WO2019178938A1 - 一种全天候自愈合可拉伸导电材料及其制备方法 - Google Patents

一种全天候自愈合可拉伸导电材料及其制备方法 Download PDF

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WO2019178938A1
WO2019178938A1 PCT/CN2018/088155 CN2018088155W WO2019178938A1 WO 2019178938 A1 WO2019178938 A1 WO 2019178938A1 CN 2018088155 W CN2018088155 W CN 2018088155W WO 2019178938 A1 WO2019178938 A1 WO 2019178938A1
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conductive material
healing
carbon film
hydrogel
stretchable conductive
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PCT/CN2018/088155
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English (en)
French (fr)
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袁宁一
丁建宁
戴胜平
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常州大学
江苏大学
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Publication of WO2019178938A1 publication Critical patent/WO2019178938A1/zh
Priority to US16/795,721 priority Critical patent/US11515059B2/en

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    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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    • H01B1/20—Conductive material dispersed in non-conductive organic material
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/04—Polyamides derived from alpha-amino carboxylic acids
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/04—Polyamides derived from alpha-amino carboxylic acids

Definitions

  • the invention belongs to the technical field of new materials, and particularly relates to an all-weather self-healing stretchable conductive material and a preparation method thereof.
  • Hydrogel is a three-dimensional network structure polymer compound that provides a large specific surface area, which has strong mechanical strength, ductility, viscosity, toughness and recoverability.
  • This type of self-healing material helps to improve the life and safety of the device.
  • Self-healing materials can be completely or partially restored to their original state after physical, chemical or mechanical damage, most of which are achieved by reversible interactions between polymer backbones such as hydrogen bonds, covalent bonds, and intermolecular forces. .
  • the comprehensive nature is still unsatisfactory, especially as the climate changes, the electrical resistance of the conductive hydrogel changes significantly with temperature and humidity, which greatly limits the development of hydrogel.
  • the conductive hydrogel is composed of an insulated multi-space skeleton and a conductive filler material, such as polypyrrole, polyaniline, polythiophene, ionic liquid, and carbon nanotubes, and the like, as an active material.
  • a conductive filler material such as polypyrrole, polyaniline, polythiophene, ionic liquid, and carbon nanotubes, and the like.
  • the technical problem to be solved by the present invention is to provide a stretchable conductive material having good self-healing ability, the conductivity remains unchanged under different temperatures and humidity conditions, and the conductivity remains unchanged in the case of stretching.
  • Variable composite conductive material and preparation method thereof are provided.
  • the design idea of the invention is: using the rich carboxyl group and Fe 3+ in acrylic acid and ⁇ -polyglutamic acid to coordinate to form a double-layer three-dimensional network structure, so that it has strong stretching and self-healing.
  • Properties by changing the solvent combination of glycerin and water, the mass change of the hydrogel remains unchanged; the intermediate layer is a composite tantalum carbon film sputtered with metal (silver, gold, copper), and the ends are self-healing.
  • the technical scheme of the invention is as follows: firstly, acrylic acid (PAA) and modified polyglutamic acid ( ⁇ -PGAA) hydrogel are used as a skeleton, and ferric chloride hexahydrate (FeCl 3 .6H 2 O) is used for metal ion complexation.
  • Agent N, N'-methylenebisacrylamide (MBAA) is a crosslinking agent, ammonium persulfate (APS) is used as an initiator, and glycerin (GC) and water (H 2 O) are used as a mixed solvent to obtain a polymerization.
  • Acrylic acid and polyglutamic acid composite hydrogel when the composite hydrogel is stretched, adhered to the sputtered metal composite smooth carbon film, shrinks to the original length and then another hydrogel Adhered to the other side of the carbon film, the intermediate layer is a sputtered metal film, and the ends are self-healing hydrogel "sandwich" structure of the stretchable conductive material.
  • the preparation method of the conductive material of the present invention is as follows:
  • Acrylic acid, modified polyglutamic acid ( ⁇ -PGAA), ferric chloride hexahydrate (FeCl 3 .6H 2 O), N,N'-methylenebisacrylamide (MBAA), ammonium persulfate (APS), glycerin (GC) and H 2 O were proportioned into a solution, uniformly mixed, and the gas in the solution was removed by nitrogen gas for 30 minutes, and polymerization was carried out at 60 ° C for 30 minutes to obtain a composite hydrogel.
