CN103643227B - A kind of polyimide silver and preparation method thereof - Google Patents
A kind of polyimide silver and preparation method thereof Download PDFInfo
- Publication number
- CN103643227B CN103643227B CN201310652754.0A CN201310652754A CN103643227B CN 103643227 B CN103643227 B CN 103643227B CN 201310652754 A CN201310652754 A CN 201310652754A CN 103643227 B CN103643227 B CN 103643227B
- Authority
- CN
- China
- Prior art keywords
- silver
- polyimide
- nano
- aqueous solution
- mixed aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a kind of polyimide silver, by preparing in polyimide surface growth silver nano flower-like, silver nano flower-like is obtained in polyimide surface assembling by Nano silver piece, and Nano silver piece is obtained along 111 crystal faces growths at polyimide surface by silver nano-grain.Preparation method: the mixed aqueous solution of configuration reductive agent and Citrate trianion, and be adjusted to pH=3.2 ~ 3.8; The surface complexation prepared by surface chemical modification-ion exchange method is had the Kapton of silver ions, at room temperature immerse in mixed aqueous solution fast, dipping time is 1 ~ 10min, and uniform speed slow stirs simultaneously; Wash away remained on surface solion with deionized water after taking-up, be statically placed in seasoning in air, polyimide silver can be obtained.The present invention is while the very good mechanical properties ensureing base polyimide film, and the silver nano flower-like of generation is evenly distributed, and density is large, gathers around and has broad application prospects.
Description
Technical field
The present invention discloses a kind of polyimide silver and preparation method thereof, relate to field of metal nano technology, be specifically related to a kind of in polyimide silver of obtaining of Kapton surface in situ growth silver nano flower-like and preparation method thereof.
Background technology
Metal Nano structure often has the character of many uniquenesses, these character make them obtain investigation and application widely in fields such as optics, electricity, magnetics, catalysis, medical and nano-devices, and wherein the nano structural material of silver is owing to having excellent electroconductibility, catalytic and SERS(metal nanoparticle surface-enhanced Raman) characteristic and be subject to extensive concern.But in actual applications, compare the powder with nanostructure and colloidal sol generally prepared at present, the film with nanostructure is more convenient for operating and reclaiming, and can not pollute.So how can when ensureing the original performance of metal Nano structure and pattern, again can high-efficient simple produce the metallic film with nanostructure or metal composite thin film is a great problem.
Prior art, as the Chinese patent application document that publication number is CN102330080A, disclosing " a kind of preparation method of silver nanoparticle film ", is the method prepared silver nanoparticle sheet film and be assembled into the silver nanostructured film of flower pattern further in silicon chip, sheet glass, metal sheet substrate.Though this patent application prepares silver nano flower-like structure at multiple inorganic material surface, then correlative study is lacked for organic materials surface, which has limited with organic flexible the application of the metal Nano structure being substrate.As everyone knows, Kapton is one of organic polymer thin-film material having outstanding over-all properties, and it has excellent mechanical property, chemical stability and resistant of high or low temperature, has been widely used in the field such as Aeronautics and Astronautics and microelectronics.
Summary of the invention
The invention provides a kind of polyimide silver and preparation method thereof, take Kapton as substrate, on Kapton, original position has prepared the silver nano flower-like assembled by Nano silver piece, obtain the laminated film of silver nano flower-like and polyimide, impart this laminated film SERS characteristic by silver nanostructured electromagnetic property, gather around and have broad application prospects.
The present invention discloses a kind of polyimide silver and preparation method thereof, relate to field of metal nano technology, be specifically related to a kind of in polyimide silver of obtaining of Kapton surface in situ growth silver nano flower-like and preparation method thereof.The present invention take Kapton as substrate, and in the process that the silver ions that film surface complexing is in advance good is reduced, obtain Nano silver piece by the crystal face growth controlling silver, Nano silver piece assembles the film forming silver nano flower-like further.The present invention is while the very good mechanical properties ensureing base polyimide film, and the silver nano flower-like of generation is evenly distributed, and density is large, gathers around and has broad application prospects.
