WO2020192312A1 - Method for preparing silk with high thermal conductivity by breeding a silkworm fed on nano-graphene, and product thereof - Google Patents

Method for preparing silk with high thermal conductivity by breeding a silkworm fed on nano-graphene, and product thereof Download PDF

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Publication number
WO2020192312A1
WO2020192312A1 PCT/CN2020/075803 CN2020075803W WO2020192312A1 WO 2020192312 A1 WO2020192312 A1 WO 2020192312A1 CN 2020075803 W CN2020075803 W CN 2020075803W WO 2020192312 A1 WO2020192312 A1 WO 2020192312A1
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silk
nano
graphene
thermal conductivity
silkworm
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PCT/CN2020/075803
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French (fr)
Chinese (zh)
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林欢
王钰婷
刘心颖
柳守婷
董华
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青岛理工大学
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01KANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K67/00Rearing or breeding animals, not otherwise provided for; New or modified breeds of animals
    • A01K67/033Rearing or breeding invertebrates; New breeds of invertebrates
    • A01K67/04Silkworms
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/20Inorganic substances, e.g. oligoelements
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K50/00Feeding-stuffs specially adapted for particular animals
    • A23K50/90Feeding-stuffs specially adapted for particular animals for insects, e.g. bees or silkworms

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  • the invention relates to the field of silk fiber and its modification, in particular to a method for preparing high-thermal-conductivity silkworm silk by adding nano-graphene to feed the silkworm and its products.
  • Silk and silk fibroin have greatly promoted the development of various new integrated and miniaturized biological functional systems.
  • the unique advantages of silk fibroin mainly include outstanding mechanical properties, excellent optical properties, and flexible chemical modification.
  • various advanced micro-nano processing technologies have been used in their micro-nano processing and structuring.
  • the characteristics of silk make silk no longer limited to the application in the traditional textile field, and begin to apply more and more researches on electronic device materials, such as implantable bioelectronic devices, optical microfluidic chips, organic light-emitting devices, micro-nano Optoelectronics subsystem.
  • the methods of modification of silk and its products mainly include physical modification, chemical modification and blending modification, etc.
  • problems such as complex procedures, high costs, and environmental pollution. Therefore, it is necessary to find new modification methods.
  • adding food and breeding silkworm method Such as adding food and breeding silkworm method.
  • the Chinese patent with publication number CN1395861A discloses a silkworm feed containing functional particles, the silk produced by the feed and the products using the silk.
  • the inventor adds functional particles such as minerals and pigments to the silkworm Silkworms are fed in the feed, and functional silks are spun through the absorption and transformation of silkworms.
  • the Chinese patent with publication number CN1608489 discloses a feed for silkworms, silk produced by feeding the feed, and silk products using the silk. This patent is to dissolve a prescribed amount of zeolite, luminous stone and other functional particles in water or other solvents and then add silkworm feed to the silkworm to obtain silk. These two patents need to screen and process the functional particles used in the feeding process.
  • the purpose of the present invention is to provide a nano-graphene feeding silkworm breeding method for preparing high thermal conductivity silk and its products, so as to improve the thermal conductivity of the silk, so that the high thermal conductivity silk can be better used in various fields.
  • the present invention provides the following solutions:
  • the invention provides a method for preparing high-thermal-conductivity silkworm silk by adding nano-graphene to feed the silkworm, coating nano-graphene dispersion on mulberry leaves and feeding silkworms, and the silkworm absorbs the nano-graphene into the silk gland and finally in the spinning process Incorporate nano-graphene into silk to obtain high thermal conductivity silk;
  • the size range of the nano graphene is a sheet diameter range of 0.5-5 ⁇ m, a thickness range of 0-0.8 nm, and a single layer rate of 80%;
  • silkworms were fed mulberry leaves without nanographene from the first to second instars, and fed with mulberry leaves with a concentration of 0.2-1 mg/mL nanographene dispersion at the third instar, until the upper cocoon formed.
  • the specific process includes the following steps:
  • nano-graphene dispersion is applied to the mulberry leaves, it is ultrasonicated for 32-50 minutes to make the nano-particles uniformly dispersed.
  • the invention also provides a high-thermal-conductivity silk obtained by the above-mentioned nano-graphene-feeding silkworm breeding method for preparing high-thermal-conductivity silk.
  • step (2) put the degummed silk into a blast drying box, set a temperature of 105°C for 120 minutes.
  • the present invention also provides a silk product made from the above-mentioned high thermal conductivity silk.
  • the silk product is knitted or woven from the high thermal conductivity silk.
  • Nanographene is a carbon material composed of carbon atoms and only one layer of atomic thickness. It is a new type of two-dimensional material with a single-layer sheet structure composed of carbon atoms. It is also a single-layer graphite sheet with perfect The hybrid structure. However, because the surface of nanographene does not contain hydroxyl groups, carboxyl groups and other groups, it is difficult to bind to silk fibroin molecules, and often exists in sericin, resulting in weak effect after silk degumming.
  • the present invention uses nano-graphene and PVP solutions in a specific size range, and combines the nano-graphene with silk through the above-mentioned feeding method, which overcomes the fact that the surface of the nano-graphene does not contain hydroxyl, carboxyl and other groups and binds with silk fibroin molecules. Difficult problem, and can further enhance the binding strength of nano-graphene and silk fibroin molecules.
  • nanographene do not change when it is divided, and its performance may be abnormal. This shows that nano-graphene can be better absorbed by silkworms, better improve the thermal conductivity of silk, and does not affect the properties of nano-graphene itself.
  • the present invention dissolves nano graphene in water, and the PVP solution is added to the water to enhance the solubility of graphene.
  • the nano-graphene in the present invention has a very small size, can be better absorbed by silkworms, and better improves the thermal conductivity of silk, and does not affect the properties of graphene itself.
