WO2019015520A1 - Procédé de modification de surface pour ruban étirable flexible, et son utilisation - Google Patents

Procédé de modification de surface pour ruban étirable flexible, et son utilisation Download PDF

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Publication number
WO2019015520A1
WO2019015520A1 PCT/CN2018/095332 CN2018095332W WO2019015520A1 WO 2019015520 A1 WO2019015520 A1 WO 2019015520A1 CN 2018095332 W CN2018095332 W CN 2018095332W WO 2019015520 A1 WO2019015520 A1 WO 2019015520A1
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line
chip
pattern
liquid metal
liquid
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PCT/CN2018/095332
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English (en)
Chinese (zh)
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蒋兴宇
成诗宇
唐立雪
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国家纳米科学中心
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05Patterning and lithography; Masks; Details of resist
    • H05K2203/0502Patterning and lithography
    • H05K2203/0528Patterning during transfer, i.e. without preformed pattern, e.g. by using a die, a programmed tool or a laser

Definitions

  • the invention belongs to the field of electronic circuits, and in particular relates to a surface modification method of a flexible stretchable line and an application thereof.
  • the method is essentially a simple and convenient and versatile liquid metal patterning technique that allows liquid metal patterning to be achieved simply and quickly on a wide variety of substrates.
  • the preparation method is simple and rapid, and the amount of liquid metal is small, no additional external force is required, the pattern does not generate cracks, the line width is controllable, and the resolution is high, and is suitable for mass production.
  • the circuit prepared according to this method has excellent flexibility and stretchability, and is suitable for circuits of various line widths (line widths up to 1 micron).
  • indium gallium, two kinds of liquid metal element compounds are various high-performance semiconductor materials which are commonly used in themselves, so the preparation method can be extended to the preparation of various semiconductors.
  • PDMS means: polydimethylsiloxane.
  • the "PDMS” solution described herein includes a prepolymer and a curing agent in a ratio of 5:1 to 50:1.
  • Smooth-on series of materials refers to a series of commercially available materials such as silicone, rubber, resin and polyurethane developed and sold by the US company Smooth-on. Such as Smooth-on Ecoflex series, Smooth-on Dragon Skin series, etc.
  • Standard-on Ecoflex Series refers to a range of silicone rubbers developed and sold by the US company Smooth-on, including Ecoflex 0010, Ecoflex 0020, Ecoflex 0030, Ecoflex 0050, and the like. It is super soft, strong and elastic after curing, and does not shrink.
  • Smooth-on Dragon Skin Series refers to a series of silicone rubber developed and sold by American smooth-on company, including Dragon Skin 10, Dragon Skin 20, Dragon Skin 30, and Dragon Skin FX. It is soft after curing and has high stretchability and recovery.
  • PET means: polyethylene terephthalate
  • polymer means a molecule having a relative molecular mass of more than 10,000.
  • lastomer means a soft material that has both flexibility and tensile properties, such as PDMS, Smooth-on series materials, and the like.
  • original patterned layer refers to a layer that is patterned on a substrate material using liquid metal particles.
  • Fibronectin means: fibronectin
  • Collagen I/III means: collagen I/III;
  • Laminin means: laminin
  • Gelatin means: gelatin
  • PLGA means: a polylactic acid-glycolic acid copolymer
  • PCL means: polycaprolactone
  • PLCL means: polylactic acid-polycaprolactone
  • PEIE means: ethoxylated polyethyleneimine.
  • a first aspect of the present invention provides a method of preparing a flexible stretchable conductive circuit, the method comprising the steps of:
  • the liquid metal in the step 1) is selected from one or more of the following: gallium, mercury, gallium indium alloy, gallium indium tin alloy and antimony tin lead indium alloy, the volatile liquid solvent is selected from the group consisting of: liquid at room temperature Alcohol, ketone or ether;
  • the method of drawing in step 2) is selected from one or more of the following: hand-drawn, missing letter plate, screen printing, inkjet printing, and microfluidic channel filling;
  • the polymer solution in the step 3) is selected from the group consisting of PDMS, modified PDMS, Smooth-on series materials, PLGA, PCL, PLCL and other degradable polymer solutions.