  • a tantalum carbon film was attached to a glass plate, and a metal (silver, gold, copper) was sputtered on a single-layered carbon film by a magnetron sputtering method to prepare a composite carbon film.
  • the hydrogel obtained in the step (1) is adhered to the composite carbon film under the condition of stretching 200 to 500%, and then shrinks to the original length, and then another hydrogel is attached to the carbon.
  • an intermediate layer is formed as a carbon film sputtered with metal (silver, gold, copper, etc.), and both ends are stretchable conductive materials of a "sandwich" structure of self-healing hydrogel.
  • the volume ratio of GC and H 2 O in step (1) is between 0:6 and 6:0, the amount of ⁇ -PGAA solution is 0%-80% of the total mass of the solution, and the amount of MBAA is 0% of the mass of acrylic acid. ⁇ 0.4%, the amount of APS is 2% by mass of acrylic acid, and the amount of FeCl 3 .6H 2 O is 1.25% of the amount of acrylic acid.
  • the amount of ⁇ -PGAA solution is 40% of the total mass of the solution
  • the amount of MBAA is 0.2% of the mass of acrylic acid
  • the amount of APS is 2% of the mass of acrylic acid
  • FeCl 3 .6H 2 O is used in an amount of 1.25% of the amount of the acrylic material, and is prepared from a hydrogel having a faster healing rate, a higher elongation at break, and a long-term storage.
  • the ⁇ -PGAA is prepared by dissolving 2 g of ⁇ -PGA and 4 g of allyl glycidyl ether in 25 mL of deionized water, adjusting the pH to 2 to 4 with acetic acid, and reacting for 36 hours at room temperature with dichloromethane. The mixture was extracted three times, and the aqueous layer was collected to obtain a ⁇ -PGAA solution, which was made into a 50 mg/mL aqueous solution of ⁇ -PGAA.
  • ⁇ -PGA is a white powder having a molecular weight of 10 to 70 w.
  • the specific method for sputtering metal on the single-layer carbon film in the step (2) is: depositing the carbon film on a glass slide having a length of 7.5 cm and a width of 2.5 cm, and sputtering on the carbon film by magnetron sputtering.
  • a metal layer having a thickness of 20 to 80 nm is irradiated, and a carbon film having a sputtered metal has a resistance of 2 to 10 ohms to obtain a composite carbon film covered with a metal layer.
  • the invention also provides an application of an all-weather self-healing composite conductive hydrogel, and the prepared composite conductive hydrogel is used in the fields of biomimetic biology, flexible electronic equipment or biosensors, wearable devices, software robots, and the like. .
  • the invention is mainly embodied in an all-weather self-healing stretchable conductive material.
  • the conductive material has the highest elongation at break of 2875% through the above preparation method; the self-healing recovery time is the fastest 3h, self-healing The efficiency is 98.8%; the sheet resistance can be as low as 2 ohms.
  • the ambient temperature is -30 ° C to 60 ° C, the resistance is maintained at about 2 ohms; when the ambient humidity is 15% to 80%, the resistance remains at 2 ohms. about.
  • the method adopts the modification of the human-friendly polyglutamic acid, ingeniously avoids the flocculation of ⁇ -polyglutamic acid and metal ions, and increases the degree of cross-linking of the three-dimensional network structure with acrylic acid.
  • the tensile strength of the hydrogel is enhanced, and the self-healing time is shortened; the prepared conductive material maintains good electrical conductivity under different conditions of temperature and humidity, and the electrical conductivity remains unchanged under the condition of stretching.
  • Example 1 is a graph showing a stress-strain curve of a hydrogel of a mixed solvent of different ratios of glycerin and water prepared according to Example 1.
  • Example 2 is a graph of stress-strain curves for hydrogels of different ⁇ -PGAA concentrations prepared according to Example 2.
  • Example 3 is a graph of stress-strain curves for hydrogels of different MBAA concentrations prepared according to Example 3.
  • Example 4 is a graph of stress-strain curves of PAA+ ⁇ -PGAA+Fe 3+ /GC+H 2 O hydrogels prepared according to Example 3 at different times.
  • Figure 5 is an infrared spectrum of a hydrogel prepared according to Examples 1, 2, and 3.
  • Example 7 is a graph of mass change rate versus time for a hydrogel prepared according to Example 3.