  • the nano-graphene feeding silkworm breeding method of the present invention eliminates the need for expensive equipment support and complicated technical means, is simple and easy to implement, saves costs, and is easy to control and has significant effects.
  • the high thermal conductivity silk of the present invention has better thermal conductivity than natural silk.
  • the thermal conductivity of the monofilament after degumming of the high thermal conductivity silk is about 1.36W/(m ⁇ K), which is the difference of ordinary silk after degumming. 1.8 times the thermal conductivity.
  • a method for preparing high-thermal-conductivity silk by adding nano-graphene to feed silkworms Firstly, prepare mulberry leaves containing medicaments, specifically:
  • the size range of the single-layer graphene powder is 0.5-1.6 ⁇ m in diameter, infinitely small-0.8nm in thickness, and nanographene with a single-layer rate of 80% dissolved in water added with PVP solution. Make nano graphene solution;
  • the prepared nano-graphene dispersion is uniformly coated on the surface of mulberry leaves, and then the mulberry leaves containing the drug are dried at room temperature and then fed to silkworms.
  • the nano-graphene is absorbed by the silkworms into the silk glands and is finally spinning In the process, the nano-graphene is incorporated into the silk to obtain silk with high thermal conductivity;
  • the silkworms were fed fresh mulberry leaves uncoated with medicine from the first to second instars, and fed mulberry leaves coated with a 0.2mg/ml nanographene dispersion on the third day of the third instar, until the upper cocoon formed During the period from the third day of the third instar to the cocoon formation of the same batch of silkworms, the additive concentration of nano-graphene on the mulberry leaves containing the drug remained unchanged.
  • the high thermal conductivity silk is removed from the sericin.
  • the specific process of removing the sericin includes the following steps:
  • step (2) put the degummed silk into a blast drying oven for drying, set a temperature of 105°C for 120 minutes.
  • the obtained silk filament after degumming has a breaking strength of 582MPa, a breaking elongation of 17.1%, a breaking energy of 63J/g, and a thermal conductivity of 1.3W/(m ⁇ K).
  • Silk products are woven from high thermal conductivity silk.
  • a method for preparing high thermal conductivity silkworm silk by adding nano-graphene to feed the silkworm Firstly, prepare the mulberry leaf containing the medicament, specifically:
  • the size range of the single-layer graphene powder is 1.7-3.5 ⁇ m in diameter, infinitely small-0.8nm in thickness, and nanographene with a single-layer rate of 80% dissolved in water added with PVP solution. Make nano graphene solution;
  • the prepared nano-graphene dispersion is uniformly coated on the surface of mulberry leaves, and then the mulberry leaves containing the drug are dried at room temperature and then fed to silkworms.
  • the nano-graphene is absorbed by the silkworms into the silk glands and is finally spinning In the process, the nano-graphene is incorporated into the silk to obtain silk with high thermal conductivity;
  • the silkworms were fed fresh mulberry leaves uncoated with medicine from the first to second instars, and fed mulberry leaves coated with the nano graphene dispersion at a concentration of 0.5mg/ml on the third day of the third instar, until the upper cocoon formed a cocoon.
  • the additive concentration of nano-graphene on the mulberry leaves containing the drug remained unchanged.
  • the high thermal conductivity silk is removed from the sericin.
  • the specific process of removing the sericin includes the following steps:
  • step (2) put the degummed silk into a blast drying oven for drying, set a temperature of 105°C for 120 minutes.
  • the obtained silk filament after degumming has a breaking strength of 582MPa, a breaking elongation of 16.8%, a breaking energy of 58J/g, and a thermal conductivity of 1.18W/(m ⁇ K).
  • Silk products are woven from high-strength silk.
  • a method for preparing high thermal conductivity silkworm silk by adding nano-graphene to feed the silkworm Firstly, prepare the mulberry leaf containing the medicament, specifically:
  • the size range of single-layer graphene powder is from 3.6 to 5 ⁇ m in diameter, infinitely small to 0.8 nm in thickness, and nano-graphene with a single layer rate of 80% in water added with PVP solution.
  • nano graphene solution Into nano graphene solution;
  • the prepared nano-graphene dispersion is uniformly coated on the surface of mulberry leaves, and then the mulberry leaves containing the drug are dried at room temperature and then fed to silkworms.
  • the nano-graphene is absorbed by the silkworms into the silk glands and is finally spinning In the process, the nano-graphene is incorporated into the silk to obtain silk with high thermal conductivity;
  • the silkworms were fed fresh mulberry leaves uncoated with medicine from the first to second instar, and fed mulberry leaves coated with the nano-graphene dispersion at a concentration of 1 mg/ml on the third day of the third instar until the upper cocoon formed.
  • the additive concentration of nano-graphene on the mulberry leaves containing the drug remains unchanged.
  • the high thermal conductivity silk is removed from the sericin.
  • the specific process of removing the sericin includes the following steps:
  • step (2) put the degummed silk into a blast drying oven for drying, set a temperature of 105°C for 120 minutes.
  • the obtained silk filament after degumming has a breaking strength of 593MPa, a breaking elongation of 17.6%, a breaking energy of 65J/g, and a thermal conductivity of 0.9W/(m ⁇ K).
  • Silk products are woven from high-strength silk.
  • Example 3 Compared with Example 3, the difference is that the mulberry leaves used for feeding silkworms do not contain nanographene, only PVP solution, and the other steps are the same as Example 3.
  • the obtained single filament after degumming has a breaking strength of 353MPa, a breaking elongation of 14.7%, a breaking energy of 29J/g, and a thermal conductivity of 0.75W/(m ⁇ K).
  • Example 2 Compared with Example 1, the difference is that the nano-graphene in the mulberry leaves used for feeding silkworms is replaced with graphene oxide with a size range of 0.5-1.6 ⁇ m, and the other steps are the same as in Example 1.
  • the obtained silk filament after degumming has a breaking strength of 486MPa, a breaking elongation of 14.6%, a breaking energy of 43J/g, and a thermal conductivity of 0.8W/(m ⁇ K).