A kind of polyimide silver of the present invention, by preparing in polyimide surface growth silver nano flower-like, described silver nano flower-like is obtained in polyimide surface assembling by Nano silver piece, and described Nano silver piece is obtained along 111 crystal faces growths at polyimide surface by silver nano-grain.
The preparation method of a kind of polyimide silver of the present invention, comprises the following steps:
The mixed aqueous solution of step one, configuration reductive agent and Citrate trianion: reductant concentration is 0.01 ~ 0.001mol/l, and citric acid salt concentration is 10 ~ 0.02mmol/l, and the concentration ratio of reductive agent and Citrate trianion is 50:1 ~ 1:1; And dropwise buffer reagent is added in mixed aqueous solution, and mixed aqueous solution is adjusted to pH=3.2 ~ 3.8, for subsequent use after stirring;
Step 2, the surface complexation prepared by surface chemical modification-ion exchange method there is the Kapton of silver ions, at room temperature immerse in the reductive agent of step 2 configuration and the mixed aqueous solution of Citrate trianion fast, dipping time is 1 ~ 10min, remains a constant speed slowly stir in dipping time with 50 ~ 100 revs/min; Wash away remained on surface solion with deionized water after taking-up, be statically placed in seasoning in air, polyimide silver can be obtained.
Further, described reductive agent selects Resorcinol, DMAB(dimethyamine borane) and xitix in one.The one in Trisodium Citrate and Tripotassium Citrate selected by described Citrate trianion.The one in citric acid and nitric acid selected by described buffer reagent.
The present invention has the Kapton of silver ions for substrate with the surface complexation prepared by surface chemical modification-ion exchange method, in the process that the silver ions that film surface complexing is in advance good is reduced, is controlled the nanotopography of silver by Citrate trianion.Citrate trianion can be adsorbed on 111 crystal faces, causes anisotropic growth, and being formed with 111 is the nanometer sheet of advantage crystal face, and Nano silver piece assembles formation silver nano flower-like further, obtains polyimide silver.The present invention is while the very good mechanical properties ensureing base polyimide film, and the silver nano flower-like of generation is evenly distributed, and density is large, gathers around and has broad application prospects.
The present invention has the following advantages:
(1) preparation method is simple, and easy to operate, cost is low.
(2) can to Kapton two sides depositing silver nano flower simultaneously.
(3) silver nano flower-like that surface growth goes out is evenly distributed, and density is large, has good electromagnetic property.
(4) remain the mechanical property that polyimide is good, and belong to flexible materials, be convenient to actually operating.
Accompanying drawing explanation
Fig. 1 is polyimide silver structural representation of the present invention;
Fig. 2 is the XRD figure spectrum on polyimide silver surface of the present invention;
Fig. 3 is the surperficial SEM microstructure figure of polyimide silver embodiment 1 of the present invention;
Fig. 4 is the surperficial SEM microstructure figure of polyimide silver embodiment 2 of the present invention;
Fig. 5 is the surperficial SEM microstructure figure of polyimide silver embodiment 3 of the present invention.
Embodiment
Tell about detailed process of the present invention by the following examples, provide embodiment to be convenience in order to understand, is never restriction the present invention.
A kind of polyimide silver of the present invention, by preparing in polyimide surface growth silver nano flower-like, described silver nano flower-like is obtained in polyimide surface assembling by Nano silver piece, and described Nano silver piece is obtained along 111 crystal faces growths at polyimide surface by silver nano-grain.As shown in Figure 1, the argent nanometer flower structure on flexible polyimide substrate and upper and lower surface is comprised.