  • Example 8 is an SEM image of the self-healing effect of the PAA+ ⁇ -PGAA+Fe 3+ /GC+H 2 O hydrogel prepared according to Example 3: (a) SEM image before self-healing, (b) from SEM image after healing.
  • Figure 10 is a graph showing temperature and resistance curves of a composite carbon film hydrogel prepared according to Example 4 and a carbon film-free hydrogel.
  • Figure 11 is a graph showing the humidity and electrical resistance of a composite carbon film hydrogel and a carbon-free film hydrogel prepared according to Example 4.
  • Figure 12 is a graph showing changes in electrical resistivity of a composite carbon film hydrogel prepared according to Example 4 under tension.
  • ⁇ -PGA white powder having a molecular weight of 10 to 70 w
  • 4 g of allyl glycidyl ether are sufficiently dissolved in 25 mL of deionized water, and the pH is adjusted to 2-4 with acetic acid, and stirred at room temperature for 36 hours. Thereafter, it was extracted three times with dichloromethane, and an upper layer of ⁇ -PGAA aqueous solution was collected to prepare a 50 mg/mL aqueous solution of ⁇ -PGAA.
  • Step (2) of Example 1 was changed to 2 g of acrylic acid, 4 mg of MBAA, 40 mg of APS, 0.056 g of FeCl 3 .6H 2 O, the volume ratio of GC:H 2 O was 5:1, and the ⁇ -PGAA solution was 0 mL, respectively. 2mL, 4mL, 6mL, 8mL, after the solution is evenly mixed, the gas in the solution is removed by nitrogen for 30 minutes, and polymerization is carried out at 60 ° C for 30 minutes to obtain a composite hydrogel with different ⁇ -PGAA content, and the remaining steps and examples 1 is the same.
  • Step (2) of Example 1 was changed to 2 g of acrylic acid, 4 mL of ⁇ -PGAA, 40 mg of APS, 0.056 g of FeCl 3 .6H 2 O, the volume ratio of GC:H 2 O was 5:1, and the mass of MBAA was 0 mg, respectively. 2 mg, 4 mg, 6 mg, 8 mg, the solution was uniformly mixed, the gas in the solution was removed by nitrogen for 30 minutes, and polymerization was carried out at 60 ° C for 30 minutes to obtain polyacrylic acid and polyglutamic acid composite hydrogels having different MBAA contents. The remaining steps are the same as in Embodiment 1.
  • a single-layered carbon film was placed on a 7.5 cm wide and 2.5 cm wide glass slide, and a silver layer of about 50 nm thick was deposited on the carbon film by magnetron sputtering, and a silver-coated composite carbon film was sputtered.
  • the resistance is about 3 ohms.
  • the volume content of the ⁇ -PGAA solution is 40%, the mass concentration of MBAA is 0.2% compared to acrylic acid, and the mass concentration of APS compared to acrylic acid is 2%, and FeCl 3 .6H 2 O is compared to acrylic acid.
  • the hydrogel prepared under the condition of a molar ratio of GC:H 2 O of 5:1 was adhered to the sputtered silver composite carbon film while being stretched by 200%. After the stretched hydrogel shrinks to its original length, another identical hydrogel is applied to the other side of the carbon film to form a composite carbon film with an intermediate layer of sputtered silver and self-healing water at both ends.
  • a "sandwich" type of conductive material for glue is
  • the mechanical properties of the hydrogels of Examples 1, 2, and 3 were separately investigated using a universal trial machine.
  • the sample size used for the tensile test was: a rectangular parallelepiped of 5 ⁇ 1 ⁇ 0.2 cm 3 , the tensile loading rate was: 10 mm / min, and the test result was the average of five tests.
  • Figures 1, 2 and 3 it was found that when the volume content of the ⁇ -PGAA solution was 40%, the mass concentration of MBAA compared to acrylic acid was 0.2%, and the mass concentration of APS compared to acrylic acid was 2%, FeCl 3 .
  • PAA + ⁇ -PGAA + Fe 3+ / GC + IR spectra of H 2 O hydrogel is marked as the telescopic shock-yl amide NH peaks transition from 3350 to 3285cm -1, 1636cm -1 is labeled at
  • the addition promotes the formation of a coordination bond between the metal and the carboxyl group.
  • the PAA+ ⁇ -PGAA+Fe 3+ /H 2 O hydrogel prepared in Example 1 was freeze-dried for 12 h, and the surface morphology of the hydrogel was observed by scanning electron microscopy (SEM, FEI Quanta 650).
