技术领域technical field
本发明属蚕丝纤维及其改性领域，涉及一种制备高性能蚕丝的纳米氧化锌添食育蚕法及其制品。The invention belongs to the field of silk fiber and its modification, and relates to a silkworm breeding method for preparing high-performance silk by adding food to nano-zinc oxide and its products.
背景技术Background technique
熟蚕结茧时由丝腺分泌出的由蛋白质组成的纺丝液，在空气中凝固形成的连续长纤维称为蚕丝。作为一种生物纤维，蚕丝不仅具有良好的光泽度和舒适的触感，还具有较强的机械性能和很好的生物相容性，在纺织、医学、化妆品及生物领域都有广泛的应用。The spinning solution composed of protein secreted by the silk gland when the silkworm cocoons, coagulates in the air to form a continuous long fiber called silk. As a biological fiber, silk not only has good gloss and comfortable touch, but also has strong mechanical properties and good biocompatibility, and is widely used in textile, medicine, cosmetics and biological fields.
脱胶蚕丝的断裂强度约为400MPa，断裂伸长率和断裂能为15％和30J/g左右，在实际应用中有待进一步提高。蚕丝本身具有一定的抗紫外和抗菌的能力，但并不显著，如未经处理的天然蚕丝在测试中并未表现出明显的抑菌圈。因此为了提高蚕丝的性能并拓宽其应用领域，需要对蚕丝进行改性。The breaking strength of degummed silk is about 400MPa, and the breaking elongation and breaking energy are about 15% and 30J/g, which need to be further improved in practical application. Silk itself has a certain ability of anti-ultraviolet and antibacterial, but it is not significant. For example, untreated natural silk did not show obvious antibacterial zone in the test. Therefore, in order to improve the performance of silk and broaden its application field, it is necessary to modify silk.
有研究通过在蚕丝表面涂布粒子的方法来增强蚕丝的性能。例如公开号为CN103572585A的中国专利公开了一种二氧化钛改性的蚕丝及其制备方法。专利中发明者以钛酸酯为反应物，以石油醚作溶剂，原位室温合成致密的水合二氧化钛，覆盖于蚕丝表面。虽然通过此方法改性的蚕丝的断裂伸长率可达到22％，断裂能为22～74J/g，强度为300～680MPa，同时其抗紫外线和抗菌能力均得到显著提高。但是这种改性天然蚕丝的方法需要使用有机溶剂，若量化生产在溶剂回收处理方面需要较多的投入。不仅如此，二氧化钛覆盖于蚕丝表面会损害蚕丝本身的色泽、触感、透气性等优秀品质。There are studies to enhance the performance of silk by coating particles on the surface of silk. For example, the Chinese patent publication number CN103572585A discloses a titanium dioxide modified silk and a preparation method thereof. The inventor in the patent uses titanate as a reactant and petroleum ether as a solvent to synthesize dense hydrated titanium dioxide in situ at room temperature and cover the surface of silk. Although the elongation at break of the silk modified by this method can reach 22%, the energy at break is 22-74J/g, and the strength is 300-680MPa, meanwhile its anti-ultraviolet and antibacterial ability are significantly improved. However, this method of modifying natural silk requires the use of organic solvents, and if quantitative production requires more investment in solvent recovery and treatment. Not only that, titanium dioxide covering the surface of silk will damage the excellent qualities of silk itself such as color, touch, and air permeability.
