15min is cooled to room temperature.Solution after cooling is placed in into illumination 5min under uviol lamp, obtain the thermochromism montmorillonite of purple-
PCDA solution.Vacuum filtration is carried out to montmorillonite-PCDA solution, montmorillonite-PCDA laminar composites are obtained.Thermogravimetric analysis shows
Show, montmorillonite mass fraction is 94.2%.Mechanics Performance Testing shows, tensile strength 56.5MPa, fracture toughness 0.28MJm-3。
Above-mentioned montmorillonite-PCDA laminar composites are impregnated into 10min in APTES, obtain strengthened montmorillonite-
PCDA-APTES thermochromism intelligent bionic stratiform montmorillonite composite materials.Thermogravimetric analysis shows that APTES mass fractions are
0.5%.Mechanics Performance Testing shows, tensile strength 101.8MPa, fracture toughness 0.65MJm-3.Ultraviolet-visible spectrum shows (attached
Fig. 3), be somebody's turn to do montmorillonite-PCDA-APTES thermochromism intelligent bionic stratiform montmorillonite composite materials can occur reversible heat
Metachromatism is caused, is occurred between 20 DEG C to 70 DEG C from purple to the change orange.
Embodiment 2
1.5g montmorillonite powder is weighed, in being dissolved in 250mL deionized waters, is persistently stirred 7 days.Will be resulting white suspended
Liquid is centrifuged twice, and rotating speed 2800rpm takes supernatant liquor, obtains montmorillonite solution, and demarcation concentration is 2.80mg/mL.
The PCDA of 10mg is weighed, in being dissolved in the NaOH solution of the 0.5mol/L of 1mL, 70 DEG C of heating 5min obtain pink colour glue
Shape solution.Above-mentioned 6.8mL montmorillonites solution is taken, is mixed with the PCDA hot solutions of 0.1mL, 70 DEG C of heating stirrings 5min stand
15min is cooled to room temperature.Solution after cooling is placed in into illumination 5min under uviol lamp, obtain the thermochromism montmorillonite of purple-
PCDA solution.Vacuum filtration is carried out to montmorillonite-PCDA solution, montmorillonite-PCDA laminar composites are obtained.Thermogravimetric analysis shows
Show, montmorillonite mass fraction is 94.2%.Mechanics Performance Testing shows, tensile strength 56.5MPa, fracture toughness 0.28MJm-3。
Above-mentioned montmorillonite-PCDA laminar composites are impregnated into 30min in APTES, thermogravimetric analysis shows, APTES matter
Amount fraction is 2.6%.Mechanics Performance Testing shows, tensile strength 89.0MPa, fracture toughness 0.52MJm-3。
3g montmorillonite powder is weighed, in being dissolved in 500mL deionized waters, is persistently stirred 7 days.By resulting white suspension
Twice, rotating speed 2800rpm takes supernatant liquor for centrifugation, obtains montmorillonite solution, and demarcation concentration is 2.80mg/mL.
Embodiment 3
1.5g montmorillonite powder is weighed, in being dissolved in 250mL deionized waters, is persistently stirred 7 days.Will be resulting white suspended
Liquid is centrifuged twice, and rotating speed 2800rpm takes supernatant liquor, obtains montmorillonite solution, and demarcation concentration is 3.10mg/mL.
The PCDA of 10mg is weighed, in being dissolved in the NaOH solution of the 0.5mol/L of 1mL, 70 DEG C of heating 5min obtain pink colour glue
Shape solution.Above-mentioned 6.1mL montmorillonites solution is taken, is mixed with the PCDA hot solutions of 0.1mL, 70 DEG C of heating stirrings 5min stand
15min is cooled to room temperature.Solution after cooling is placed in into illumination 5min under uviol lamp, obtain the thermochromism montmorillonite of purple-
PCDA solution.Vacuum filtration is carried out to montmorillonite-PCDA solution, montmorillonite-PCDA laminar composites are obtained.Thermogravimetric analysis shows
Show, montmorillonite mass fraction is 94.2%.Mechanics Performance Testing shows, tensile strength 56.5MPa, fracture toughness 0.28MJm-3。
Above-mentioned montmorillonite-PCDA laminar composites are impregnated into 60min in APTES, thermogravimetric analysis shows, APTES matter
Amount fraction is 6.5%.Mechanics Performance Testing shows, tensile strength 85.0MPa, fracture toughness 0.33MJm-3。
Embodiment 4
1.5g montmorillonite powder is weighed, in being dissolved in 250mL deionized waters, is persistently stirred 7 days.Will be resulting white suspended
Liquid is centrifuged twice, and rotating speed 2800rpm takes supernatant liquor, obtains montmorillonite solution, and demarcation concentration is 2.78mg/mL.