  • the gel is a porous network structure as shown in FIG.
  • the O-hydrogel was placed at room temperature to record the change rate of the mass change of the four hydrogels with time.
  • PAA hydrogel, PAA+ ⁇ -PGAA/H 2 O hydrogel, PAA+ ⁇ -PGAA+Fe The mass of the 3+ /H 2 O hydrogel gradually decreased, while the mass of the PAA+ ⁇ -PGAA+Fe 3+ /GC+H 2 O hydrogel did not change much, as shown in FIG. 7 .
  • the composite carbon film hydrogel prepared in Example 4 was subjected to an experiment of humidity and temperature versus electrical conductivity. As shown in Figures 10 and 11, when the temperature is -30 degrees Celsius, the resistance of the PAA+ ⁇ -PGAA+Fe 3+ /GC+H 2 O hydrogel reaches 290K ohms, and the water condensation after the addition of the composite carbon film The rubber resistance is around 10 ohms and does not change much. Similarly, when the humidity changes from 14% to 80%, the resistance of the PAA+ ⁇ -PGAA+Fe 3+ /GC+H 2 O hydrogel reaches 160K ohms, while the hydrogel resistance after the addition of the composite carbon film remains At around 10 euros.
  • the composite carbon membrane hydrogel has stable electrical conductivity and does not change with changes in humidity and temperature.
  • the composite carbon film hydrogel has almost the same resistivity within 200% tensile strength, as shown in FIG. This will have a good application prospect in the fields of biomimetic biology, flexible electronic devices, biosensors, wearable devices, and software robots.

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Abstract

一种全天候自愈合可拉伸导电材料的制备方法，以丙烯酸和改性聚谷氨酸为基材，加入Fe 3+形成配位，调节水和甘油的体积比，加热后发生自由基聚合反应，生成均一的双层三维网状结构，得到的聚丙烯酸和聚谷氨酸复合水凝胶具有好的机械性能，还具有快速自愈合的特性。采用磁控溅射方法在单层顺排碳膜上沉积20nm～80nm厚的金属层制备复合碳膜，然后再在复合碳膜上下两面粘附复合水凝胶，形成一种三明治结构的全天候自愈合可拉伸导电材料。该方法简单，原料来源广泛，制得的材料具有良好的电学和机械性能，在柔性可拉伸器件及可穿戴设备、软体机器人等领域具有广阔的应用前景。

Description