其他的一些研究则使用丝素溶液中添加金属氧化物的纳米粒子再用人工方法纺成纤维的方法来提高蚕丝的性能。例如公开号为CN102912470A的中国专利公开了一种金属氧化物纳米粒子增强增韧的再生蚕丝纤维及其制备方法。该发明中研究者将天然蚕丝脱胶后制成再生丝素蛋白溶液，调节其钙离子浓度到0.15～0.3mol/L，然后与一定比例的金属氧化物(TiO2、Fe3O4、ZnO、Al2O3或ZrO2)水溶胶混合，浓缩，在室温下干纺成丝，最后用乙醇-水混合液进行后处理，得到的再生蚕丝纤维断裂伸长率为50％～150％，断裂能为30～100J/g，断裂强度为50～250MPa。公开号为CN103572395A的中国专利公开了一种增强增韧再生蚕丝纤维及其制备方法。研究者在前述公开号为CN102912470A的基础上，在再生丝素蛋白溶液中又加入了氧化石墨烯溶液，使用同样的方法制得再生丝素纤维。此方法得到的再生蚕丝纤维断裂伸长率为20％～150％，断裂能为30～100J/g，断裂强度为70～380MPa。这两种方法对蚕丝的韧性均有很大的提高，但是却未能保持其断裂强度在一个较好的水平，专利中也并未提到可使蚕丝获得其他功能性。而且通过再生丝素蛋白溶液纺丝的过程操作复杂、条件苛刻、周期长、产量低，工业化的可能性非常小。Other studies have used the method of adding metal oxide nanoparticles to silk fibroin solution and artificially spinning fibers to improve the performance of silk. For example, the Chinese patent with publication number CN102912470A discloses a regenerated silk fiber reinforced and toughened by metal oxide nanoparticles and a preparation method thereof. In this invention, researchers degummed natural silk to make regenerated silk fibroin solution, adjusted its calcium ion concentration to 0.15-0.3mol/L, and then mixed it with a certain proportion of metal oxides (TiO2 , Fe3 O4 , ZnO, Al2 O3 or ZrO2 ) water sols are mixed, concentrated, dry-spun into silk at room temperature, and finally post-treated with ethanol-water mixture, and the elongation at break of the obtained regenerated silk fiber is 50% to 150%. The energy is 30~100J/g, and the breaking strength is 50~250MPa. The Chinese patent with the publication number CN103572395A discloses a reinforced and toughened regenerated silk fiber and a preparation method thereof. On the basis of the aforementioned publication number CN102912470A, the researchers added graphene oxide solution to the regenerated silk fibroin solution, and used the same method to prepare regenerated silk fibroin fibers. The elongation at break of the regenerated silk fiber obtained by the method is 20%-150%, the break energy is 30-100J/g, and the break strength is 70-380MPa. These two methods have greatly improved the toughness of silk, but failed to maintain its breaking strength at a good level, and the patent did not mention that silk can obtain other functions. Moreover, the process of spinning through regenerated silk fibroin solution is complex in operation, harsh in conditions, long in cycle and low in yield, and the possibility of industrialization is very small.
也有研究者在家蚕饲料中添加一些功能性微粒，从而得到具有某些特定功能的蚕丝。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力学性能特征，仅表示所得蚕丝具有一些所添加的微粒的功能，可应用范围窄。There are also researchers who add some functional particles to silkworm feed to obtain silk with certain specific functions. The Chinese patent with the publication number CN1395861A discloses a silkworm feed containing functional microparticles, silk produced by feeding the feed, and products using the silk. In this patent, the inventor adds functional microparticles such as minerals and pigments to the silkworm feed Feed the silkworm in the middle, and spin the functional silk through the absorption and transformation of the silkworm. Publication number is that the Chinese patent of CN1608489 discloses a kind of feed for silkworms and silk produced by feeding the feed and silk products using the silk. This patent is to dissolve a specified amount of functional particles such as zeolite and luminous stone in water or other solvents, and then add them to silkworm feed to feed silkworms 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 growth of silkworms, resulting in a decrease in silk quality and yield. The results also show that more functional particles exist in sericin, and most of the silk needs to be degummed when it is used, so that its modification effect is negligible. Moreover, both of them do not give the mechanical property characteristics of the obtained silk, but only indicate that the obtained silk has some functions of the added particles, and the applicable range is narrow.