  • Example 2 Compared with Example 2, the difference is that the nano-graphene in the mulberry leaves used for feeding silkworms is replaced with graphene oxide with a size range of 1.7-3.5 ⁇ m, and the other steps are the same as in Example 2.
  • the obtained silk filament after degumming has a breaking strength of 487MPa, a breaking elongation of 14.9%, a breaking energy of 42J/g, and a thermal conductivity of 0.5W/(m ⁇ K).
  • Example 3 Compared with Example 3, the difference is that the nano-graphene in the mulberry leaves used for feeding silkworms is replaced with graphene oxide with a size range of 1.7-3.5 ⁇ m, and the other steps are the same as in Example 3.
  • the obtained silk filament after degumming has a breaking strength of 356MPa, a breaking elongation of 13.6%, a breaking energy of 38J/g, and a thermal conductivity of 0.55W/(m ⁇ K).

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Abstract

A method for preparing silk with high thermal conductivity by breeding a silkworm fed on nano-graphene, and a product thereof. Specifically, nano-graphene is evenly coated on mulberry leaves. The nano-graphene is absorbed and converted by the bodily functions of the silkworm and enters the silk gland, and after the silkworm forms a cocoon, silk with high thermal conductivity containing nano-graphene is obtained. The method modifies the silk without damaging the natural quality of the silk, and the resulting silk has better thermal conductivity.

Description

一种制备高导热蚕丝的纳米石墨烯添食育蚕法及其制品Nanographene feeding silkworm breeding method for preparing high thermal conductivity silk and its products 技术领域Technical field
本发明涉及蚕丝纤维及其改性领域,特别是涉及一种制备高导热蚕丝的纳米石墨烯添食育蚕法及其制品。The invention relates to the field of silk fiber and its modification, in particular to a method for preparing high-thermal-conductivity silkworm silk by adding nano-graphene to feed the silkworm and its products.
背景技术Background technique
蚕丝和丝素蛋白极大地促进着各种新型集成化、小型化生物功能化系统的开发。除了生物材料的共有特性,丝素蛋白的独特优点主要有突出的机械特性、优秀的光学性质,灵活的化学修饰等。作为丝素蛋白基微纳器件与系统的技术基石,各种先进的微纳加工技术已经被用于其微纳加工与结构化。蚕丝的特点使蚕丝不再局限于传统纺织领域的应用,开始越来越多地应用电子器件材料等学科的研究,例如可植入生物电子器件、光学微流控芯片、有机发光器件、微纳光电子系统。目前,蚕丝及其制品改性的方法主要有物理改性、化学改性和共混改性等,但往往存在工序复杂、成本较高、污染环境等问题,因此需要寻找新的改性方法,如添食育蚕法。Silk and silk fibroin have greatly promoted the development of various new integrated and miniaturized biological functional systems. In addition to the common characteristics of biological materials, the unique advantages of silk fibroin mainly include outstanding mechanical properties, excellent optical properties, and flexible chemical modification. As the technical cornerstone of silk fibroin-based micro-nano devices and systems, various advanced micro-nano processing technologies have been used in their micro-nano processing and structuring. The characteristics of silk make silk no longer limited to the application in the traditional textile field, and begin to apply more and more researches on electronic device materials, such as implantable bioelectronic devices, optical microfluidic chips, organic light-emitting devices, micro-nano Optoelectronics subsystem. At present, the methods of modification of silk and its products mainly include physical modification, chemical modification and blending modification, etc. However, there are often problems such as complex procedures, high costs, and environmental pollution. Therefore, it is necessary to find new modification methods. Such as adding food and breeding silkworm method.
蚕丝本身导热性能不佳,影响了这些应用的发展,因此增加蚕丝的导热性就成为了研究的重点。近期研究表明,通过粒子添食育蚕法可直接制备功能蚕丝,简便易行。而碳纳米管和氧化石墨烯被广泛研究用作增强材料。因此将氧化石墨烯、石墨混入家蚕饲料,利用家蚕的生物反应器,使纳米粒子进入家蚕丝腺与丝素蛋白相互作用并结合,最终由家蚕结茧获得改性蚕丝就成为一种改性蚕丝的新的研究方法。The poor thermal conductivity of silk itself affects the development of these applications. Therefore, increasing the thermal conductivity of silk has become the focus of research. Recent studies have shown that the functional silkworm silk can be directly prepared by feeding the silkworm with particles, which is simple and easy to implement. And carbon nanotubes and graphene oxide are widely studied as reinforcing materials. Therefore, graphene oxide and graphite are mixed into the silkworm feed, and the bioreactor of the silkworm is used to make the nanoparticles enter the silk gland of the silkworm to interact and combine with the silk fibroin. Finally, the modified silk obtained from the cocoon of the silkworm becomes a modified silk. New research methods.
例如公开号为CN1395861A的中国专利公开了一种含有功能性微粒的蚕饲料和用该饲料喂食生产的蚕丝及使用该蚕丝的制品,该专利中,发明者将矿物、色素等功能性微粒加入蚕饲料中喂食家蚕,通过蚕吸收转化作用纺出功能蚕丝。公开号为CN1608489的中国专利公开了一种蚕用饲料和喂饲该饲料而生产的丝以及使用该丝的丝制品。这项专利则是将规定量的沸石、夜光石等功能性微粒溶于水或其他溶剂再加入蚕饲料中喂食家蚕得到蚕丝。这两项专利在添食过程中需要将所用功能性微粒进行筛选和处理,由于微粒粒径较大,很容易影响 家蚕的进食生长,导致蚕丝质量和产量下降。其结果又表明,功能性微粒较多存在于丝胶中,而蚕丝在使用时,大多需要脱胶,这样一来其改性效果就微乎其微了。而且二者均未给出所得蚕丝的导热性能特征,仅表示所得蚕丝具有一些所添加微粒的功能,可应用范围窄。For example, the Chinese patent with publication number CN1395861A discloses a silkworm feed containing functional particles, the silk produced by the feed and the products using the silk. In this patent, the inventor adds functional particles such as minerals and pigments to the silkworm Silkworms are fed in the feed, and functional silks are spun through the absorption and transformation of silkworms. The Chinese patent with publication number CN1608489 discloses a feed for silkworms, silk produced by feeding the feed, and silk products using the silk. This patent is to dissolve a prescribed amount of zeolite, luminous stone and other functional particles in water or other solvents and then add silkworm feed to the silkworm to obtain silk. These two patents need to screen and process the functional particles used in the feeding process. Due to the large particle size, it is easy to affect the feeding and growth of the silkworm, resulting in a decline in silk quality and yield. The results also show that more functional particles are present in sericin, and most of the silk needs to be degummed when it is used, so its modification effect is minimal. Moreover, neither of the two give the characteristics of the thermal conductivity of the obtained silk, which only means that the obtained silk has some functions of the added particles, and the applicable range is narrow.