一种全天候自愈合可拉伸导电材料及其制备方法 技术领域
本发明属于新材料技术领域，具体涉及一种全天候自愈合可拉伸导电材料及其制备方法。
背景技术
自20世纪40年代以来，水凝胶在仿生、化学、医药等领域的研究从不间断。水凝胶是一种三维网状结构的高分子化合物，能提供巨大的比表面积，使其具有较强的机械强度、延展性、粘性、韧性和可恢复性等特点。20世纪80年代，科学家受自我修复生物体系的触发而发展的一类能进行自我修复的新型材料，这类自愈合材料有助于提高器件的寿命和安全性。自愈合材料在受到物理、化学或者机械损伤后能够完全或者部分恢复到原状，大多数通过聚合物骨架之间可逆的相互作用如：氢键、共价键、分子间作用力等方式来实现。但综合性质还是不能让人满意，尤其是随着气候的改变，导电水凝胶的电阻随着温度和湿度发生显著变化，这极大的束缚了水凝胶的发展。
近年来，人们对便携式电子设备的要求不断提高，可穿戴电子设备、电子皮肤等柔性器件材料研究的越来越多，而环境友好，性能稳定，使用寿命等特点备受关注。一般而言，导电水凝胶由绝缘的多空骨架和导电填充材料构成，如聚吡咯、聚苯胺、聚噻吩、离子液体和碳纳米管等导电高分子为活性材料。导电水凝胶的导电能力和机械强 度到目前为止还没有达到人们的要求，因此通过简单便捷的方法制备机械强度高，电化学性能优异稳定的导电水凝胶材料具有重大的研究意义。
发明内容
本发明所要解决的技术问题是提供一种具有良好的自愈合能力的可拉伸导电材料，在不同的温度和湿度的情况下导电性保持不变，在拉伸的情况下电导率保持不变的复合导电材料及其制备方法。
本发明的设计思路是：利用丙烯酸和γ-聚谷氨酸中富含丰富的羧基和Fe 3+进行配位形成双层三维网状结构，使其具有很强的拉伸和自愈合的性质；通过改变甘油与水的溶剂组合，使得水凝胶的质量变化保持不变；再制作中间层为溅射过金属(银、金、铜)的复合顺排碳膜，两端为自愈合水凝胶的一种“三明治”结构的复合导电材料。该导电材料在不同的温度和湿度的情况下导电性保持不变，在拉伸的情况下电导率保持不变。
本发明的技术方案为：首先是以丙烯酸(PAA)和改性聚谷氨酸(γ-PGAA)水凝胶为骨架，六水合氯化铁(FeCl 3.6H 2O)为金属离子络合剂，N,N’-亚甲基双丙烯酰胺(MBAA)为交联剂，过硫酸胺(APS)为引发剂，以甘油(GC)和水(H 2O)作为混合溶剂，制得聚丙烯酸和聚谷氨酸复合水凝胶；将复合水凝胶在拉伸的情况下，粘附在溅射过金属的复合顺排碳膜上，收缩至原来的长度后将另一块水凝胶贴在碳膜的另一侧，形成中间层为溅射过金属的碳膜，两端为自愈合水凝胶的“三明治”结构的可拉伸导电材料。
本发明的导电材料的制备方法如下：
(1)将丙烯酸，改性聚谷氨酸(γ-PGAA)，六水合氯化铁(FeCl 3.6H 2O)，N,N’-亚甲基双丙烯酰胺(MBAA)，过硫酸胺(APS)，甘油(GC)和H 2O按比例配成溶液，混合均匀后通氮气30分钟除去溶液中的气体，60℃下发生聚合反应30分钟，得到复合水凝胶。
(2)将顺排碳膜贴在玻璃板上，采用磁控溅射方法在单层顺排碳膜上溅射金属(银、金、铜)，制备复合碳膜。
(3)将步骤(1)得到的水凝胶在拉伸200～500％的情况下，粘附到复合碳膜上，然后收缩至原来的长度后，再将另一块水凝胶贴在碳膜的另一侧，形成中间层为溅射过金属(银、金、铜等)的碳膜，两端为自愈合水凝胶的“三明治”结构的可拉伸导电材料。
步骤(1)所述GC和H 2O的体积比为0:6到6:0之间，γ-PGAA溶液的用量为溶液总质量的0％～80％，MBAA用量为丙烯酸质量的0％～0.4％，APS用量为丙烯酸质量的2％，FeCl 3.6H 2O用量为丙烯酸物质的量的1.25％。当GC:H 2O的体积比为5:1，γ-PGAA溶液的用量为溶液总质量的40％，MBAA用量为丙烯酸质量的0.2％，APS用量为丙烯酸质量的2％，FeCl 3.6H 2O用量为丙烯酸物质的量的1.25％，制备自愈合速度较快，断裂伸长率较大，长时间保存的水凝胶。
所述γ-PGAA的制备方法为：将2gγ-PGA和4g烯丙基缩水甘油醚充分溶解在25mL去离子水中，用乙酸调节pH为2～4，室温下反应36小时后，用二氯甲烷萃取三次，收集水层得到γ-PGAA溶液，配制成50mg/mL的γ-PGAA水溶液。其中，γ-PGA为分子量为10～70w 的白色粉末。