发明内容Contents of the invention
本发明的目的是提供一种制备高性能蚕丝的纳米氧化锌添食育蚕法及其制品，更好地用于组织支架工程、纺织及医学等领域。在本发明中，将纳米氧化锌混合在蚕饲料中喂食家蚕，通过家蚕自身的吸收，使纳米氧化锌混合进入蚕丝，以提高蚕丝的机械性能以及抗菌和抗紫外能力。本方法得到的高性能蚕丝，纳米氧化锌中的锌元素通过氢键、螯合方式与丝素蛋白发生相互作用并形成界面层，脱胶丝能保持很好的改性效果。本方法在提高蚕丝的机械性能的同时，还能提高其抗菌和抗紫外能力，并且不会损害蚕丝其他的优良品质。整个过程绿色环保，简便易行，在正常的家蚕饲养过程中即可实施，可实现工业化生产。The object of the present invention is to provide a method of raising silkworms by adding food to nano-zinc oxide for preparing high-performance silk and its products, which can be better used in the fields of tissue scaffold engineering, textile and medicine. In the present invention, the nano-zinc oxide is mixed in the silkworm feed to feed the silkworm, and the nano-zinc oxide is mixed into the silk through the absorption of the silkworm itself, so as to improve the mechanical properties, antibacterial and anti-ultraviolet capabilities of the silk. In the high-performance silk obtained by the method, the zinc element in the nano-zinc oxide interacts with the silk fibroin through hydrogen bonding and chelation to form an interface layer, and the degummed silk can maintain a good modification effect. While improving the mechanical properties of the silk, the method can also improve its antibacterial and anti-ultraviolet capabilities without damaging other good qualities of the silk. The whole process is environmentally friendly, simple and easy to implement, can be implemented in the normal silkworm breeding process, and can realize industrial production.
本发明的一种制备高性能蚕丝的纳米氧化锌添食育蚕法，在家蚕人工饲料即蚕饲料中添加纳米氧化锌并喂养蚕，由蚕吸收纳米氧化锌进入丝腺并最终在纺丝过程中将纳米氧化锌结合进入蚕丝，即获得高性能蚕丝；A method of adding food to silkworms with nano-zinc oxide for preparing high-performance silk of the present invention, adding nano-zinc oxide to the artificial feed of silkworms, that is, silkworm feed, and feeding silkworms, and the silkworms absorb nano-zinc oxide into silk glands and finally in silkworm spinning In the process, nano-zinc oxide is combined into silk to obtain high-performance silk;
具体为：蚕在一龄到四龄喂食未添加纳米氧化锌的蚕饲料，五龄第二天开始喂食添加了质量百分数为0.5～2％纳米氧化锌的复合饲料，直至上蔟结茧。家蚕在五龄期腺体比重急增，五龄饲料蛋白在其丝腺的留存率由9％逐渐增加到96％，可见其丝蛋白的合成主要在五龄期进行。因此选择五龄期添食纳米氧化锌可获得最高原料利用率和最佳效果。Specifically, silkworms are fed silkworm feed without adding nano-zinc oxide from the first to fourth instar, and feed compound feed added with 0.5-2% nano-zinc oxide by mass percentage on the second day of the fifth instar until cocoons are formed in the upper cocoon. The proportion of silkworm glands increases sharply at the fifth instar, and the retention rate of fifth instar feed protein in silk glands gradually increases from 9% to 96%. It can be seen that the synthesis of silk protein is mainly carried out at the fifth instar. Therefore, choosing the five-year-old to add nano-zinc oxide can obtain the highest raw material utilization rate and the best effect.
有研究通过多脉冲气相渗透法把钛、铝、锌等元素渗透到天然蛛丝中，反应物进入之后与蛋白质分子以共价键或配位键连接，形成金属-蛋白质络合物。蜘蛛丝无定型区内的蛋白质分子由金属连接，因此其力学性能大大提高。本发明则通过添食育蚕法将纳米氧化锌溶入到蚕丝中，使锌元素与丝素蛋白分子以共价键或配位键连接，形成锌-蛋白质络合物，提高蚕丝的力学性能；同时，由于锌元素与丝素蛋白分子能形成配位键和氢键，阻碍无规构象和α螺旋构象向β折叠构象的转变，导致蚕丝的结晶度降低；因此，综合考虑，若纳米氧化锌的添加量过高，进入丝腺的纳米粒子浓度过高，则不利于丝蛋白结晶；并且过多的添加物必然会影响家蚕的正常生长，因此本发明所需纳米氧化锌的添加量较低，质量百分数仅为0.5～2％，实验表明此添加量未影响蚕的正常进食量、进食速度、生长和结茧。Some studies have infiltrated titanium, aluminum, zinc and other elements into natural spider silk by multi-pulse gas-phase infiltration. After entering, the reactants are connected with protein molecules by covalent bonds or coordination bonds to form metal-protein complexes. The protein molecules in the amorphous region of spider silk are linked by metal, so its mechanical properties are greatly improved. The present invention dissolves nano-zinc oxide into silk by adding food and raising silkworms, so that the zinc element and silk fibroin molecules are connected by covalent bonds or coordination bonds to form zinc-protein complexes and improve the mechanical properties of silk ; At the same time, since zinc and silk fibroin molecules can form coordination bonds and hydrogen bonds, which hinder the transformation of random conformation and α-helical conformation to β-sheet conformation, resulting in a decrease in the crystallinity of silk; therefore, comprehensive consideration, if nano-oxidation The addition of zinc is too high, and the concentration of nanoparticles entering the silk gland is too high, which is unfavorable for silk protein crystallization; and too many additions will inevitably affect the normal growth of silkworms, so the addition of nano-zinc oxide required by the present invention is relatively high. Low, the mass percentage is only 0.5-2%. Experiments show that this addition does not affect the normal feeding amount, feeding speed, growth and cocooning of silkworms.