发明内容Summary of the invention
本发明的目的是提供一种制备高导热蚕丝的纳米石墨烯添食育蚕法及其制品,以提高蚕丝导热性能,使该高导热蚕丝在各领域中获得更好的应用。The purpose of the present invention is to provide a nano-graphene feeding silkworm breeding method for preparing high thermal conductivity silk and its products, so as to improve the thermal conductivity of the silk, so that the high thermal conductivity silk can be better used in various fields.
为实现上述目的,本发明提供了如下方案:In order to achieve the above objective, the present invention provides the following solutions:
本发明提供一种制备高导热蚕丝的纳米石墨烯添食育蚕法,在桑叶上涂覆纳米石墨烯分散液并喂养蚕,由蚕吸收纳米石墨烯进入丝腺并最终在纺丝过程中将纳米石墨烯结合进入蚕丝,即获得高导热蚕丝;The invention provides a method for preparing high-thermal-conductivity silkworm silk by adding nano-graphene to feed the silkworm, coating nano-graphene dispersion on mulberry leaves and feeding silkworms, and the silkworm absorbs the nano-graphene into the silk gland and finally in the spinning process Incorporate nano-graphene into silk to obtain high thermal conductivity silk;
所述纳米石墨烯的尺寸范围是片径范围为0.5-5μm,厚度范围为0-0.8nm,单层率为80%;The size range of the nano graphene is a sheet diameter range of 0.5-5 μm, a thickness range of 0-0.8 nm, and a single layer rate of 80%;
具体为:蚕在一龄到二龄喂食未添加纳米石墨烯的桑叶,三龄开始喂食添加了质量分数浓度为0.2-1mg/mL纳米石墨烯分散液的桑叶,直至上蔟结茧。Specifically, silkworms were fed mulberry leaves without nanographene from the first to second instars, and fed with mulberry leaves with a concentration of 0.2-1 mg/mL nanographene dispersion at the third instar, until the upper cocoon formed.
进一步地,在桑叶上涂覆纳米石墨烯分散液,具体过程包括以下步骤:Further, coating the nano graphene dispersion on the mulberry leaves, the specific process includes the following steps:
(1)将纳米石墨烯溶于水中,水中加入了PVP(聚乙烯吡咯烷酮)溶液,制成纳米石墨烯分散液;(1) Dissolve nano-graphene in water, add PVP (polyvinylpyrrolidone) solution to the water to prepare nano-graphene dispersion;
(2)将纳米石墨烯分散液均匀的涂抹在桑叶上,并且晾干。(2) The nano graphene dispersion is evenly smeared on the mulberry leaves and dried.
进一步地,所述纳米石墨烯分散液涂覆于桑叶前,先超声32-50min,使纳米粒子分散均匀。Further, before the nano-graphene dispersion is applied to the mulberry leaves, it is ultrasonicated for 32-50 minutes to make the nano-particles uniformly dispersed.
进一步地,同一批蚕从三龄到上蔟结茧期间,所喂桑叶中,石墨烯分散液的浓度不变。Furthermore, during the period from the third instar to cocooning of the same batch of silkworms, the concentration of graphene dispersion in the fed mulberry leaves remained unchanged.
本发明还提供一种上述制备高导热蚕丝的纳米石墨烯添食育蚕法所获得的高导热蚕丝。The invention also provides a high-thermal-conductivity silk obtained by the above-mentioned nano-graphene-feeding silkworm breeding method for preparing high-thermal-conductivity silk.
进一步地,所述脱除丝胶的具体过程包括以下步骤:Further, the specific process of removing sericin includes the following steps:
(1)将蚕茧剪开除去内部蚕蛹;(1) Cut the cocoon to remove the inner silkworm pupa;
(2)将蚕茧置于质量分数0.5%的Na 2CO 3水溶液中,煮沸30min,然后用40℃的去离子水清洗; (2) Put the silkworm cocoons in a 0.5% Na 2 CO 3 aqueous solution, boil for 30 min, and then wash with deionized water at 40°C;
(3)重复步骤(2),将脱胶完成的蚕丝放入鼓风干燥箱,设定温度105℃,时间120min。(3) Repeat step (2), put the degummed silk into a blast drying box, set a temperature of 105°C for 120 minutes.
本发明还提供一种采用上述高导热蚕丝制得的蚕丝制品,该蚕丝制品是由高导热蚕丝经编织或纺织而成的。The present invention also provides a silk product made from the above-mentioned high thermal conductivity silk. The silk product is knitted or woven from the high thermal conductivity silk.