  • the ratio of the PDMS prepolymer to the curing agent can be 5:1 to 30:1, preferably 5:1 to 25:1, more preferably 10:1 to 20:1, most preferably 10:1;
  • the modified PDMS components include a prepolymer, a curing agent , PEIE (ethoxylated polyethyleneimine), the ratio is 100:20:1 to 600:20:1, preferably 200:20:1 to 600:20:1, more preferably 200:20:1 400:20:1, most preferably 200:20:1,
  • the proportion of Smooth–on AB components is 1:1 to 4:1, preferably 1:1 to 3:1, more preferably 1:1 to 2: 1, most preferably 1:1.
  • the method further comprises:
  • step 4 performing direct surface modification or multiple surface modification on the flexible stretchable conductive circuit obtained in the step 4), wherein the direct surface modification is directly performing surface bioactive substance modification, and the multiple surface modification is chemical modification first.
  • the direct surface modification is directly performing surface bioactive substance modification, and the multiple surface modification is chemical modification first.
  • the surface bioactive substance modification comprises: using a microfluidic technology, designing a microfluidic chip suitable for the shape of the line for different circuit patterns, adding extracellular matrix proteins, cells/bioactive substances or organisms to the chip. Active topical modification of the active drug; and/or
  • the chemical modification comprises: reacting the inorganic salt with the liquid metal and the surface oxide layer, and depositing the formed nanoparticles on the surface of the line to form a surface metal layer with a controllable thickness of several nanometers to several micrometers.
  • the extracellular matrix protein is selected from one or more of the group consisting of fibronectin, collagen I/III, laminin and gelatin;
  • the cell/biologically active substance is selected from one or more of the following: DNA, RNA, and protein;
  • the bioactive drug is selected from one or more of the group consisting of rapamycin, everolimus, and paclitaxel; and/or
  • the inorganic salt is selected from one or more of the group consisting of HAuCl 4 , AgNO 3 , CuCl 2 , HCl, Na 2 CO 3 and NaHCO 3 .
  • the polymeric elastomer is selected from one or more of the following: PET, polydimethylsiloxane, and Smooth-on series materials, preferably, the Smooth-on series material is selected from the group consisting of Smooth-on Ecoflex series and Smooth-on Dragon Skin collection.
  • a second aspect of the invention provides a flexible stretchable electrically conductive circuit produced by the method of the first aspect.
  • a third aspect of the invention provides an implantable medical device comprising the stretchable conductive circuit of the second aspect.
  • a fourth aspect of the invention provides an electrostimulation chip/electrode or electrotransfection chip/electrode, the chip/electrode of the stretchable conductive line of the second aspect.
  • a fifth aspect of the present invention provides a wearable electronic device, the wearable electronic device comprising:
  • a chip/electrode according to the fourth aspect of the invention is a chip/electrode according to the fourth aspect of the invention.
  • a sixth aspect of the invention provides an electrical stimulation treatment method, the method comprising:
  • a stretchable conductive circuit as in the second aspect of the invention is provided.
  • a seventh aspect of the invention provides a gene transfection method, the method comprising:
  • a stretchable conductive circuit as in the second aspect of the invention is provided.
  • An eighth aspect of the invention provides a protein transfection method, the method comprising:
  • a stretchable conductive circuit as in the second aspect of the invention is provided.
  • a ninth aspect of the invention provides the use of a flexible stretchable electrically conductive circuit made in accordance with the method of the first aspect of the invention in the manufacture of a device or device medical device for use in surgery and/or electrical stimulation therapy.
  • a tenth aspect of the invention provides a method of preparing a semiconductor material, the method comprising the steps of:
  • the surface chemical technology and microfluidic technology are mainly used to surface modify the flexible circuit based on liquid metal and polymer to improve its functionality and improve its biocompatibility. On this basis, expand the relevant biological applications.
  • liquid metal mainly: gallium, mercury, gallium indium alloy, gallium indium tin alloy, antimony tin, lead indium alloy and other low melting point metals
  • volatile liquids mainly refers to low boiling solvents such as liquid alcohol at room temperature
  • a substance, a ketone substance or an ether substance, etc. is mixed with ultrasonic waves to prepare a liquid metal particle having a core-shell structure.