Embodiment one:
The mixed aqueous solution of configuration xitix and Trisodium Citrate, ascorbic acid concentrations is 0.01mol/l, sodium citrate concentration is 0.2mmol/l, in mixed aqueous solution, the concentration ratio of xitix and Trisodium Citrate is 50:1, buffer reagent citric acid is dropwise added in this mixed aqueous solution, the pH regulating this mixed aqueous solution is 3.2, for subsequent use after slowly stirring; The surface complexation prepared by surface chemical modification-ion exchange method there is the Kapton of silver ions, at room temperature immerse fast in the mixed aqueous solution of the above-mentioned xitix that configures and Trisodium Citrate, dipping time is 2min, remains a constant speed slowly stir in dipping time with 50 revs/min; Fully clean with deionized water after taking-up, wash away remained on surface solution, be statically placed in seasoning in air, obtain polyimide silver.
By X-ray diffraction analysis, the X ray diffracting spectrum of the polyimide silver surface composition that embodiment one prepares, according to the characteristic peak of collection of illustrative plates, shows that film surface composition is argent, as shown in Figure 2.By scanning electronic microscope, microscopic appearance observation is carried out to the polyimide silver surface that embodiment one prepares, the nano flower be assembled into by Nano silver piece of Surface Creation can be seen, even compact, monolithic Nano silver piece length is about 300 ~ 800nm, thickness 20 ~ 40nm, as shown in Figure 3.
Embodiment two:
The mixed aqueous solution of configuration Resorcinol and Tripotassium Citrate, Resorcinol concentration is 0.01mol/l, concentration of potassium citrate is 1mmol/l, in mixed aqueous solution, the concentration ratio of Resorcinol and Tripotassium Citrate is 10:1, buffer reagent citric acid is dropwise added in this mixed aqueous solution, the pH regulating mixed aqueous solution is 3.5, for subsequent use after slowly stirring; The surface complexation prepared by surface chemical modification-ion exchange method there is the Kapton of silver ions, at room temperature immerse fast in the mixed aqueous solution of Resorcinol and the Tripotassium Citrate configured, dipping time is 1min, remains a constant speed slowly stir in dipping time with 80 revs/min; Fully clean with deionized water after taking-up, wash away remained on surface solution, be statically placed in seasoning in air, obtain polyimide silver.
By scanning electronic microscope, microscopic appearance observation is carried out to the polyimide silver surface that embodiment two prepares, the nano flower be assembled into by Nano silver piece of Surface Creation can be seen, even compact, monolithic Nano silver piece length is about 200 ~ 400nm, thickness 20 ~ 40nm, as shown in Figure 4.
Embodiment three:
The mixed aqueous solution of configuration DMAB and Trisodium Citrate, DMAB concentration is 0.001mol/l, and sodium citrate concentration is 1mmol/l, in mixing solutions, the concentration ratio of DMAB and Trisodium Citrate is 1:1, dropwise add buffer reagent citric acid, the pH regulating mixed aqueous solution is 3.8, for subsequent use after slowly stirring; The surface complexation prepared by surface chemical modification-ion exchange method there is the Kapton of silver ions, at room temperature immerse fast in the mixed aqueous solution of DMAB and the Trisodium Citrate configured, dipping time is 5min, remains a constant speed slowly stir in dipping time with 100 revs/min; Fully clean with deionized water after taking-up, wash away remained on surface solution, be statically placed in seasoning in air, obtain polyimide silver.
By scanning electronic microscope, microscopic appearance observation is carried out to the polyimide silver surface that embodiment three prepares, the nano flower be assembled into by Nano silver piece of Surface Creation can be seen, even compact, monolithic Nano silver piece length is about 500 ~ 900nm, thickness 20 ~ 40nm, as shown in Figure 5.
Although invention has been described for composition graphs above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; instead of it is restrictive; those of ordinary skill in the art is under enlightenment of the present invention; when not departing from present inventive concept, can also make a lot of distortion, these all belong within protection of the present invention.
Claims (5)
1. a polyimide silver, it is characterized in that, by preparing in polyimide surface growth silver nano flower-like, described silver nano flower-like is obtained in polyimide surface assembling by Nano silver piece, and described Nano silver piece is obtained along 111 crystal faces growths at polyimide surface by silver nano-grain.