作为优选的技术方案：As a preferred technical solution:
如上所述的一种制备高性能蚕丝的纳米氧化锌添食育蚕法，所述复合饲料是指在蚕饲料中均匀混入一定量的纳米氧化锌并加热熟制的饲料；所述复合饲料的具体制备过程包括以下步骤：As mentioned above, a nano-zinc oxide method for preparing high-performance silk by adding food to silkworms, the compound feed refers to a feed that is evenly mixed with a certain amount of nano-zinc oxide in the silkworm feed and cooked by heating; the compound feed Concrete preparation process comprises the following steps:
(1)将纳米氧化锌溶于水中，制成纳米氧化锌溶液；(1) dissolving nano zinc oxide in water to make nano zinc oxide solution;
(2)将纳米氧化锌溶液与蚕饲料搅拌均匀，然后加热，冷却后即制成复合饲料；(2) Stir the nanometer zinc oxide solution and the silkworm feed evenly, then heat, and promptly make compound feed after cooling;
其中，水的质量为蚕饲料的2～3倍。Among them, the quality of water is 2 to 3 times that of silkworm feed.
如上所述的一种制备高性能蚕丝的纳米氧化锌添食育蚕法，所述纳米氧化锌溶液在与蚕饲料混合前，先超声15～30min，使纳米粒子分散均匀。According to the method for preparing high-performance silkworm silk by adding food to nano-zinc oxide and raising silkworms, the nano-zinc oxide solution is ultrasonicated for 15-30 minutes before being mixed with silkworm feed, so that the nanoparticles are evenly dispersed.
如上所述的一种制备高性能蚕丝的纳米氧化锌添食育蚕法，所述加热是指放入微波炉中加热3～6min，微波炉的输出功率为800～1000W。In the aforementioned method for preparing high-performance silkworm silk by adding food to nano-zinc oxide, the heating refers to heating in a microwave oven for 3-6 minutes, and the output power of the microwave oven is 800-1000W.
如上所述的一种制备高性能蚕丝的纳米氧化锌添食育蚕法，所述纳米氧化锌的尺寸范围为40～200nm。According to the above-mentioned method for preparing high-performance silkworm silk by adding food to nano-zinc oxide, the size range of the nano-zinc oxide is 40-200nm.
本发明所用氧化锌尺寸很小，并且具有较好的水溶性，经过超声之后可稳定分散于水中，再与饲料混合均匀。复合饲料经过微波加热，冷却成型，可保持适宜的湿度，利于家蚕进食。氧化锌被家蚕摄入体内之后，很快扩散进入其身体的各个器官，包括丝腺，氧化锌即与蛋白质结合，最终在家蚕的纺丝过程中进入蚕丝。由于家蚕自身的吸收转化作用，氧化锌可与蚕丝蛋白稳定结合，并均匀分布于蚕丝中，有效提高蚕丝的性能。The zinc oxide used in the invention has a small size and good water solubility, can be stably dispersed in water after being ultrasonicated, and then mixed evenly with feed. The compound feed is heated by microwaves, cooled and molded to maintain a suitable humidity, which is beneficial for silkworms to eat. After zinc oxide is ingested by silkworms, it quickly diffuses into various organs of the body, including silk glands. Zinc oxide binds to proteins and finally enters silk during the silk spinning process of silkworms. Due to the absorption and transformation of silkworm itself, zinc oxide can be stably combined with silk protein and evenly distributed in silk, effectively improving the performance of silk.