步骤(2)所述在单层碳膜上溅射金属的具体方法为：将碳膜铺到长为7.5cm，宽为2.5cm的载玻片上，采用磁控溅射方法在碳膜上溅射20～80nm厚的金属层，溅射过金属的碳膜电阻为2～10欧，得到金属层覆盖的复合碳膜。
本发明还提供了一种全天候自愈合复合导电水凝胶的应用，将所制得的复合导电水凝胶用于仿生生物学，柔性电子设备或生物传感器、可穿戴设备、软体机器人等领域。
本发明主要体现在一种具有全天候自愈合可拉伸导电材料，所述导电材料通过以上制备方法，其断裂伸长率最高达到2875％；自愈合恢复时间最快为3h，自愈合效率为98.8％；方块电阻电阻最小能达到2欧，当环境温度为-30℃到60℃时，电阻保持在2欧左右；当环境湿度为15％到80％时，电阻仍然保持在2欧左右。该方法采用对人体友好的聚谷氨酸进行改性，巧妙的避免了γ-聚谷氨酸能和金属离子产生絮状沉淀，并且增加了与丙烯酸间的三维网状结构的交联程度，增强了水凝胶的拉伸强度，缩短了自愈合时间；制备得到的导电材料在不同的温度和湿度的情况下良好导电性保持不变，在拉伸的情况下电导率保持不变。
附图说明
图1为根据实施例1制备的不同比例甘油和水的混合溶剂的水凝胶的应力-应变曲线图。
图2为根据实施例2制备的不同γ-PGAA浓度的水凝胶的应力- 应变曲线图。
图3为根据实施例3制备的不同MBAA浓度的水凝胶的应力-应变曲线图。
图4为根据实施例3制备的PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶在不同时间下的应力-应变曲线图。
图5为根据实施例1，2，3制备的水凝胶的红外光谱图。
图6为根据实施例3制备的PAA+γ-PGAA+Fe 3+/H 2O水凝胶的SEM图。
图7为根据实施例3制备的水凝胶的质量变化率与时间的曲线图。
图8为根据实施例3制备的PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶自愈合效果的SEM图：(a)自愈合前的SEM图，(b)自愈合后的SEM图。
图9为根据实施例3制备的PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶的电自愈合电流与时间曲线图。
图10为根据实施例4制备的复合碳膜水凝胶与没加碳膜水凝胶的温度与电阻曲线图。
图11为根据实施例4制备的复合碳膜水凝胶与没加碳膜水凝胶的湿度与电阻曲线图。
图12为根据实施例4制备的复合碳膜水凝胶在拉伸情况下电阻率的变化曲线图。
具体实施方式
下面通过实施例对本发明做进一步详细说明，这些实施例仅用来说明本发明，并不限制本发明的范围，结合实例说明实施方式，具体工艺如下：
实施例1
(1)将2gγ-PGA(分子量为10～70w的白色粉末)，和4g烯丙基缩水甘油醚充分溶解在25mL去离子水中，用乙酸调节pH为2-4，室温下搅拌，反应36小时后，用二氯甲烷萃取三次，收集上层γ-PGAA水溶液，配制得到50mg/mL的γ-PGAA水溶液。
(2)取2g丙烯酸，4mL γ-PGAA溶液，4mg MBAA，40mg APS，0.056g FeCl 3.6H 2O，在体积比为0:6，1:5，3:3，5:1，6:0的GC:H 2O中混合均匀，通氮气30分钟除去溶液中的气体，60℃下发生聚合反应30分钟，得到不同溶剂体积比的复合水凝胶。当γ-PGAA溶液含量为0mL，FeCl 3.6H 2O含量为0mg，GC:H 2O的体积比为0:6时标记为PAA水凝胶；当γ-PGAA溶液含量为4mL，FeCl 3.6H 2O含量为0mg，GC:H 2O的体积比为0:6时标记为PAA+γ-PGAA/H 2O水凝胶；当γ-PGAA溶液含量为4mL，FeCl 3.6H 2O含量为0.056g，GC:H 2O体积比为0:6时标记为PAA+γ-PGAA+Fe 3+/H 2O水凝胶；当γ-PGAA溶液含量为4mL，FeCl 3.6H 2O含量为0.056g，GC:H 2O体积比为5:1时标记为PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶。
实施例2
将实施例1步骤(2)改为取2g丙烯酸，4mg MBAA，40mg APS，0.056g FeCl 3.6H 2O，在GC:H 2O的体积比为5:1，γ-PGAA溶液分别为 0mL，2mL，4mL，6mL，8mL，溶液混合均匀后，通氮气30分钟除去溶液中的气体，60℃下发生聚合反应30分钟，得到不同γ-PGAA含量的复合水凝胶，其余步骤和实施例1相同。