The PCDA of 10mg is weighed, in being dissolved in the NaOH solution of the 0.5mol/L of 1mL, 70 DEG C of heating 5min obtain pink colour glue
Shape solution.Above-mentioned 6.8mL montmorillonites solution is taken, is mixed with the PCDA hot solutions of 0.1mL, 70 DEG C of heating stirrings 5min stand
15min is cooled to room temperature.Solution after cooling is placed in into illumination 5min under uviol lamp, obtain the thermochromism montmorillonite of purple-
PCDA solution.Vacuum filtration is carried out to montmorillonite-PCDA solution, montmorillonite-PCDA laminar composites are obtained.Thermogravimetric analysis shows
Show, montmorillonite mass fraction is 94.2%.Mechanics Performance Testing shows, tensile strength 56.5MPa, fracture toughness 0.28MJm-3。
Above-mentioned montmorillonite-PCDA laminar composites are impregnated into 120min in APTES, thermogravimetric analysis shows, APTES matter
Amount fraction is 10.9%.Mechanics Performance Testing shows, tensile strength 80.1MPa, fracture toughness 0.33MJm-3。
In a word, the present invention uses for reference the microstructure of natural seashell, from montmorillonite as base by the strategy of bionical preparation
First material, it is compound with the carbon diacetylenic acids (PCDA) of 10,12- 25 to obtain thermochromism intelligent bionic stratiform montmorillonite Composite
Material.The material not only can occur in a heated condition from purple to orange reversible color change, also with higher drawing
Stretch intensity.This intelligent artificial shell material has potentially using front in fields such as sensing detection, national defense industry, Aero-Space
Scape.
It should be noted that according to the various embodiments described above of the present invention, those skilled in the art are can to realize this completely
The four corner of bright independent claims and appurtenance, realize process and the same the various embodiments described above of method；And the present invention is not
Elaborate and partly belong to techniques well known.
The above, part specific embodiment only of the present invention, but protection scope of the present invention is not limited thereto, and appoints
What those skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in all should be covered
Within protection scope of the present invention.
Claims (10)
1. a kind of method of thermochromism bionic intelligence nano composite material, it is characterised in that as follows including step：
(1) montmorillonite solution is obtained using the method for stirring, centrifugation；The carbon diacetylenic acids (PCDA) of 10,12- 25 are dissolved in
In NaOH solution, in heating a moment, PCDA solution is obtained；
(2) montmorillonite solution and PCDA solution are placed in into illumination under uviol lamp with certain proportion mixing, obtain the thermic of purple
Discoloration montmorillonite-PCDA solution；
(3) the thermochromism montmorillonite-PCDA solution obtained by step (2) is carried out into vacuum filtration, using vacuum filtration induction certainly
Assemble method carries out induction self assembly, obtains montmorillonite-PCDA laminar composites；
(4) ratio of montmorillonite solution and PCDA solution in step (2) is changed, repeat step (2), (3), regulation and control montmorillonite-
The content of montmorillonite in PCDA laminar composites, in determining the optimal montmorillonite-PCDA laminar composites of mechanical property
Montmorillonite content；
(5) by the optimal montmorillonite-PCDA laminar composites of the mechanical property of gained in step (4) in the ethoxy of 3- aminopropyls three
Dipping, obtains strengthened montmorillonite-PCDA-APTES thermochromisms intelligent bionic stratiform montmorillonite in base silane (APTES)
Composite；Different dip times are set, regulate and control the content of APTES, determine the optimum montmorillonite-PCDA-APTES of mechanical property
The content of the APTES in thermochromism intelligent bionic stratiform montmorillonite composite material.