如上所述的一种制备高性能蚕丝的纳米氧化锌添食育蚕法，同一批蚕从五龄第二天到上蔟结茧期间，所述复合饲料中，纳米氧化锌的添食浓度保持不变。As mentioned above, a nano-zinc oxide feeding silkworm breeding method for preparing high-performance silk, during the same batch of silkworms from the second day of the fifth instar to cocooning in the upper sack, in the compound feed, the feeding concentration of nano-zinc oxide remains constant. constant.
一种制备高性能蚕丝的纳米氧化锌添食育蚕法所获得的高性能蚕丝，所述高性能蚕丝在脱除丝胶之后单丝的断裂强度为390～500MPa，断裂伸长率为15～20％，断裂能为30～70J/g。所述的高性能蚕丝脱除丝胶之后经光强为1245μW/cm2且波长为390nm的紫外光照射3h后断裂强度无明显损失，对大肠杆菌的抑菌圈大于10mm。A high-performance silk obtained by adding food to silkworms with nano-zinc oxide for preparing high-performance silk, the high-performance silk has a monofilament breaking strength of 390-500 MPa after removing sericin, and a breaking elongation of 15-500 MPa. 20%, the breaking energy is 30-70J/g. After removing the sericin, the high-performance silk is irradiated with ultraviolet light with a light intensity of 1245 μW/cm2 and a wavelength of 390 nm for 3 hours without obvious loss of breaking strength, and the bacteriostatic zone against Escherichia coli is greater than 10 mm.
纳米氧化锌具一定的散射紫外线能力，其粒径小于紫外线的波长，因而具有较强的吸收紫外线能力。纳米氧化锌在阳光尤其是在紫外光的照射下，能分解出自由电子，留下带正电的空穴，空穴可激活氧变成活性氧，可氧化多种微生物，起到杀菌作用。因此结合了纳米氧化锌的蚕丝抗菌性和抗紫外性能都有较大提高。Nano-zinc oxide has a certain ability to scatter ultraviolet rays, and its particle size is smaller than the wavelength of ultraviolet rays, so it has a strong ability to absorb ultraviolet rays. Nano-zinc oxide can decompose free electrons under the irradiation of sunlight, especially ultraviolet light, leaving positively charged holes, which can activate oxygen to become active oxygen, oxidize various microorganisms, and play a bactericidal effect. Therefore, the antibacterial and anti-ultraviolet properties of silk combined with nano-zinc oxide are greatly improved.
如上所述的高性能蚕丝，所述脱除丝胶的具体过程包括以下步骤：As above-mentioned high-performance silk, the concrete process of described removing sericin comprises the following steps:
(1)将蚕茧剪开除去内部蚕蛹；(1) cutting the silkworm cocoon to remove the inner silkworm chrysalis;
(2)将蚕茧置于质量百分数为0.5～1％的Na2CO3水溶液中，煮沸20～30min，然后用去离子水清洗；(2) Put silkworm cocoons in 0.5-1% Na2 CO3 aqueous solution, boil them for 20-30 minutes, and then wash them with deionized water;
(3)重复第(2)步2～3次，将脱胶完成的蚕丝悬挂于室内自然风干。(3) Repeat step (2) 2 to 3 times, and hang the degummed silk in the room to dry naturally.
丝胶对于蚕丝纤维的力学性能影响不大，在实际应用中，大多需要脱除丝胶，因此本发明采用脱胶丝的力学性能来表现改性效果，同时证明本发明中氧化锌与丝素蛋白的相互作用及有效结合。Sericin has little effect on the mechanical properties of silk fibers. In practical applications, sericin needs to be removed mostly. Therefore, the present invention uses the mechanical properties of degummed silk to show the modification effect, and at the same time proves that zinc oxide and silk fibroin in the present invention interaction and effective combination.
一种蚕丝制品，由高性能蚕丝经编织或纺织而成的。A silk product, which is woven or woven from high-performance silk.