  • the upper pattern is drawn on the original pattern layer material selected by hand drawing, missing letter board, screen printing, ink jet printing, and micro flow channel filling.
  • a pattern composed of liquid metal particles is left, and a polymer solution such as PDMS, Smooth-on series materials or the like is cast on the pattern to form a peeling layer.
  • the liquid polymer can partially penetrate into the gaps of the stacked liquid metal particles to form a porous structure.
  • the thickness of the release layer is determined by the speed and time of the silicone rubber.
  • the amount of liquid metal contained in the pattern formed on the original pattern layer and the peeling layer is also different depending on the affinity (adhesion) force of the original pattern layer and the peeling layer.
  • affinity adheresion
  • different types of lines having the shape and thickness as shown in FIG. 1 can be prepared on a large scale.
  • Direct surface modification refers to the use of microfluidic technology to design a microfluidic chip suitable for the shape of the line for different line patterns (Fig. 2), and to add extracellular matrix proteins to the chip (eg Fibronectin, Collagen I/III, Laminin). , Gelatin, etc., cells/bioactive substances (such as DNA, RNA, protein, etc.), or bioactive drugs (such as rapamycin, everolimus, paclitaxel, etc.) and other substances for local surface modification to enhance their biology Compatibility ( Figure 3), line stability, improved degradability, etc.
  • extracellular matrix proteins eg Fibronectin, Collagen I/III, Laminin
  • Gelatin etc.
  • cells/bioactive substances such as DNA, RNA, protein, etc.
  • bioactive drugs such as rapamycin, everolimus, paclitaxel, etc.
  • Directly surface modified lines can be used for electrical conduction, directly for use or by polymer elastomer surface encapsulation (PET, different ratios of polydimethylsiloxane [PDMS] ] and Smooth-on series materials [such as Smooth-on Ecoflex series, Smooth-on Dragon Skin series] are used for implant lines ( Figure 4).
  • PET polymer elastomer surface encapsulation
  • PDMS polydimethylsiloxane
  • Smooth-on series materials such as Smooth-on Ecoflex series, Smooth-on Dragon Skin series
  • the surface modification method of the flexible stretchable line of the present invention may have, but is not limited to, the following beneficial effects:
  • the method has the advantages of simple steps, easy operation, surface treatment without special instruments, and large-scale preparation of functional flexible circuits;
  • Flexible stretchable lines with direct surface modification or multiple surface modification can be widely used in conductive lines in direct contact or indirect contact with cells or tissues for tissue engineering, biosensing, optoelectronic materials, etc.;
  • Figure 1 shows a liquid metal ink used in the method of the present invention and a prepared flexible conductive circuit
  • Figure 2 shows a mold design, a physical map and a microfluidic chip used in the method of the present invention
  • Figure 3 shows a microfluidic chip after partial surface modification using the method of the present invention.
  • a is a checkerboard pattern in which liquid metal and PDMS alternate;
  • b is a partial enlarged view of a;
  • c is an endothelial cell The state of adhesion on the liquid metal;
  • df is a fluorescent confocal pattern obtained by using the cell death staining kit after one week of culture, and the cell activity is very good;
  • gh is a three-dimensional reconstructed fluorescent confocal pattern corresponding to df;
  • Figure 4 shows the circuit before and after surface encapsulation using the method of the present invention
  • Figure 5 is a circuit diagram showing before and after partial surface chemical modification using the method of the present invention.
  • Figure 6 shows a flexible conductive circuit prepared in Embodiment 2 of the present invention
  • Figure 7 shows electrical stimulation of rat lymph nodes by an electro-stimulation chip/electrode prepared by the method of the present invention
  • FIG. 8 shows the delivery and expression of green fluorescent protein particle DNA by an electrotransfection chip/electrode prepared by the method of the present invention.
  • PET was purchased from Sigma Aldrich Company of the United States
  • PDMS and cell culture dishes were purchased from Dow-corning Company
  • rapamycin, everolimus and paclitaxel were purchased from Shanghai Maclean Biochemical Technology Co., Ltd.;
  • HAuCl 4 AgNO 3 , CuCl 2 , HCl, Na 2 CO 3 , NaHCO 3 , purchased from Sigma Aldrich, USA;
  • Fibronectin Collagen I/III, Laminin, Gelatin, purchased from Sigma Aldrich, USA;
  • DMEM Opti-DMEM cell culture fluid, purchased from Life technologies, USA;
  • Fibroblasts were purchased from ScienCell, USA.