本发明公开了以下技术效果:The present invention discloses the following technical effects:
氧化石墨烯表面丰富的羧基、羟基等基团,与蚕丝丝素蛋白分子所带的羧基、胺基等形成氢键,对纤维起增强作用,但是该方法会导致蚕丝丝素蛋白分子的界面作用,阻碍了无规构象和α螺旋构象向β折叠构象的转变,导致蚕丝的结晶度降低,效果提升有限。The abundant carboxyl and hydroxyl groups on the surface of graphene oxide form hydrogen bonds with the carboxyl and amine groups carried by the silk fibroin molecules to strengthen the fiber, but this method will cause the interface effect of the silk fibroin molecules , Which hinders the transformation of random conformation and α-helical conformation to β-sheet conformation, resulting in a decrease in the crystallinity of silk and limited effect.
纳米石墨烯是由碳原子组成的且只有一层原子厚度的碳材料,它是一种由碳原子构成的单层片状结构的新型二维材料,也是一种单层的石墨薄片,有完美的杂化结构。但由于纳米石墨烯表面不含羟基、羧基等基团,其与蚕丝丝素蛋白分子结合困难,往往存在于丝胶中,导致蚕丝脱胶后效果微弱。Nanographene is a carbon material composed of carbon atoms and only one layer of atomic thickness. It is a new type of two-dimensional material with a single-layer sheet structure composed of carbon atoms. It is also a single-layer graphite sheet with perfect The hybrid structure. However, because the surface of nanographene does not contain hydroxyl groups, carboxyl groups and other groups, it is difficult to bind to silk fibroin molecules, and often exists in sericin, resulting in weak effect after silk degumming.
本发明使用特定尺寸范围的纳米石墨烯、PVP溶液,并通过上述的喂养方法使纳米石墨烯与蚕丝结合,克服了纳米石墨烯表面不含羟基、羧基等基团,与蚕丝丝素蛋白分子结合困难的问题,并能进一步增强纳米石墨烯与蚕丝丝素蛋白分子的结合强度。The present invention uses nano-graphene and PVP solutions in a specific size range, and combines the nano-graphene with silk through the above-mentioned feeding method, which overcomes the fact that the surface of the nano-graphene does not contain hydroxyl, carboxyl and other groups and binds with silk fibroin molecules. Difficult problem, and can further enhance the binding strength of nano-graphene and silk fibroin molecules.
最重要的是纳米石墨烯被分割时其基本物理性能并不改变,而且其性能还有可能异常发挥。这表明,纳米石墨烯可以被蚕更好地吸收,更好地提高蚕丝的导热性能,并且不影响纳米石墨烯本身的性质。The most important thing is that the basic physical properties of nanographene do not change when it is divided, and its performance may be abnormal. This shows that nano-graphene can be better absorbed by silkworms, better improve the thermal conductivity of silk, and does not affect the properties of nano-graphene itself.
本发明将纳米石墨烯溶于水中,水中加入了PVP溶液,可增强石墨烯的可溶性。The present invention dissolves nano graphene in water, and the PVP solution is added to the water to enhance the solubility of graphene.
本发明中纳米石墨烯尺寸非常小,可以被蚕更好地吸收,更好地提高蚕丝的导热性能,并且不影响石墨烯本身的性质。The nano-graphene in the present invention has a very small size, can be better absorbed by silkworms, and better improves the thermal conductivity of silk, and does not affect the properties of graphene itself.
本发明的纳米石墨烯添食育蚕法相对于现有技术的改性方法,省去了昂贵 的设备支持和复杂的技术手段,不仅简便易行、节约成本,而且易于控制、效果显著。Compared with the modification method of the prior art, the nano-graphene feeding silkworm breeding method of the present invention eliminates the need for expensive equipment support and complicated technical means, is simple and easy to implement, saves costs, and is easy to control and has significant effects.
本发明的高导热蚕丝,具有比天然蚕丝具有更好的导热性能,高导热性蚕丝在脱胶后单丝的导热系数约为1.36W/(m·K),为普通蚕丝在脱胶后单丝的导热系数的1.8倍。The high thermal conductivity silk of the present invention has better thermal conductivity than natural silk. The thermal conductivity of the monofilament after degumming of the high thermal conductivity silk is about 1.36W/(m·K), which is the difference of ordinary silk after degumming. 1.8 times the thermal conductivity.
具体实施方式detailed description
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.
实施例1Example 1
一种制备高导热蚕丝的纳米石墨烯添食育蚕法,首先制备含药剂的桑叶,具体为:A method for preparing high-thermal-conductivity silk by adding nano-graphene to feed silkworms. Firstly, prepare mulberry leaves containing medicaments, specifically:
(1)将单层石墨烯粉末的尺寸范围为片径范围是0.5~1.6μm,厚度范围为无限小~0.8nm,单层率为80%的纳米石墨烯溶于加入了PVP溶液的水中,制成纳米石墨烯溶液;(1) The size range of the single-layer graphene powder is 0.5-1.6μm in diameter, infinitely small-0.8nm in thickness, and nanographene with a single-layer rate of 80% dissolved in water added with PVP solution. Make nano graphene solution;
(2)纳米石墨烯溶液超声30min,使纳米粒子分散均匀,得到纳米石墨烯分散液;(2) Ultrasonic the nano graphene solution for 30 minutes to make the nano particles uniformly dispersed to obtain a nano graphene dispersion;
将制得的纳米石墨烯分散液均匀涂覆于桑叶表面,然后将含药剂的桑叶置于室温条件下晾干后喂养蚕,由蚕吸收纳米石墨烯进入丝腺并最终在纺丝过程中将纳米石墨烯结合进入蚕丝,即获得高导热性能蚕丝;The prepared nano-graphene dispersion is uniformly coated on the surface of mulberry leaves, and then the mulberry leaves containing the drug are dried at room temperature and then fed to silkworms. The nano-graphene is absorbed by the silkworms into the silk glands and is finally spinning In the process, the nano-graphene is incorporated into the silk to obtain silk with high thermal conductivity;
具体为:蚕在一龄到二龄喂食未涂覆药剂的新鲜桑叶,三龄第三天开始喂食涂覆了浓度为0.2mg/ml纳米石墨烯分散液的桑叶,直至上蔟结茧,同一批蚕从三龄第三天到上蔟结茧期间,所述含药剂的桑叶上,纳米石墨烯的添加浓度保持不变。Specifically: the silkworms were fed fresh mulberry leaves uncoated with medicine from the first to second instars, and fed mulberry leaves coated with a 0.2mg/ml nanographene dispersion on the third day of the third instar, until the upper cocoon formed During the period from the third day of the third instar to the cocoon formation of the same batch of silkworms, the additive concentration of nano-graphene on the mulberry leaves containing the drug remained unchanged.