有益效果：Beneficial effect:
本发明的纳米氧化锌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 silkworm breeding method of adding food with nano-zinc oxide of the present invention saves expensive equipment support and complicated technical means, is not only simple and easy to implement, saves costs, but also is easy to control and has remarkable effects.
本发明的高性能蚕丝，具有比天然蚕丝具有更好的机械性能，同时还具有较好的抗菌和抗紫外能力。The high-performance silk of the present invention has better mechanical properties than natural silk, and also has better antibacterial and anti-ultraviolet capabilities.
具体实施方式Detailed ways
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in combination with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
本发明中使用的蚕饲料，呈干燥粉末状，其主要成分及配制比例范围列于表1。The silkworm feed used in the present invention is dry powder, and its main components and preparation ratio range are listed in Table 1.
表1实验用蚕饲料的组成Table 1 The composition of the silkworm feed used in the experiment
实施例1Example 1
一种制备高性能蚕丝的纳米氧化锌添食育蚕法，首先制备复合饲料，具体为：A kind of method for raising silkworms by adding food to nano-zinc oxide for preparing high-performance silk, at first preparing compound feed, specifically:
(1)将尺寸范围为40～200nm的纳米氧化锌溶于水中，制成纳米氧化锌溶液；(1) dissolving nano-zinc oxide with a size range of 40 to 200nm in water to make a nano-zinc oxide solution;
(2)先将纳米氧化锌溶液超声15min，使纳米粒子分散均匀，将纳米氧化锌溶液与蚕饲料搅拌均匀，然后放入微波炉中加热3min，微波炉的输出功率为800W，冷却后即制成复合饲料；其中，水的质量为蚕饲料的2倍；(2) Ultrasonic the nano-zinc oxide solution for 15 minutes to disperse the nanoparticles evenly, stir the nano-zinc oxide solution and silkworm feed evenly, then put it into a microwave oven and heat it for 3 minutes. Feed; Wherein, the quality of water is 2 times of silkworm feed;
然后在家蚕人工饲料即蚕饲料中添加纳米氧化锌并喂养蚕，由蚕吸收纳米氧化锌进入丝腺并最终在纺丝过程中将纳米氧化锌结合进入蚕丝，即获得高性能蚕丝；Then add nano-zinc oxide to silkworm artificial feed, that is, silkworm feed, and feed silkworms. The silkworm absorbs nano-zinc oxide and enters the silk gland, and finally combines nano-zinc oxide into silk during the spinning process to obtain high-performance silk;
具体为：蚕在一龄到四龄喂食未添加纳米氧化锌的蚕饲料，五龄第二天开始喂食添加了质量百分数为0.5％纳米氧化锌的复合饲料，直至上蔟结茧，同一批蚕从五龄第二天到上蔟结茧期间，复合饲料中，纳米氧化锌的添食浓度保持不变。Specifically: the silkworms were fed silkworm feed without adding nano-zinc oxide from the first to the fourth instar, and the compound feed added with 0.5% nano-zinc oxide by mass percentage was fed on the second day of the fifth instar until the upper cocoons were cocooned. From the second day of the fifth instar to the period of cocooning in the upper bundle, the concentration of nano-zinc oxide in the compound feed remained unchanged.
一种制备高性能蚕丝的纳米氧化锌添食育蚕法所获得的高性能蚕丝，将高性能蚕丝进行脱除丝胶，脱除丝胶的具体过程包括以下步骤：A high-performance silk obtained by adding food to silkworms with nano-zinc oxide for preparing high-performance silk. The high-performance 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) cutting the silkworm cocoon to remove the inner silkworm chrysalis;
(2)将蚕茧置于质量百分数为0.5％的Na2CO3水溶液中，煮沸20min，然后用去离子水清洗；(2) Put silkworm cocoons in 0.5% Na2 CO3 aqueous solution, boil them for 20 minutes, and then wash them with deionized water;
(3)重复第(2)步2次，将脱胶完成的蚕丝悬挂于室内自然风干。高性能蚕丝在脱除丝胶之后单丝的断裂强度为390MPa，断裂伸长率为15％，断裂能为30J/g。高性能蚕丝脱除丝胶之后经光强为1245μW/cm2且波长为390nm的紫外光照射3h后断裂强度无明显损失，对大肠杆菌的抑菌圈大于10mm。(3) Repeat step (2) twice, and hang the degummed silk in the room to dry naturally. After removing the sericin, the high-performance silk has a breaking strength of 390 MPa, a breaking elongation of 15%, and a breaking energy of 30 J/g. After removing the sericin, the high-performance silk has no obvious loss of breaking strength after being irradiated with ultraviolet light with a light intensity of 1245 μW/cm2 and a wavelength of 390 nm for 3 hours, and the inhibition zone against Escherichia coli is greater than 10 mm.