  • Vacuum oven purchased from Shanghai Qixin Scientific Instrument Co., Ltd., model DZF-6020; oven, purchased from Shanghai Pudong Rongfeng Scientific Instrument Co., Ltd., model DHG-9030A; ultrasonic cell crusher, purchased from Bianxin Ultrasonic Company, model S-450D; scanning electron microscope, purchased from Hitachi, model S4800; manual screen printing station, purchased from Guangzhou Junyu screen printing equipment, model 23*30cm; precision universal meter purchased from Fluke electronic instrumentation company, model 8846A; dynamic machinery Analyzer, model DMA Q800.
  • Piezoelectric nozzle purchased from Konica Corporation of Japan, model KM512NX 35PL.
  • HD video microscope optilia purchased from the Swedish optilia company, model M30X-E320.
  • Electroporation instrument, model BTX ECM830 was purchased from BTX Corporation of the United States.
  • the cell incubator, model was purchased from Thermo 371 and was purchased from Thermo Scientific, USA.
  • This example is intended to illustrate a flexible stretchable conductive circuit prepared using the method of the present invention.
  • the PET film was selected as the original pattern layer, and the PDMS solution was configured in a ratio of PDMS prepolymer: curing agent mass ratio of 10:1.
  • An electrode pattern of 500 micrometers line width (Fig. 5) was prepared on a PET film using screen printing techniques and its width was measured with a high definition video microscope. The pattern was placed in an oven at 80 degrees Celsius for 30 minutes. The PDMS solution was cast over the pattern on the PET film, degassed in a vacuum oven for 10 min, placed in a silicone machine at a speed of 500 rpm for 60 s to obtain a thickness of 220 micron PDMS. It was then cured in an oven at 80 degrees Celsius for 30 minutes. After the PDMS was cured, the PDMS was carefully peeled off from the original pattern layer (PET film). Thus, the pattern of liquid metal is transferred to the PDMS and has good electrical conductivity to obtain a flexible stretchable conductive line.
  • This example is intended to illustrate a flexible stretchable conductive circuit prepared using the method of the present invention.
  • the metal was dispersed into small particles of innumerable micro-nano size, and the average particle size of the small particles was 800 nm.
  • the core of the small particles is a liquid metal, and the outside is surrounded by a thin oxide film.
  • the PET film was selected as the original pattern layer, and the PDMS solution was disposed in a ratio of PDMS prepolymer: curing agent mass ratio of 10:1.
  • An electrode pattern of 200 micrometers line width (Fig. 6) was fabricated on a PET film using screen printing techniques and its width was measured with a high definition video microscope. The pattern was placed in an oven at 80 degrees Celsius for 30 minutes. The PDMS solution was cast over the pattern on the PET film, degassed in a vacuum oven for 10 min, and placed in a silicone machine at a speed of 2000 rpm for 120 s to obtain a thickness of 50 micron PDMS. It was then cured in an oven at 80 degrees Celsius for 30 minutes. After the PDMS was cured, the PDMS was carefully peeled off from the original pattern layer (PET film). Thus, the pattern of liquid metal is transferred to the PDMS and has good electrical conductivity to obtain a flexible stretchable conductive line.
  • This example is intended to illustrate the direct surface modification of flexible stretchable conductive traces using the method of the present invention.
  • microfluidic technology design a microfluidic chip suitable for the shape of the line for different line patterns (Fig. 2), add 1ml of Fibronectin solution with a concentration of 1mg/ml to the chip, cover the surface of the stretched line, and at 37 °C After incubating for 4 hours in the incubator, it was taken out and gently washed once with PBS solution of pH 7.4, and used directly for planting cells.
  • the surface-modified tensile conductive line exhibited good biocompatibility, the cells adhered well to the surface, and remained well active after 7 days of culture (Fig. 3).
  • This example is intended to illustrate the direct surface modification of flexible stretchable conductive traces using the method of the present invention.