将高导热性蚕丝进行脱除丝胶,脱除丝胶的具体过程包括以下步骤:The high thermal conductivity silk is removed from the sericin. The specific process of removing the sericin includes the following steps:
(1)将蚕茧剪开除去内部蚕蛹;(1) Cut the cocoon to remove the inner silkworm pupa;
(2)将蚕茧置于质量分数为0.5%的Na 2CO 3水溶液中,煮沸30min,然后用40℃的去离子水清洗; (2) Put the silkworm cocoons in a 0.5% Na 2 CO 3 aqueous solution, boil for 30 min, and then wash with deionized water at 40°C;
(3)重复第(2)步骤,将脱胶完成的蚕丝放入鼓风干燥箱烘干,设定温度105℃,时间120min。(3) Repeat step (2), put the degummed silk into a blast drying oven for drying, set a temperature of 105°C for 120 minutes.
经检测,所得蚕丝在脱胶之后单丝,断裂强度为582MPa,断裂伸长率为17.1%,断裂能为63J/g,导热系数为1.3W/(m·K)。After testing, the obtained silk filament after degumming has a breaking strength of 582MPa, a breaking elongation of 17.1%, a breaking energy of 63J/g, and a thermal conductivity of 1.3W/(m·K).
由高导热蚕丝经编织而成蚕丝制品。Silk products are woven from high thermal conductivity silk.
实施例2Example 2
一种制备高导热性蚕丝的纳米石墨烯添食育蚕法,首先制备含药剂的桑叶,具体为:A method for preparing high thermal conductivity silkworm silk by adding nano-graphene to feed the silkworm. Firstly, prepare the mulberry leaf containing the medicament, specifically:
(1)将单层石墨烯粉末的尺寸范围为片径范围是1.7~3.5μm,厚度范围为无限小~0.8nm,单层率为80%的纳米石墨烯溶于加入了PVP溶液的水中,制成纳米石墨烯溶液;(1) The size range of the single-layer graphene powder is 1.7-3.5μm in diameter, infinitely small-0.8nm in thickness, and nanographene with a single-layer rate of 80% dissolved in water added with PVP solution. Make nano graphene solution;
(2)纳米石墨烯溶液超声40min,使纳米粒子分散均匀,得到纳米石墨烯分散液;(2) Ultrasound the nano-graphene solution for 40 minutes to make the nano-particles uniformly dispersed to obtain a nano-graphene dispersion;
将制得的纳米石墨烯分散液均匀涂覆于桑叶表面,然后将含药剂的桑叶置于室温条件下晾干后喂养蚕,由蚕吸收纳米石墨烯进入丝腺并最终在纺丝过程中将纳米石墨烯结合进入蚕丝,即获得高导热性能蚕丝;The prepared nano-graphene dispersion is uniformly coated on the surface of mulberry leaves, and then the mulberry leaves containing the drug are dried at room temperature and then fed to silkworms. The nano-graphene is absorbed by the silkworms into the silk glands and is finally spinning In the process, the nano-graphene is incorporated into the silk to obtain silk with high thermal conductivity;
具体为:蚕在一龄到二龄喂食未涂覆药剂的新鲜桑叶,三龄第三天开始喂食涂覆了浓度为0.5mg/ml纳米石墨烯分散液的桑叶,直至上蔟结茧,同一批蚕从三龄第三天到上蔟结茧期间,所述含药剂的桑叶上,纳米石墨烯的添加浓度保持不变。Specifically: the silkworms were fed fresh mulberry leaves uncoated with medicine from the first to second instars, and fed mulberry leaves coated with the nano graphene dispersion at a concentration of 0.5mg/ml on the third day of the third instar, until the upper cocoon formed a cocoon. During the period from the third day of the third instar to the cocoon formation of the same batch of silkworms, the additive concentration of nano-graphene on the mulberry leaves containing the drug remained unchanged.
将高导热性蚕丝进行脱除丝胶,脱除丝胶的具体过程包括以下步骤:The high thermal conductivity silk is removed from the sericin. The specific process of removing the sericin includes the following steps:
(1)将蚕茧剪开除去内部蚕蛹;(1) Cut the cocoon to remove the inner silkworm pupa;
(2)将蚕茧置于质量分数为0.5%的Na 2CO 3水溶液中,煮沸30min,然后用40℃的去离子水清洗; (2) Put the silkworm cocoons in a 0.5% Na 2 CO 3 aqueous solution, boil for 30 min, and then wash with deionized water at 40°C;
(3)重复第(2)步骤,将脱胶完成的蚕丝放入鼓风干燥箱烘干,设定温度 105℃,时间120min。(3) Repeat step (2), put the degummed silk into a blast drying oven for drying, set a temperature of 105°C for 120 minutes.
经检测,所得蚕丝在脱胶之后单丝,断裂强度为582MPa,断裂伸长率为16.8%,断裂能为58J/g,导热系数为1.18W/(m·K)。After testing, the obtained silk filament after degumming has a breaking strength of 582MPa, a breaking elongation of 16.8%, a breaking energy of 58J/g, and a thermal conductivity of 1.18W/(m·K).
由高强度蚕丝经编织而成蚕丝制品。Silk products are woven from high-strength silk.