由高性能蚕丝经编织而成蚕丝制品。Silk products are woven from high-performance silk.
实验用蚕饲料的组成如下：The composition of the silkworm feed used in the experiment is as follows:
实施例2Example 2
一种制备高性能蚕丝的纳米氧化锌添食育蚕法，首先制备复合饲料，具体为：A kind of method for raising silkworms by adding food to nano-zinc oxide for preparing high-performance silk, at first preparing compound feed, specifically:
(1)将尺寸范围为40～200nm的纳米氧化锌溶于水中，制成纳米氧化锌溶液；(1) dissolving nano-zinc oxide with a size range of 40 to 200nm in water to make a nano-zinc oxide solution;
(2)先将纳米氧化锌溶液超声30min，使纳米粒子分散均匀，将纳米氧化锌溶液与蚕饲料搅拌均匀，然后放入微波炉中加热6min，微波炉的输出功率为1000W，冷却后即制成复合饲料；其中，水的质量为蚕饲料的3倍；(2) Ultrasonic the nano-zinc oxide solution for 30 minutes to disperse the nanoparticles evenly, stir the nano-zinc oxide solution and silkworm feed evenly, then put it into a microwave oven and heat it for 6 minutes. Feed; Wherein, the quality of water is 3 times of silkworm feed;
然后在家蚕人工饲料即蚕饲料中添加纳米氧化锌并喂养蚕，由蚕吸收纳米氧化锌进入丝腺并最终在纺丝过程中将纳米氧化锌结合进入蚕丝，即获得高性能蚕丝；Then add nano-zinc oxide to silkworm artificial feed, that is, silkworm feed, and feed silkworms. The silkworm absorbs nano-zinc oxide and enters the silk gland, and finally combines nano-zinc oxide into silk during the spinning process to obtain high-performance silk;
具体为：蚕在一龄到四龄喂食未添加纳米氧化锌的蚕饲料，五龄第二天开始喂食添加了质量百分数为2％纳米氧化锌的复合饲料，直至上蔟结茧，同一批蚕从五龄第二天到上蔟结茧期间，所述复合饲料中，纳米氧化锌的添食浓度保持不变。Specifically: the silkworms were fed the silkworm feed without adding nano-zinc oxide from the first to the fourth instar, and the compound feed added with 2% by mass percentage of nano-zinc oxide was fed on the second day of the fifth instar until the upper cocoons were cocooned. From the second day of the fifth instar to the period of cocooning in the upper bundle, in the compound feed, the concentration of nano-zinc oxide added remained unchanged.
一种制备高性能蚕丝的纳米氧化锌添食育蚕法所获得的高性能蚕丝，将高性能蚕丝进行脱除丝胶，脱除丝胶的具体过程包括以下步骤：A high-performance silk obtained by adding food to silkworms with nano-zinc oxide for preparing high-performance silk. The high-performance 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) cutting the silkworm cocoon to remove the inner silkworm chrysalis;
(2)将蚕茧置于质量百分数为1％的Na2CO3水溶液中，煮沸20min，然后用去离子水清洗；(2) Put silkworm cocoons in a1 %Na2CO3 aqueous solution by mass, boil them for 20 minutes, and then wash them with deionized water;
(3)重复第(2)步3次，将脱胶完成的蚕丝悬挂于室内自然风干。高性能蚕丝在脱除丝胶之后单丝的断裂强度为500MPa，断裂伸长率为20％，断裂能为70J/g。高性能蚕丝脱除丝胶之后经光强为1245μW/cm2且波长为390nm的紫外光照射3h后断裂强度无明显损失，对大肠杆菌的抑菌圈大于10mm。(3) Repeat step (2) for 3 times, and hang the degummed silk in the room to dry naturally. After the sericin is removed, the high-performance silk has a single filament breaking strength of 500 MPa, a breaking elongation of 20%, and a breaking energy of 70 J/g. After removing the sericin, the high-performance silk has no obvious loss of breaking strength after being irradiated with ultraviolet light with a light intensity of 1245 μW/cm2 and a wavelength of 390 nm for 3 hours, and the inhibition zone against Escherichia coli is greater than 10 mm.