  • microfluidic technology design a microfluidic chip suitable for the shape of the line for different line patterns. Add 2ml of Fibronectin solution with a concentration of 1mg/ml to the chip, cover the surface of the stretched line, and incubate in a 37°C incubator. After 6 hours, it was taken out and gently washed once with a PBS solution of pH 7.4, and it was directly used for planting cells.
  • the surface-modified tensile conductive line exhibits good biocompatibility, the cells adhere well to the surface, and maintain good activity after 7 days of culture.
  • This example is intended to illustrate the multiple surface modification of flexible stretchable conductive traces using the method of the present invention.
  • the tensile conductive line prepared in Example 1 was placed in a 50 ml solution of 0.01 mol/L of HAuCl 4 and taken out after soaking for 3 minutes; in the process, HAuCl 4 was reacted with the liquid metal and the surface oxide layer to be replaced.
  • the formed Au nanoparticles are deposited on the surface of the wiring to form a surface metal layer of a controllable thickness of several nanometers to several micrometers (Fig. 5), thereby greatly enhancing the surface conductivity.
  • the above treated sample was taken out in 50 ml of a 0.1 mol/L NaHCO 3 solution, and further taken out for 3 minutes; in the process, NaHCO 3 reacted with the remaining HAuCl 4 in the sample to remove it.
  • the treated sample was placed in a beaker containing 2 L of high-purity water, stirred at a low speed for 4 hours or more, and water was changed every hour; in the process, the inorganic salts remaining in the sample were mostly removed.
  • the surface bioactive substance was modified, and the modification method was the same as in Example 2.
  • This embodiment is for explaining the surface sealing method of the polymer elastomer provided by the present invention.
  • the liquid metal of the flexible conductive line obtained in Example 1 was faced upward, the PDMS solution was disposed in a ratio of a PDMS prepolymer: curing agent mass ratio of 10:1, and the flexible circuit was poured with a pre-configured PDMS solution, and The air bubbles were degassed in a vacuum oven for 10 min, and placed in a silicone machine at a speed of 500 rpm for 60 s to obtain a package having a total thickness of 450 ⁇ m. Then, it is cured in an oven at 80 degrees Celsius for 30 minutes. After curing, the packaged conductive lines are cut according to the needs of the line, that is, the surface of the polymer elastomer is encapsulated (Fig. 4).
  • This embodiment is for explaining the preparation method of the electro-stimulation chip/electrode provided by the present invention.
  • a certain chip/electrode pattern was designed in advance by CAD software, and the corresponding screen printing template was processed, and the electrode pattern shown in FIG. 7 was obtained on the PET film by screen printing technology.
  • the pattern was placed in an oven at 80 degrees Celsius for 30 minutes.
  • the PDMS solution was cast over the pattern on the PET film, degassed in a vacuum oven for 10 min, placed in a silicone machine at a speed of 1000 rpm for 60 s to obtain a thickness of 80 micron PDMS. It was then cured in an oven at 80 degrees Celsius for 30 minutes. After the PDMS was cured, the PDMS was carefully peeled off from the original pattern layer (PET film). Thus, the pattern of liquid metal is transferred to the PDMS and has good electrical conductivity.
  • the above sample was cut and subjected to direct surface modification using the method described in Example 2 to obtain a flexible stretchable chip/electrode as shown in Fig. 7 for lymph node electrical stimulation.
  • This embodiment is for explaining the preparation method of the electrotransfection chip/electrode provided by the present invention.
  • a certain chip/electrode pattern was designed in advance by CAD software, and the corresponding screen printing template was processed, and the electrode pattern shown in FIG. 5 was obtained on the PET film by screen printing technology.
  • the pattern was placed in an oven at 80 degrees Celsius for 30 minutes.
  • the PDMS solution was cast over the pattern on the PET film, degassed in a vacuum oven for 10 min, placed in a silicone machine at a speed of 1000 rpm for 60 s to obtain a thickness of 80 micron PDMS. It was then cured in an oven at 80 degrees Celsius for 30 minutes. After the PDMS was cured, the PDMS was carefully peeled off from the original pattern layer (PET film). Thus, the pattern of liquid metal is transferred to the PDMS and has good electrical conductivity.
