CN113845673B - Preparation method of step-cured silica gel film and application of step-cured silica gel film in field of skin electronics - Google Patents
Preparation method of step-cured silica gel film and application of step-cured silica gel film in field of skin electronics Download PDFInfo
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- CN113845673B CN113845673B CN202110597378.4A CN202110597378A CN113845673B CN 113845673 B CN113845673 B CN 113845673B CN 202110597378 A CN202110597378 A CN 202110597378A CN 113845673 B CN113845673 B CN 113845673B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/05—Polysiloxanes containing silicon bound to hydrogen
Abstract
The invention relates to a preparation method of a step curing silica gel film and application thereof in the field of surface electronics, wherein a gradient curing polysiloxane system is designed, and a gradient curing polysiloxane film is prepared according to the principle of catalyst concentration gradient diffusion, so that one side of the film has large modulus and can be used for subsequent treatment such as a deposition circuit system and the like; the other side has small modulus and adhesion, and can be attached to any surface. Such a substrate material can make conformal contact with and adhere strongly to the skin; meanwhile, the whole mechanical property of the thickened film is not damaged, one surface of the fully solidified film can be used for mounting devices, the fully solidified film can be used in the wearable electronic field such as skin electronics, and the high integration level and reliability of the devices are ensured while the comfort and adhesiveness of the fully solidified film to human bodies are improved.
Description
Technical Field
The invention belongs to the field of flexible materials and electronic packaging materials, and particularly relates to a preparation method of a stepped curing silica gel film and application of the stepped curing silica gel film in the field of skin electronics.
Background
Skin electronics, i.e., wearable electronics attached to the skin, is a new form of development in the field of wearable electronics in recent years, exhibiting great advantages in many fields of health monitoring, human-machine interaction, electronic skin, athletic monitoring, and clinical medicine due to its comfort of wear (no contact pressure applied to the wearer), high fidelity and reliability of captured physiological signals, and the ability to monitor in long-term, real-time [1-3] . However, the development of epidermal electrons remains a challenge, particularly the interface between epidermal electrons and skin should be sufficiently soft and adhesive. In order to avoid abrasion and damage to the skin and to improve the wearable comfort, the interface of the epidermal electrons with the skin preferably has a modulus similar to that of the skin (0.5 to 1.95 MPa) [4] . At the same time, firm adhesion of the epidermal electrons to the skin is critical to ensure conformal contact with the skin for accurate measurement and elimination of motion artifacts [5,6] 。
An effective way to achieve skin-device interface softness and adhesion is to modify the polymeric material to have a modulus low enough, typically less than 100KPa. This is not only soft, but it can form a pressure sensitive adhesive that can achieve instantaneous adhesion to the skin at normal temperature. However, if the entire device substrate is made of pressure sensitive adhesive, it is susceptible to impurities and dust, resulting in device contamination andand (3) failure. In addition, when the modulus of the whole device substrate is too low, the device is easy to damage and creep during use, and the device integration on the substrate surface is difficult. Because the modulus of typical chips and components is in the GPa scale, the integration of these components generally requires that the substrate be sufficiently stiff to maintain system stability and reliability [7,8] . However, general rigid printed circuit boards (PCB boards) cannot be used for skin electronics, and polysiloxanes are currently the most widely used stretchable electronic substrate materials due to their high stretchability, transparency, chemical stability, mechanical stability and biocompatibility [9,10,11,12] . Although the modulus of silicones is also on the order of several MPa and the modulus of ICs is still on the order of several orders of magnitude different, various strain isolation strategies have been developed to successfully integrate circuits on silicone substrates via scalable interconnects. However, polysiloxanes are not an intrinsic adhesive, and the bonding to the skin is only through very weak van der waals interactions. Thus, it would be highly desirable to design a skin electronic substrate that has excellent adhesion, soft and comfortable skin interface, and stability of electronic device integration, but appears to be difficult to achieve simultaneously.