实施例3Example 3
一种制备高导热性蚕丝的纳米石墨烯添食育蚕法,首先制备含药剂的桑叶,具体为:A method for preparing high thermal conductivity silkworm silk by adding nano-graphene to feed the silkworm. Firstly, prepare the mulberry leaf containing the medicament, specifically:
(1)将单层石墨烯粉末的尺寸范围为片径范围是3.6~5μm,厚度范围为无限小~0.8nm,单层率为80%的纳米石墨烯溶于加入了PVP溶液的水中,制成纳米石墨烯溶液;(1) The size range of single-layer graphene powder is from 3.6 to 5 μm in diameter, infinitely small to 0.8 nm in thickness, and nano-graphene with a single layer rate of 80% in water added with PVP solution. Into nano graphene solution;
(2)纳米石墨烯溶液超声45min,使纳米粒子分散均匀,得到纳米石墨烯分散液;(2) Ultrasound the nano-graphene solution for 45 minutes to make the nano-particles uniformly dispersed to obtain a nano-graphene dispersion;
将制得的纳米石墨烯分散液均匀涂覆于桑叶表面,然后将含药剂的桑叶置于室温条件下晾干后喂养蚕,由蚕吸收纳米石墨烯进入丝腺并最终在纺丝过程中将纳米石墨烯结合进入蚕丝,即获得高导热性能蚕丝;The prepared nano-graphene dispersion is uniformly coated on the surface of mulberry leaves, and then the mulberry leaves containing the drug are dried at room temperature and then fed to silkworms. The nano-graphene is absorbed by the silkworms into the silk glands and is finally spinning In the process, the nano-graphene is incorporated into the silk to obtain silk with high thermal conductivity;
具体为:蚕在一龄到二龄喂食未涂覆药剂的新鲜桑叶,三龄第三天开始喂食涂覆了浓度为1mg/ml纳米石墨烯分散液的桑叶,直至上蔟结茧,同一批蚕从三龄第三天到上蔟结茧期间,所述含药剂的桑叶上,纳米石墨烯的添加浓度保持不变。Specifically: the silkworms were fed fresh mulberry leaves uncoated with medicine from the first to second instar, and fed mulberry leaves coated with the nano-graphene dispersion at a concentration of 1 mg/ml on the third day of the third instar until the upper cocoon formed. During the period from the third day of the third instar to the cocoon formation of the same batch of silkworms, the additive concentration of nano-graphene on the mulberry leaves containing the drug remains unchanged.
将高导热性蚕丝进行脱除丝胶,脱除丝胶的具体过程包括以下步骤:The high thermal conductivity silk is removed from the sericin. The specific process of removing the sericin includes the following steps:
(1)将蚕茧剪开除去内部蚕蛹;(1) Cut the cocoon to remove the inner silkworm pupa;
(2)将蚕茧置于质量分数为0.5%的Na 2CO 3水溶液中,煮沸30min,然后用40℃的去离子水清洗; (2) Put the silkworm cocoons in a 0.5% Na 2 CO 3 aqueous solution, boil for 30 min, and then wash with deionized water at 40°C;
(3)重复第(2)步骤,将脱胶完成的蚕丝放入鼓风干燥箱烘干,设定温度105℃,时间120min。(3) Repeat step (2), put the degummed silk into a blast drying oven for drying, set a temperature of 105°C for 120 minutes.
经检测,所得蚕丝在脱胶之后单丝,断裂强度为593MPa,断裂伸长率为17.6%,断裂能为65J/g,导热系数为0.9W/(m·K)。After testing, the obtained silk filament after degumming has a breaking strength of 593MPa, a breaking elongation of 17.6%, a breaking energy of 65J/g, and a thermal conductivity of 0.9W/(m·K).
由高强度蚕丝经编织而成蚕丝制品。Silk products are woven from high-strength silk.
对比例1Comparative example 1
与实施例3相比,区别在于:用于喂食蚕的桑叶中不含有纳米石墨烯,只有PVP溶液,其它步骤与实施例3相同。Compared with Example 3, the difference is that the mulberry leaves used for feeding silkworms do not contain nanographene, only PVP solution, and the other steps are the same as Example 3.
经检测,所得蚕丝在脱胶之后单丝,断裂强度为353MPa,断裂伸长率为14.7%,断裂能为29J/g,导热系数为0.75W/(m·K)。After testing, the obtained single filament after degumming has a breaking strength of 353MPa, a breaking elongation of 14.7%, a breaking energy of 29J/g, and a thermal conductivity of 0.75W/(m·K).
对比例2Comparative example 2
与实施例1相比,区别在于:用于喂食蚕的桑叶中纳米石墨烯替换为尺寸范围为0.5~1.6μm的氧化石墨烯,其它步骤与实施例1相同。Compared with Example 1, the difference is that the nano-graphene in the mulberry leaves used for feeding silkworms is replaced with graphene oxide with a size range of 0.5-1.6 μm, and the other steps are the same as in Example 1.
经检测,所得蚕丝在脱胶之后单丝,断裂强度为486MPa,断裂伸长率为14.6%,断裂能为43J/g,导热系数为0.8W/(m·K)。After testing, the obtained silk filament after degumming has a breaking strength of 486MPa, a breaking elongation of 14.6%, a breaking energy of 43J/g, and a thermal conductivity of 0.8W/(m·K).
对比例3Comparative example 3
与实施例2相比,区别在于:用于喂食蚕的桑叶中纳米石墨烯替换为尺寸范围为1.7~3.5μm的氧化石墨烯,其它步骤与实施例2相同。Compared with Example 2, the difference is that the nano-graphene in the mulberry leaves used for feeding silkworms is replaced with graphene oxide with a size range of 1.7-3.5 μm, and the other steps are the same as in Example 2.
经检测,所得蚕丝在脱胶之后单丝,断裂强度为487MPa,断裂伸长率为14.9%,断裂能为42J/g,导热系数为0.5W/(m·K)。After testing, the obtained silk filament after degumming has a breaking strength of 487MPa, a breaking elongation of 14.9%, a breaking energy of 42J/g, and a thermal conductivity of 0.5W/(m·K).