2. a preparation method for polyimide silver as claimed in claim 1, is characterized in that: comprise the following steps:
The mixed aqueous solution of step one, configuration reductive agent and Citrate trianion: reductant concentration is 0.01 ~ 0.001mol/l, and citric acid salt concentration is 10 ~ 0.02mmol/l, and the concentration ratio of reductive agent and Citrate trianion is 50:1 ~ 1:1; And dropwise buffer reagent is added in mixed aqueous solution, and mixed aqueous solution is adjusted to pH=3.2 ~ 3.8, for subsequent use after stirring;
Step 2, the surface complexation prepared by surface chemical modification-ion exchange method there is the Kapton of silver ions, at room temperature immerse in the reductive agent of step one configuration and the mixed aqueous solution of Citrate trianion fast, dipping time is 1 ~ 10min, remains a constant speed slowly stir in steeping process with 50 ~ 100 revs/min; Wash away remained on surface solion with deionized water after taking-up, be statically placed in seasoning in air, polyimide silver can be obtained.
3. according to a kind of described in claim 2 preparation method of polyimide silver, it is characterized in that, the one in Resorcinol, DMAB and xitix selected by described reductive agent.
4. according to a kind of described in claim 2 preparation method of polyimide silver, it is characterized in that, the one in Trisodium Citrate and Tripotassium Citrate selected by described Citrate trianion.
5. according to a kind of described in claim 2 preparation method of polyimide silver, it is characterized in that, the one in citric acid and nitric acid selected by described buffer reagent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652754.0A CN103643227B (en) | 2013-12-04 | 2013-12-04 | A kind of polyimide silver and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652754.0A CN103643227B (en) | 2013-12-04 | 2013-12-04 | A kind of polyimide silver and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103643227A CN103643227A (en) | 2014-03-19 |
| CN103643227B true CN103643227B (en) | 2016-02-03 |
Family
ID=50248506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310652754.0A Expired - Fee Related CN103643227B (en) | 2013-12-04 | 2013-12-04 | A kind of polyimide silver and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103643227B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105158227B (en) * | 2015-06-05 | 2018-03-06 | 中物院成都科学技术发展中心 | A kind of method for preparing SERS substrates |
| CN106546720B (en) * | 2016-10-31 | 2020-05-05 | 山东师范大学 | Preparation method of three-dimensional graphene/silver nanoflower stretchable biosensor material |
| CN110216295B (en) * | 2019-07-08 | 2023-06-16 | 鲁东大学 | Room temperature water phase preparation method of silver nano flowers and glucose electrocatalytic oxidation thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958197A (en) * | 2006-11-16 | 2007-05-09 | 中国科学院长春应用化学研究所 | Method for preparing Nano silver piece |
| CN102330080A (en) * | 2011-07-14 | 2012-01-25 | 东北师范大学 | Method for preparing silver nano flower-like film |
| CN102490423A (en) * | 2011-11-25 | 2012-06-13 | 桂林电器科学研究院 | Conductive polyimide film and preparation method thereof |
| CN203151767U (en) * | 2013-02-01 | 2013-08-21 | Kmt纳米科技（香港）有限公司 | Nano composite current-guide electric heating film |
| CN103280466A (en) * | 2013-05-09 | 2013-09-04 | 南开大学 | High-reflection and high-velvet-degree back electrode based on AlOx/Ag/ZnO structure |
| CN103337985A (en) * | 2013-07-12 | 2013-10-02 | 北京大学 | Single-surface friction power generator based on transverse friction and preparation method of single-surface friction power generator |
-
2013
- 2013-12-04 CN CN201310652754.0A patent/CN103643227B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958197A (en) * | 2006-11-16 | 2007-05-09 | 中国科学院长春应用化学研究所 | Method for preparing Nano silver piece |
| CN102330080A (en) * | 2011-07-14 | 2012-01-25 | 东北师范大学 | Method for preparing silver nano flower-like film |