Reference to the literature
[1]，Ji-Won Seo,Hyojung Kim, KyuHanKimet al. Calcium-Modified Silk as a Biocompatible and Strong Adhesive for Epidermal Electronics[J]. Advanced Functional Materials, 2018, 28（36）: 1800802；
[2]，Jan Roth,Victoria Albrecht, MirkoNitschkeet al. Surface Functionalization of Silicone Rubber for Permanent Adhesion Improvement[J]. Langmuir, 2008, 24（21）: 12603-12611；
[3]，Xian Huang,Yuhao Liu, KaileChenet al. Stretchable, Wireless Sensors and Functional Substrates for Epidermal Characterization of Sweat[J]. Small, 2014, 10（15）: 3083-3090；
[4]，Woon-Hong Yeo,Yun-Soung Kim, JongwooLeeet al. Multifunctional Epidermal Electronics Printed Directly Onto the Skin[J]. Advanced Materials, 2013, 25（20）: 2773-2778；
[5]，Kyung-In Jang,Sang Youn Han, Sheng Xuet al. Rugged and breathable forms of stretchable electronics with adherent composite substrates for transcutaneousmonitoring[J]. Nature Communications, 2014, 5（1）:4779；
[6]，Taehoon Kim,Junyong Park, JongmooSohnet al. Bioinspired, Highly Stretchable, and Conductive Dry Adhesives Based on 1D–2D Hybrid Carbon Nanocomposites for All-in-OneECG Electrodes[J]. ACS Nano, 2016, 10（4）: 4770-4778；
[7]，Dirk-M.Drotlef, MortezaAmjadi, Muhammad Yunusaet al. Bioinspired Composite Microfibers for Skin Adhesion and Signal Amplification of Wearable Sensors[J]. Advanced Materials, 2017, 29（28）: 1701353；
[8]，FrancescaTramacere, Nicola M. Pugno, Michael J. Kubaet al. Unveiling the morphology of the acetabulum in octopus suckers and its role in attachment[J]. Interface focus, 2015, 5（1）: 20140050；
[9]，Bong Kuk Lee,Jin HwaRyu, In-Bok Baeket al. Silicone-Based Adhesives with Highly Tunable Adhesion Force for Skin-Contact Applications[J]. Advanced Healthcare Materials, 2017, 6（22）: 1700621；
[10]，SeungHeeJeong,Shuo Zhang, KlasHjortet al. PDMS-Based Elastomer Tuned Soft, Stretchable, and Sticky for Epidermal Electronics[J]. Advanced Materials, 2016, 28（28）: 5830-5836；
[11]，Junhyung Kim,Yujin Hwang, SunhoJeonget al. An elastomer for epidermal electronics with adjustable adhesion force and stretchabilityobtainedviaareverse-micelle-induced process[J]. Journal of Materials Chemistry C, 2018, 6（9）: 2210-2215；
[12]，EmreKizilkan,Stanislav N. Gorb. Bioinspired Further Enhanced Dry Adhesive by the Combined Effect of the Microstructure and Surface Free-Energy Increase[J]. ACS Applied Materials&Interfaces, 2018, 10（31）: 26752-26758；
[13]，Zhuo Li,Kristen Hansen, YagangYaoet al. The conduction development mechanism of silicone-based electrically conductive adhesives[J]. Journal of Materials Chemistry C, 2013, 1（28）: 4368。
Disclosure of Invention
The invention aims to provide a preparation method of a step curing silica gel film and application of the step curing silica gel film in the field of epidermis electronics. One common way of curing polysiloxanes at room temperature in the curing mechanism is to obtain crosslinked organosilicon compounds by hydrosilylation reaction of Si-H bonds with c=c double bonds (platinum catalysis) [13]. When Pt encounters electron rich elements such as N, P of the V main group and O, S of the VI main group, it forms a complex with Pt, which becomes "poisoned" by the platinum catalyst and loses catalytic activity for the PDMS crosslinking reaction. In the present invention, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane (AEAPS) is supported on a glass sheet, and the AEAPS is immobilized on the surface of the glass sheet by hydrolysis of the three methoxy groups in the AEAPS to form silicon hydroxyl groups and condensation of the hydroxyl groups on the surface of the glass to form covalent bonds. And then the polysiloxane prepolymer is coated on the surface of the glass sheet treated by AEAPS, and two amino groups of AEAPS are complexed with Pt atoms to form a stable five-membered ring structure, so that Pt in polysiloxane at the contact surface with glass is captured, and the concentration of Pt on the surface is rapidly reduced. The concentration of Pt catalyst in polysiloxane far from the glass surface is higher than that in the glass surface, and therefore, the concentration difference causes the Pt catalyst to start to diffuse into the glass surface, thereby forming a gradient