  • This test example is used to illustrate that the electro-stimulation chip/electrode prepared by the present invention is used for electrically stimulating rat lymph nodes.
  • a rat weighing 300 g was pre-injected with 2 ml of a pentobarbital solution having a mass ratio of 0.5%. After about 15 minutes, the rats were fully anesthetized. Next, the subcutaneous layer of the rat was opened using a pre-sterilized scalpel to find the lymph node. Then, the two semi-circular electrodes of the flexible electro-stimulation chip prepared in Example 6 are closely attached to the lymph nodes, and the other end of the chip is respectively connected to the positive and negative electrodes of the electroporation device, and electrical stimulation is performed, and the voltage is 100 V, and the voltage pulse pulse is applied. The width is 100ms and the pulse interval is 1s for 6 times. After the operation, disinfection and suture were performed, and normal feeding was performed. After 1 week, changes in physiological indexes related to lymph nodes were detected.
  • This test example is intended to illustrate that the electrostimulation chip/electrode prepared by the present invention is used to effect gene transfection.
  • the electrotransfection chip prepared in Example 8 was placed in a cell culture dish, and a pre-prepared DMEM cell culture medium containing fibroblasts was added and cultured in a 37 ° C cell incubator for 3 days until the cell fusion degree After reaching 80-90% or more, it was subjected to electrotransfection experiments.
  • the above-mentioned chip covered with fibroblasts was washed three times with a PBS solution having a pH of 7.4, and the PBS solution was discarded. Then, 2 ml of a pre-configured green fluorescent protein DNA solution was added over the electrode at a concentration of 40 ug/ml and incubated for 5 minutes at room temperature.
  • the chip was connected to the positive and negative electrodes of the electroporation device (Fig. 8), and electrical stimulation was performed.
  • the voltage was 80 V
  • the voltage pulse width was 100 ⁇ s
  • the pulse interval was 1 s, which lasted 5 times.
  • place the above electrode in a new cell culture dish add 15 ml of Opti-DMEM solution specially used for electroporation cell culture, and place it in a 37 °C cell incubator for 24 hours.
  • the observation of green fluorescent protein expression by focusing microscope showed that green fluorescent protein was successfully transfected and expressed, and the transfection efficiency was above 95% (Fig. 8).

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Abstract

La présente invention concerne un procédé de modification de surface pour un ruban étirable flexible, et son utilisation. Ledit procédé peut améliorer significativement la cytocompatibilité et l'histocompatibilité d'un ruban conducteur et la stabilité du ruban conducteur en contact direct avec la cellule/le tissu, et les performances de conductivité peuvent encore être bien maintenues après une co-culture cellulaire ou une implantation in vivo de longue durée; l'effet de cage de Faraday provoqué par une couche d'oxyde de surface est surmonté, et l'électrode formée peut générer un champ électrique stable, améliorant la fonctionnalité du ruban conducteur; ledit procédé comporte des étapes simples et est facile à mettre en oeuvre, permet d'effectuer un traitement de surface sans instrument spécial, et est utilisé pour la préparation à grande échelle d'un ruban flexible fonctionnel; un ruban étirable flexible soumis à une modification de surface directe ou à de multiples modifications de surface peut être largement utilisé dans des rubans conducteurs qui sont en contact direct ou indirect avec des cellules ou des tissus, et peuvent être utilisés dans les domaines de l'ingénierie tissulaire, la biodétection, les matériaux photoélectriques, etc. Ledit procédé permet de réaliser rapidement une préparation industrielle à grande échelle, et peut être utilisé dans les domaines des dispositifs électroniques portables, des instruments médicaux implantés, etc.
PCT/CN2018/095332 2017-07-20 2018-07-11 Procédé de modification de surface pour ruban étirable flexible, et son utilisation WO2019015520A1 (fr)

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CN113171094A (zh) * 2021-04-30 2021-07-27 华中科技大学 人体情绪状态信息柔性检测电路、制备方法和集成系统
CN115433379A (zh) * 2022-08-12 2022-12-06 哈尔滨工业大学(深圳) 一种具有高可拉伸性的柔性导体及其制备方法
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