2. the method for a kind of thermochromism bionic intelligence nano composite material according to claim 1, it is characterised in that：Institute
In stating step (1), the process for obtaining montmorillonite solution using the method for stirring, centrifugation is as follows：1.5-3g montmorillonites are dissolved in
In 250-500mL deionized waters, after stirring 7-10 days, take suspension and be centrifuged several times, rotating speed is 2800-3000 rpm,
Take supernatant and obtain montmorillonite solution.
3. the method for a kind of thermochromism bionic intelligence nano composite material according to claim 1, it is characterised in that：Institute
In stating step (1), the 1-2mL 0.5mol/L NaOH solutions that 10-20mg 10, the carbon diacetylenic acids (PCDA) of 12- 25 are dissolved in
In, 70-80 DEG C of heating 5-10min obtains PCDA solution.
4. the method for a kind of thermochromism bionic intelligence nano composite material according to claim 1, it is characterised in that：Institute
In stating step (1), the concentration of montmorillonite solution is 2.7mg/mL to 3.2mg/mL.
5. the method for a kind of thermochromism bionic intelligence nano composite material according to claim 1, it is characterised in that：Institute
In stating step (2), by montmorillonite solution and PCDA solution with certain proportion mixing, i.e., the quality of PCDA accounts for montmorillonite and PCDA two
The 40% of person's gross mass, needs 70-80 DEG C of heating stirring 5-10min, after being well mixed, is sufficiently cooled to room temperature, and stands 15-
30min。
6. the method for a kind of thermochromism bionic intelligence nano composite material according to claim 1, it is characterised in that：Institute
In stating step (2), illumination 5min to 10min under uviol lamp is placed in so that PCDA molecules occur polymerisation, obtain the heat of purple
Mutagens color montmorillonite-PCDA solution.
7. the method for a kind of thermochromism bionic intelligence nano composite material according to claim 1, it is characterised in that：Institute
In stating step (3), adopt vacuum filtration induction self-assembling method implement process for：First by uniform montmorillonite-PCDA
Mixed solution is added in vacuum filtration bottle；Start vavuum pump, carry out vacuum filtration；With the carrying out of suction filtration, montmorillonite-based nano piece
Layer is slowly self-assembled into layer structure under flow action, treats that suction filtration is completed, that is, obtain montmorillonite-PCDA laminar composites.
8. the method for a kind of thermochromism bionic intelligence nano composite material according to claim 1, it is characterised in that：Institute
The thickness range for stating the montmorillonite-PCDA laminar composites of step (3) preparation is 5-20 microns.
9. the method for a kind of thermochromism bionic intelligence nano composite material according to claim 1, it is characterised in that：Institute
In stating step (4), the content for regulating and controlling montmorillonite is respectively 60%, 70%, 80%, 90%, 95%, that is, the quality of the PCDA for adding
The 40% of both montmorillonite and PCDA gross mass, 30%, 20%, 10%, 5% is accounted for, by the illiteracy for characterizing different montmorillonite contents
The mechanical property of de- soil-PCDA laminar composites, determines the montmorillonite mass fraction of optimum performance.
10. the method for a kind of thermochromism bionic intelligence nano composite material according to claim 1, it is characterised in that：
In the step (5). the dip time of regulation and control APTES is respectively 10min, 30min, 60min, 120min；It is different by characterizing
The mechanical property of the montmorillonite-PCDA-APTES thermochromism intelligent bionic stratiform montmorillonite composite materials of APTES contents, it is determined that
The APTES mass fractions of optimum performance.
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| CN114920295A (en) * | 2022-06-06 | 2022-08-19 | 济南大学 | Thermochromic composite nanomaterial, preparation method and application thereof, and composite film formed by thermochromic composite nanomaterial |
| CN115073820A (en) * | 2022-04-18 | 2022-09-20 | 华南理工大学 | Magadiite/polydiacetylene multiple-stimulus response composite material and preparation method thereof |
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