of Pt in the thickness direction perpendicular to the glass surface. At this time, the polysiloxane was heated to rapidly cure, and the diffusion of Pt after curing was suppressed, and according to the concentration gradient of Pt in the thickness direction at this time, a polysiloxane film having a gradient cross-linking density was obtained. The surface close to the glass has low Pt concentration and low crosslinking density, so that the glass is soft and sticky, can be used for attaching skin, and can obtain close contact with the skin in the bending and stretching processes and good measurement signals. The surface far away from the glass, namely the interface contacted with air, is completely solidified, so that the original mechanical performance is maintained for supporting high-integration and complex circuit systems. Thus realizing the softness and strong adhesion of the contact surface with the skin; but also realizes enough strength and hardness away from the skin surface to ensure stable integration of components.
The invention provides a preparation method of a step curing silica gel film, which comprises the following specific steps:
(1) Load of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane (AEAPS) on hydroxyl-containing substrate surface
(1.1) cleaning of substrates
(1.1.1) ultrasonic cleaning the substrate by deionized water for 5-30 minutes, and then drying by nitrogen;
(1.1.2) removing organic matters on the surface of the blow-dried substrate by adopting a manner of etching with a piranha solution, plasma or UV-O3 and the like, and generating more hydroxyl groups on the surface of the blow-dried substrate;
(1.2) bonding of the substrate to the surface of the silane coupling agent
(1.2.1) preparing AEAPS solution with concentration of 1-5% by using methanol or ethanol as solvent and AEAPS as solute;
(1.2.2) immersing the treated substrate in the AEAPS solution obtained in the step (1.2.1) for 1-2 hours;
(1.2.3) taking out the substrate, placing the substrate in a blast oven, heating to 100-105 ℃, and keeping the temperature for 8-12 minutes to evaporate water generated by combining AEAPS with hydroxyl on the surface of the substrate, so as to realize covalent bonding of the substrate and the AEAPS;
(2) Preparation of gradient cured polysiloxane films
(2.1) surrounding a groove mold with a depth of 0.1-3 mm on the substrate with the AEAPS loaded on the surface; the two components of the polysiloxane already containing the Pt catalyst (typically 5-50ppm Pt catalyst) are stoichiometric with Si-H bonds and Si-c=c bonds in a ratio of 1:1, then pouring the mixture into a groove die, respectively placing the mixture, controlling the time to be 15-240 minutes, and allowing the Pt catalyst to diffuse for different durations; particularly, when the AEAPS concentration is 1-3%, the surrounding groove depth is 0.2 mm, and the diffusion time is 15-45min, the obtained ladder cured polysiloxane has proper bonding strength;
and (2.2) putting the polysiloxane diffused for a certain time into a blast oven for heating and curing, thus obtaining the gradient cured step cured silica gel film.
In the invention, the substrate in the step (1.1.1) is any one of glass, silicon wafer, metal, plastic or paper.
In the invention, the AEAPS solution with the concentration of 1% -3% is prepared in the step (1.1.1), so that the skin adhesive strength is better.
In the invention, the AEAPS concentration is 1-3% in the step (2.1), the surrounding groove depth is 0.2 mm, and the diffusion time is 15-45min, so that the obtained step curing polysiloxane has proper bonding strength.
In the invention, the obtained step curing silica gel film is soft and sticky on one side, can be used for attaching skin, and can obtain close contact with the skin in the bending and stretching processes and good measurement signals. The other side of the device maintains the original mechanical performance and can support high-integration and complex circuit systems. Thus realizing the softness and strong adhesion of the contact surface with the skin; but also realizes enough strength and hardness away from the skin surface to ensure stable integration of components.