对比例4Comparative example 4
与实施例3相比,区别在于:用于喂食蚕的桑叶中纳米石墨烯替换为尺寸范围为1.7~3.5μm的氧化石墨烯,其它步骤与实施例3相同。Compared with Example 3, the difference is that the nano-graphene in the mulberry leaves used for feeding silkworms is replaced with graphene oxide with a size range of 1.7-3.5 μm, and the other steps are the same as in Example 3.
经检测,所得蚕丝在脱胶之后单丝,断裂强度为356MPa,断裂伸长率为13.6%,断裂能为38J/g,导热系数为0.55W/(m·K)。After testing, the obtained silk filament after degumming has a breaking strength of 356MPa, a breaking elongation of 13.6%, a breaking energy of 38J/g, and a thermal conductivity of 0.55W/(m·K).
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。The above-mentioned embodiments only describe the preferred mode of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, those of ordinary skill in the art have made various contributions to the technical solutions of the present invention. Variations and improvements should fall within the protection scope determined by the claims of the present invention.

Claims (7)

  1. 一种制备高导热蚕丝的纳米石墨烯添食育蚕法,其特征在于:在桑叶上涂覆纳米石墨烯分散液并喂养蚕,由蚕吸收纳米石墨烯进入丝腺并最终在纺丝过程中将纳米石墨烯结合进入蚕丝,即获得高导热蚕丝;A method for preparing high thermal conductivity silkworm silk by adding nano-graphene to feed silkworms, which is characterized in that: coating nano-graphene dispersion on mulberry leaves and feeding silkworms, the silkworms absorb nano-graphene into the silk glands and are finally spinning In the process, the nano-graphene is incorporated into the silk to obtain high thermal conductivity silk;
    所述纳米石墨烯的尺寸范围是片径范围为0.5-5μm,厚度范围为0-0.8nm,单层率为80%;The size range of the nano graphene is a sheet diameter range of 0.5-5 μm, a thickness range of 0-0.8 nm, and a single layer rate of 80%;
    具体为:蚕在一龄到二龄喂食未添加纳米石墨烯的桑叶,三龄开始喂食添加了质量分数浓度为0.2-1mg/mL纳米石墨烯分散液的桑叶,直至上蔟结茧。Specifically, silkworms were fed mulberry leaves without nanographene from the first to second instars, and fed with mulberry leaves with a concentration of 0.2-1 mg/mL nanographene dispersion at the third instar, until the upper cocoon formed.
  2. 根据权利要求1所述的一种制备高导热蚕丝的纳米石墨烯添食育蚕法,其特征在于,在桑叶上涂覆纳米石墨烯分散液,具体过程包括以下步骤:The nano-graphene feeding silkworm breeding method for preparing high thermal conductivity silk according to claim 1, wherein the nano-graphene dispersion is coated on the mulberry leaf, and the specific process includes the following steps:
    (1)将纳米石墨烯溶于水中,水中加入了PVP溶液,制成纳米石墨烯分散液;(1) Dissolve nano-graphene in water, add PVP solution to the water to prepare nano-graphene dispersion;
    (2)将纳米石墨烯分散液均匀的涂抹在桑叶上,并且晾干。(2) The nano graphene dispersion is evenly smeared on the mulberry leaves and dried.
  3. 根据权利要求1所述的一种制备高导热蚕丝的纳米石墨烯添食育蚕法,其特征在于,所述纳米石墨烯分散液涂覆于桑叶前,先超声32-50min。The nano-graphene feeding silkworm breeding method for preparing high thermal conductivity silk according to claim 1, wherein the nano-graphene dispersion liquid is ultrasonicated for 32-50 minutes before coating the mulberry leaves.
  4. 根据权利要求1所述的一种制备高导热蚕丝的纳米石墨烯添食育蚕法,其特征在于,同一批蚕从三龄到上蔟结茧期间,所喂桑叶中,石墨烯分散液的浓度不变。The nanographene feeding method for preparing high thermal conductivity silkworm silk according to claim 1, characterized in that, during the period from the third instar to the cocoon formation of the same batch of silkworms, the graphene dispersion liquid in the mulberry leaves fed The concentration remains unchanged.
  5. 一种权利要求1-4任一项所述的制备高导热蚕丝的纳米石墨烯添食育蚕法所获得的高导热蚕丝。A high-thermal-conductivity silk obtained by the method of feeding silkworms with nano-graphene for preparing high-thermal-conductivity silk according to any one of claims 1-4.
  6. 根据权利要求5所述的高导热蚕丝,其特征在于,所述脱除丝胶的具体过程包括以下步骤:The high thermal conductivity silk of claim 5, wherein the specific process of removing the sericin comprises the following steps:
    (1)将蚕茧剪开除去内部蚕蛹;(1) Cut the cocoon to remove the inner silkworm chrysalis;
    (2)将蚕茧置于质量分数0.5%的Na 2CO 3水溶液中,煮沸30min,然后用40℃的去离子水清洗; (2) Put the silkworm cocoons in a 0.5% Na 2 CO 3 aqueous solution, boil for 30 min, and then wash with deionized water at 40°C;
    (3)重复步骤(2),将脱胶完成的蚕丝放入鼓风干燥箱,设定温度105℃,时间120min。(3) Repeat step (2), put the degummed silk into a blast drying oven, set a temperature of 105°C for 120 minutes.
  7. 一种采用如权利要求5所述的高导热蚕丝制得的蚕丝制品,其特征在 于,该蚕丝制品是由高导热蚕丝经编织或纺织而成的。A silk product made by using the high thermal conductivity silk as claimed in claim 5, characterized in that the silk product is knitted or woven from high thermal conductivity silk.
PCT/CN2020/075803 2019-03-26 2020-02-19 Method for preparing silk with high thermal conductivity by breeding a silkworm fed on nano-graphene, and product thereof WO2020192312A1 (en)

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