实施例3
将实施例1步骤(2)改为取2g丙烯酸，4mLγ-PGAA，40mg APS，0.056g FeCl 3.6H 2O，在GC:H 2O的体积比为5:1，MBAA的质量分别为0mg，2mg，4mg，6mg，8mg，溶液混合均匀后，通氮气30分钟除去溶液中的气体，60℃下发生聚合反应30分钟，得到不同MBAA含量的聚丙烯酸和聚谷氨酸复合水凝胶。其余步骤和实施例1相同。
实施例4
(1)将单层顺排碳膜铺在7.5cm，宽为2.5cm的载玻片上，采用磁控溅射方法在碳膜上沉积约50nm厚的银层，溅射过银的复合碳膜电阻为3欧左右。
(2)将γ-PGAA溶液的体积含量为40％，MBAA相比于丙烯酸的质量浓度为0.2％，APS相比于丙烯酸的质量浓度为2％，FeCl 3.6H 2O相比于丙烯酸的物质的量浓度为1.25％，GC:H 2O的体积比为5:1条件下制备的水凝胶，在拉伸200％的情况下粘附在溅射过银的复合碳膜上，待拉伸的水凝胶收缩至原来的长度后将另外一块相同的水凝胶贴在碳膜的另一侧，形成中间层为溅射过银的复合碳膜，两端为自愈合水凝胶的一种“三明治”型的导电材料。
采用万能试用机分别对实施例1,2,3中水凝胶进行机械性能研究。拉伸试验使用的样品大小为：5×1×0.2cm 3的长方体，拉伸加载速率 为：10mm/min，测试结果为五次测试的平均值。如图1,2,3所示，发现当γ-PGAA溶液的体积含量为40％，MBAA相比于丙烯酸的质量浓度为0.2％，APS相比于丙烯酸的质量浓度为2％，FeCl 3.6H 2O相比于丙烯酸的物质的量浓度为1.25％，GC:H 2O的体积比为0:6条件下制备的水凝胶的断裂伸长率达到2875％。如图4所示为不同时间下PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶的应力-应变曲线图，通过不同时间段，水凝胶恢复的断裂伸长率来判断自愈合程度。在1.5h之前，自愈合效率达到65.4％，之后自愈合速度变慢，自愈合恢复的时间为3h，自愈合效率为98.8％。
采用傅里叶红外光谱仪对PAA水凝胶，PAA+γ-PGAA/H 2O水凝胶，PAA+Fe 3+/H 2O水凝胶，PAA+γ-PGAA+Fe 3+/H 2O水凝胶和PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶的结构进行分析，如图5所示，PAA水凝胶在3350,1636,1457和1256cm -1四处峰，分别归功于酰胺基中N-H的伸缩震动峰，C＝O的伸缩震动，O-H的变形震动和C-O的伸缩震动。PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶的红外光谱图中，被标记为酰胺基中N-H的伸缩震动峰从3350跃迁到3285cm -1，1636cm -1处被标记为C＝O的伸缩震动峰出现减弱的现象，这很有可能是由于甘油的加入，增强了水凝胶中氢键的作用。于此同时，1709cm -1处被标记为C＝O的伸缩震动峰出现逐渐增强，以及被标记为O-H的变形震动峰从1459跃迁到1457cm -1处，这很有可能是由于Fe 3+的加入促进了金属与羧基之间形成配位键的结果。
对实施例1中制备的PAA+γ-PGAA+Fe 3+/H 2O水凝胶，进行冷冻干 燥12h后，采用扫描电镜(SEM,FEI Quanta650)观察水凝胶表面形貌结构，发现水凝胶为多孔网状结构，如图6所示。对PAA水凝胶，PAA+γ-PGAA/H 2O水凝胶，PAA+γ-PGAA+Fe 3+/H 2O水凝胶和PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶放置在室温下记录下四种水凝胶质量变化率与时间的变化曲线，发现PAA水凝胶，PAA+γ-PGAA/H 2O水凝胶，PAA+γ-PGAA+Fe 3+/H 2O水凝胶的质量逐渐减少，而PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶的质量变化不大，如图7所示。
对实施例3中制备的PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶自愈合前后进行SEM观察，发现切断部分已完全愈合如图8中的(a)和(b)所示。通过电化学工作站测得水凝胶的电自愈合曲线，如图9所示，发现水凝胶在0.6秒内电信号能恢复到正常状态。