In the invention, the bonding strength of the semi-cured side of the obtained step cured silica gel film on the skin of a human body can be adjusted within the range of 0-18N/m (90 DEG peeling method).
In the present invention, the thickness of the semi-cured PDMS film can be adjusted between 0.1 and 3 millimeters by adjusting the thickness of the mold on the AEAPS substrate sheet.
The step curing silica gel film prepared by the preparation method can be applied to the field of epidermis electronics, and an electronic device flexible circuit and the like can be loaded on the obtained film to realize epidermis electronic functions such as myoelectricity, electrocardiosignal detection and the like; the method comprises the following specific steps:
(1) Two components of 184 silica gel Polydimethylsiloxane (PDMS) were combined at 10:1, adding 3 times of silver powder by mass, and uniformly stirring to obtain Ag/PDMS conductive adhesive;
(2) Coating the Ag/PDMS conductive adhesive obtained in the step (1) on the step curing silica gel film, loading the surface skin electronic device, heating and curing in a 160 ℃ oven for 1 hour, and then carrying out electrocardiogram measurement (ECG).
The invention has the beneficial effects that: the invention designs a gradient cured polysiloxane system, and prepares a gradient cured polysiloxane film according to the principle of catalyst concentration gradient diffusion, so that one side of the gradient cured polysiloxane film has large modulus and can be used for subsequent treatment such as a deposition circuit system and the like; the other side has small modulus and adhesion, and can be attached to any surface. Such a substrate material can make conformal contact with and adhere strongly to the skin; meanwhile, the whole mechanical property of the thickened film is not damaged, one surface of the fully solidified film can be used for mounting devices, the fully solidified film can be used in the wearable electronic field such as skin electronics, and the high integration level and reliability of the devices are ensured while the comfort and adhesiveness of the fully solidified film to human bodies are improved.
Drawings
FIG. 1 is a flow chart of the present invention; (a) A structural schematic diagram of AEAPS, (b) Pt capture by AEAPS for a substrate load;
the XPS analysis result of the pretreated glass surface in fig. 2 shows that the characteristic peak of C, N, O, si element can be recognized. Indicating that AEAPS has been loaded on the glass;
FIG. 3 (a) is a process of peeling off the gradient cured polysiloxane after contacting the skin away from the non-tacky side of the glass; (b) The process of peeling the gradient cured PDMS after contacting the skin close to one surface of the glass shows that the obtained polysiloxane film is adhesive after one surface is incompletely cured, and the other surface is completely cured and has no adhesive;
FIG. 4 shows the measured 90 peel strength of gradient cured polysiloxane films on human skin at AEAPS of 1%, 2%, 3%, platinum catalyst diffusion times of 15 minutes, 30 minutes, 45 minutes, respectively;
FIGS. 5 (a) and (b) are graphs showing stress-strain curves obtained by stretching a gradient cured polysiloxane film sample having a diffusion time of 30 minutes and 45 minutes, respectively.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
Load of AEAPS on glass surface
(1) Cleaning glass
a) Putting a proper amount of deionized water into a beaker, putting a glass slide into the beaker, and carrying out ultrasonic treatment for 10 minutes, and then drying with nitrogen;
b) The blow-dried glass was immersed in a piranha solution (98% concentrated sulfuric acid: 30% hydrogen peroxide solution 1: 1) Heating at 100deg.C for 10 min to remove organic matters such as oil on the surface of glass, washing with deionized water to remove piranha solution, and blow-drying with nitrogen;
(2) Surface bonding of glass to silane coupling agent
a) Methanol is used as a solvent, AEAPS is used as a solute, and AEAPS solution with the concentration of 1% is prepared;
b) Soaking the cleaned glass in AEAPS methanol solution for one hour;
c) Taking out the glass sheet, placing the glass sheet in a blast oven, heating to 110 ℃, and keeping the temperature for 10 minutes to evaporate water generated by combining AEAPS with hydroxyl groups on the surface of the glass so as to realize covalent bonding of the glass and the AEAPS;
2. preparation of gradient cured PDMS
a) Surrounding a glass sheet with AEAPS loaded on the surface with a groove mold with the depth of 200 micrometers; two components of PDMS were combined at 10:1, pouring the mixture into a mould, and standing for 30 minutes to diffuse the platinum catalyst;
b) Putting the diffused PDMS into a blast oven, heating to 100 ℃ and keeping the temperature for one hour for curing to obtain a gradient cured PDMS film;
the adhesive surface of the obtained step curing PDMS film is stuck on the skin of a human body, and the peeling strength is measured by 90 DEG peeling, and is measured to be 12N/m, and the adhesive strength of the substrate of the skin electronic PDMS film on the surface of the skin of the human body is slightly lower.