| CN102490423A (en) * | 2011-11-25 | 2012-06-13 | 桂林电器科学研究院 | Conductive polyimide film and preparation method thereof |
| CN203151767U (en) * | 2013-02-01 | 2013-08-21 | Kmt纳米科技（香港）有限公司 | Nano composite current-guide electric heating film |
| CN103280466A (en) * | 2013-05-09 | 2013-09-04 | 南开大学 | High-reflection and high-velvet-degree back electrode based on AlOx/Ag/ZnO structure |
| CN103337985A (en) * | 2013-07-12 | 2013-10-02 | 北京大学 | Single-surface friction power generator based on transverse friction and preparation method of single-surface friction power generator |
Non-Patent Citations (1)
| Title |
|---|
| Formation of conductive and reflective silver nanolayers on plastic films via ion doping and solid-liquid interfacial reduction at ambient temperature;Guanghui Cui等;《Acta Materialia》;20130503;第61卷(第11期);摘要第3-5行，第4082页左栏第3段-右栏第1段，附图1、4、6、8、9 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103643227A (en) | 2014-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Acharya et al. | Ethylenediamine-mediated wurtzite phase formation in ZnS | |
| Li et al. | Direct electrodeposition of ZnO nanotube arrays in anodic alumina membranes | |
| Wu et al. | Synthesis of Eu2O3 nanotube arrays through a facile sol− gel template approach | |
| Peng et al. | Morphological selection of electroless metal deposits on silicon in aqueous fluoride solution | |
| Lu et al. | Facile electrochemical synthesis of single crystalline CeO2 octahedrons and their optical properties | |
| Desai et al. | Facile soft solution route to engineer hierarchical morphologies of ZnO nanostructures | |
| Shanmugasundaram et al. | Hierarchical mesoporous In2O3 with enhanced CO sensing and photocatalytic performance: distinct morphologies of In (OH) 3 via self assembly coupled in situ solid–solid transformation | |
| CN102275981B (en) | Preparation method of self-substrate SnO2 nanorod array | |
| CN103643227B (en) | A kind of polyimide silver and preparation method thereof | |
| Fukuda et al. | Kinetics and mechanisms of the thermal decomposition of copper (II) hydroxide: A consecutive process comprising induction period, surface reaction, and phase boundary-controlled reaction | |
| Kitabayashi et al. | Physico-geometrical mechanism and overall kinetics of thermally induced oxidative decomposition of tin (II) oxalate in air: Formation process of microstructural tin (IV) oxide | |
| CN105112897A (en) | Preparation method for porous copper-gold composite nanometer film material | |
| CN105543817A (en) | Gold-sliver alloy two-dimensional ordered nano film prepared by in-situ interface transformation and method for preparing gold-sliver alloy two-dimensional ordered nano film | |
| Yu et al. | Facile synthesis of three dimensional porous ZnO films with mesoporous walls and gas sensing properties | |
| CN104607657A (en) | Copper-silver double-metal nanowire and preparation method thereof | |
| CN104404504A (en) | Universal method for controllably preparing nano particles on graphene sheet | |
| Xu et al. | Effects of electroless nickel plating method for low temperature joining ZnS ceramics | |
| Wang et al. | Self-assembled synthesis of Ag nanodendrites and their applications to SERS | |
| Song et al. | Molybdenum nitride porous prisms with a strong plasmon resonance effect in the visible region for surface-enhanced Raman spectroscopy | |
| Dinda et al. | Amino acid-based redox active amphiphiles to in situ synthesize gold nanostructures: from sphere to multipod | |
| CN102990077B (en) | Method for growing bismuth nanoparticles on oxide substrate in situ | |
| CN104649273A (en) | Preparation method of low-doped porous P-type silicon nanowire | |
| CN104988476A (en) | Method for plating nano-silver on surface of diamond micro-powder | |
| CN105290419A (en) | Fishbone-shaped core-shell structure nanometer nickel-copper alloy powder and preparation method thereof | |
| Xu et al. | Temperature-controlled growth of ZnO nanowires and nanoplates in the temperature range 250− 300 C |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160203 Termination date: 20211204 |