对实施例4中制备的复合碳膜水凝胶进行湿度与温度对导电性能的实验。如图10,11所示，当温度在-30摄氏度下时，PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶的电阻达到290K欧，而加入复合碳膜后的水凝胶电阻在10欧左右，不发生太大变化。相类似的当湿度从14％变化到80％时，PAA+γ-PGAA+Fe 3+/GC+H 2O水凝胶的电阻达到160K欧，而加入复合碳膜后的水凝胶电阻仍然在10欧左右。说明复合碳膜水凝胶具有稳定的导电性能，不随湿度和温度的改变而发生改变。复合碳膜水凝胶在拉伸强度为200％内其电阻率几乎保持不变，如图12所示。这将在仿生生物学，柔性电子设备，生物传感器、可穿戴设备、软体机器人等领域具有很好的应用前景。

Claims (9)

  1. 一种全天候自愈合可拉伸导电材料，其特征在于：所述可拉伸导电材料以溅射过金属的复合碳膜作为中间层，两边粘附聚丙烯酸和聚谷氨酸复合水凝胶，形成的一种“三明治”结构的全天候自愈合可拉伸导电材料。
  2. 一种如权利要求1所述的全天候自愈合可拉伸导电材料的制备方法，其特征在于：包括以下步骤：
    (1)将丙烯酸，改性聚谷氨酸(γ-PGAA)，六水合氯化铁(FeCl 3.6H 2O)，N,N’‐亚甲基双丙烯酰胺(MBAA)，过硫酸胺(APS)，甘油(GC)和H 2O按比例配成溶液，混合均匀后通氮气30分钟除去溶液中的气体，60℃下进行聚合反应30分钟，得到聚丙烯酸和聚谷氨酸复合水凝胶；
    (2)采用磁控溅射方法在单层顺排碳膜上溅射金属，制备复合碳膜；
    (3)将步骤(1)中得到的水凝胶在拉伸200～500％的情况下，粘附到溅射过金属的复合碳膜上，然后待该水凝胶收缩至原来的长度后，再将另一块水凝胶贴在碳膜的另一侧，形成中间层为溅射过金属的复合碳膜，两端为自愈合水凝胶的“三明治”结构的可拉伸导电材料。
  3. 如权利要求2所述的全天候自愈合可拉伸导电材料的制备方法，其特征在于：步骤(1)所述改性聚谷氨酸(γ-PGAA)的制备方 法为：将2gγ-PGA和4g烯丙基缩水甘油醚充分溶解在25mL去离子水中，用乙酸调节pH值为2～4，室温下反应36小时后，用二氯甲烷萃取三次，收集水层得到改性聚谷氨酸(γ-PGAA)溶液，配制成50mg/mL的改性聚谷氨酸(γ-PGAA)水溶液。
  4. 如权利要求3所述的全天候自愈合可拉伸导电材料的制备方法，其特征在于：所述γ-PGA为分子量为10～70w的白色粉末。
  5. 如权利要求2所述的全天候自愈合可拉伸导电材料的制备方法，其特征在于：步骤(1)所述甘油(GC)和H 2O的体积比为0:6～6:0，改性聚谷氨酸(γ-PGAA)溶液的用量为溶液总质量的0％～80％，N,N’-亚甲基双丙烯酰胺(MBAA)用量为丙烯酸质量的0％～0.4％，过硫酸胺(APS)用量为丙烯酸质量的2％，六水合氯化铁(FeCl 3.6H 2O)用量为丙烯酸物质的量的1.25％。
  6. 如权利要求5所述的全天候自愈合可拉伸导电材料的制备方法，其特征在于：步骤(1)所述甘油(GC):H 2O的体积比为5:1，改性聚谷氨酸(γ-PGAA)溶液的用量为溶液总质量的40％，N,N’-亚甲基双丙烯酰胺(MBAA)用量为丙烯酸质量的0.2％，过硫酸胺(APS)用量为丙烯酸质量的2％，六水合氯化铁(FeCl 3.6H 2O)用量为丙烯酸物质的量的1.25％。
  7. 如权利要求2所述的全天候自愈合可拉伸导电材料的制备方法，其特征在于：步骤(2)所述的在单层顺排碳膜上溅射金属的具体方法为：将碳膜铺在长为7.5cm，宽为2.5cm的载玻片上，采用磁控溅射方法在单层顺排碳膜上溅射金属，制备金属层为20nm～80nm 厚的复合碳膜，其电阻为2～10欧。
  8. 如权利要求2所述的全天候自愈合可拉伸导电材料的制备方法，其特征在于：步骤(2)所述的在单层顺排碳膜上溅射金属的种类为：金、银或铜。
  9. 一种如权利要求2所述方法制得的全天候自愈合可拉伸导电材料的应用，其特征在于：所述导电材料用于仿生生物学，柔性电子设备、生物传感器、可穿戴设备、软体机器人领域。
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