Example 2
As in example 1, but changing the AEAPS loaded substrate to an aluminum sheet, treating the surface of the aluminum sheet with plasma for 5min;
the adhesive surface of the obtained ladder cured polysiloxane film is stuck on the skin of a human body, and the peeling strength is 11N/m after 90-degree peeling measurement, so that the effective adhesion of the skin electronic polysiloxane film substrate on the skin surface of the human body can be satisfied.
Example 3
As in example 1, but the AEAPS methanol or ethanol concentration was changed to 2%;
the adhesive surface of the obtained ladder cured polysiloxane film is stuck on the skin of a human body, and the peeling strength is measured to be 17.5N/m through 90 DEG peeling, so that the effective adhesion of the skin electron PDMS film substrate on the surface of the skin of the human body can be satisfied.
Example 4
As in example 1, but the AEAPS methanol or ethanol concentration was changed to 3%;
the adhesive surface of the obtained ladder cured polysiloxane film is stuck on the skin of a human body, and the peeling strength is measured by 90 DEG peeling, and is 17.7N/m, and the adhesive strength of the adhesive surface of the ladder cured polysiloxane film substrate used for the skin of the human body is slightly lower.
Example 5
As in example 1, but with the AEAPS methanol or ethanol concentration changed to 3%, the groove depth changed to 1.5 mm, and the diffusion time changed to 1 hour;
the adhesive surface of the obtained ladder cured polysiloxane film is stuck on the skin of a human body, and the peeling strength is measured to be 14.5N/m through 90 DEG peeling, so that the effective adhesion of the skin electron PDMS film substrate on the surface of the skin of the human body can be satisfied.
Example 6
An Ag/PDMS conductive paste was coated on the step cure adhesive silicone film substrate obtained in example 3, and skin electronics were supported, and heat-cured in an oven at 160 ℃ for one hour, followed by Electrocardiographic (ECG) measurement. As shown in FIG. 5, the step-cured PDMS film substrate electronic skin has an electrocardiosignal acquisition effect comparable to that of a commercial electrode.
The above detailed description of the preparation method of the stepped cured silicone film and its application in the field of skin electronics with reference to the examples is illustrative and not restrictive, and several examples can be enumerated according to the scope of the present invention, and therefore variations and modifications are within the scope of the present invention without departing from the general inventive concept.
Claims (6)
1. The preparation method of the step curing silica gel film is characterized by comprising the following specific steps:
(1) Load of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane (AEAPS) on hydroxyl-containing substrate surface
(1.1) cleaning of substrates
(1.1.1) ultrasonic cleaning the substrate by deionized water for 5-30 minutes, and then drying by nitrogen;
(1.1.2) removing organic matters on the surface of the blow-dried substrate by adopting a piranha solution etching, plasma or UV-O3 mode, and generating more hydroxyl groups on the surface of the blow-dried substrate;
(1.2) bonding of the substrate to the surface of the silane coupling agent
(1.2.1) preparing AEAPS solution with concentration of 1-5% by using methanol or ethanol as solvent and AEAPS as solute;
(1.2.2) immersing the treated substrate in the AEAPS solution obtained in the step (1.2.1) for 1-2 hours;
(1.2.3) taking out the substrate, placing the substrate in a blast oven, heating to 100-105 ℃, and keeping the temperature for 8-12 minutes to evaporate water generated by combining AEAPS with hydroxyl on the surface of the substrate, so as to realize covalent bonding of the substrate and the AEAPS;
(2) Preparation of gradient cured polysiloxane films
(2.1) surrounding a groove mold with a depth of 0.1-3 mm on the substrate with the AEAPS loaded on the surface; the two components of the polysiloxane already containing 5-50ppm of Pt catalyst were stoichiometrically 1 with Si-H bonds and Si-c=c bonds: 1, then pouring the mixture into a groove die, placing the mixture for 15 to 240 minutes, and allowing the Pt catalyst to diffuse for different durations; when the AEAPS concentration is 1-3%, the surrounding groove depth is 0.2 mm, and the diffusion time is 15-45min, the obtained ladder cured polysiloxane has proper bonding strength;
and (2.2) putting the polysiloxane diffused for a certain time into a blast oven for heating and curing, thus obtaining the gradient cured step cured silica gel film.
2. The method according to claim 1, wherein the substrate in step (1.1.1) is any one of glass, silicon wafer, metal, plastic or paper.
3. The method of claim 1, wherein the aeaps solution having a concentration of 1% -3% is formulated in step (1.1.1) to provide improved skin adhesion.
4. The preparation method according to claim 1, wherein the step (2.1) is carried out so that the AEAPS concentration is 1-3%, the groove depth is 0.2 mm, and the diffusion time is 15-45min, and the obtained step-cured polysiloxane has a proper adhesive strength.
5. The preparation method of claim 1, wherein the obtained step-cured silica gel film is soft and sticky on one side and is used for attaching skin to obtain close contact with the skin and good measurement signals in the bending and stretching processes, and the other side keeps original mechanical properties to support a high-integration and complex circuit system, so that the soft and strong adhesion with the skin contact surface is realized; but also realizes enough strength and hardness away from the skin surface to ensure stable integration of components.
6. The application of the step curing silica gel film obtained by the preparation method of claim 1 in the field of skin electronics is characterized in that an electronic device flexible circuit is loaded on the obtained step curing silica gel film to realize the skin electronics function, and the specific steps are as follows:
(1) Two components of 184 silica gel Polydimethylsiloxane (PDMS) were combined at 10:1, adding 3 times of silver powder by mass, and uniformly stirring to obtain Ag/PDMS conductive adhesive;
(2) Coating the Ag/PDMS conductive adhesive obtained in the step (1) on the step curing silica gel film, loading the surface skin electronic device, heating and curing in a 160 ℃ oven for 1 hour, and then carrying out electrocardiogram measurement (ECG).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101629881A (en) * | 2009-08-05 | 2010-01-20 | 中国科学院南京地理与湖泊研究所 | Phosphorus fixing film applied to diffusive gradients in thin-films measurement technology |
| WO2019129387A1 (en) * | 2018-01-01 | 2019-07-04 | Rhodia Operations | Structured composites useful as low force sensors |
| CN110054788A (en) * | 2019-04-04 | 2019-07-26 | 华南理工大学 | A kind of elastomer and its preparation method and application that low temperature rapidly self-healing closes |
| CN111228572A (en) * | 2020-01-09 | 2020-06-05 | 天新福（北京）医疗器材股份有限公司 | Artificial skin and preparation method and application thereof |
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| AU2002368540A1 (en) * | 2001-05-16 | 2005-02-14 | North Carolina State University | Methods for forming tunable molecular gradients on substrates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629881A (en) * | 2009-08-05 | 2010-01-20 | 中国科学院南京地理与湖泊研究所 | Phosphorus fixing film applied to diffusive gradients in thin-films measurement technology |
| WO2019129387A1 (en) * | 2018-01-01 | 2019-07-04 | Rhodia Operations | Structured composites useful as low force sensors |
| CN110054788A (en) * | 2019-04-04 | 2019-07-26 | 华南理工大学 | A kind of elastomer and its preparation method and application that low temperature rapidly self-healing closes |
| CN111228572A (en) * | 2020-01-09 | 2020-06-05 | 天新福（北京）医疗器材股份有限公司 | Artificial skin and preparation method and application thereof |
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