由高性能蚕丝经纺织而成的蚕丝制品。Silk products made of high-performance silk through weaving.
实验用蚕饲料的组成如下：The composition of the silkworm feed used in the experiment is as follows:
实施例3Example 3
一种制备高性能蚕丝的纳米氧化锌添食育蚕法，首先制备复合饲料，具体为：A kind of method for raising silkworms by adding food to nano-zinc oxide for preparing high-performance silk, at first preparing compound feed, specifically:
(1)将尺寸范围为40～200nm的纳米氧化锌溶于水中，制成纳米氧化锌溶液；(1) dissolving nano-zinc oxide with a size range of 40 to 200nm in water to make a nano-zinc oxide solution;
(2)先将纳米氧化锌溶液超声20min，使纳米粒子分散均匀，将纳米氧化锌溶液与蚕饲料搅拌均匀，然后放入微波炉中加热4min，微波炉的输出功率为900W，冷却后即制成复合饲料；其中，水的质量为蚕饲料的2.5倍；(2) Ultrasonic the nano-zinc oxide solution for 20 minutes to disperse the nanoparticles evenly, stir the nano-zinc oxide solution and silkworm feed evenly, then put it into a microwave oven and heat it for 4 minutes. Feed; Wherein, the quality of water is 2.5 times of silkworm feed;
然后在家蚕人工饲料即蚕饲料中添加纳米氧化锌并喂养蚕，由蚕吸收纳米氧化锌进入丝腺并最终在纺丝过程中将纳米氧化锌结合进入蚕丝，即获得高性能蚕丝；Then add nano-zinc oxide to silkworm artificial feed, that is, silkworm feed, and feed silkworms. The silkworm absorbs nano-zinc oxide and enters the silk gland, and finally combines nano-zinc oxide into silk during the spinning process to obtain high-performance silk;
具体为：蚕在一龄到四龄喂食未添加纳米氧化锌的蚕饲料，五龄第二天开始喂食添加了质量百分数为1.5％纳米氧化锌的复合饲料，直至上蔟结茧，同一批蚕从五龄第二天到上蔟结茧期间，所述复合饲料中，纳米氧化锌的添食浓度保持不变。Specifically: the silkworms were fed the silkworm feed without adding nano-zinc oxide from the first to the fourth instar, and fed the compound feed added with 1.5% nano-zinc oxide on the second day of the fifth instar until the upper cocoons were cocooned. From the second day of the fifth instar to the period of cocooning in the upper bundle, in the compound feed, the concentration of nano-zinc oxide added remained unchanged.
一种制备高性能蚕丝的纳米氧化锌添食育蚕法所获得的高性能蚕丝，将高性能蚕丝进行脱除丝胶，脱除丝胶的具体过程包括以下步骤：A high-performance silk obtained by adding food to silkworms with nano-zinc oxide for preparing high-performance silk. The high-performance 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) cutting the silkworm cocoon to remove the inner silkworm chrysalis;
(2)将蚕茧置于质量百分数为0.6％的Na2CO3水溶液中，煮沸25min，然后用去离子水清洗；(2) Put silkworm cocoons in a 0.6% Na2 CO3 aqueous solution by mass, boil them for 25 minutes, and then wash them with deionized water;
(3)重复第(2)步3次，将脱胶完成的蚕丝悬挂于室内自然风干。高性能蚕丝在脱除丝胶之后单丝的断裂强度为490MPa，断裂伸长率为18％，断裂能为60J/g。高性能蚕丝脱除丝胶之后经光强为1245μW/cm2且波长为390nm的紫外光照射3h后断裂强度无明显损失，对大肠杆菌的抑菌圈大于10mm。(3) Repeat step (2) for 3 times, and hang the degummed silk in the room to dry naturally. After removing the sericin, the high-performance silk has a breaking strength of 490 MPa, a breaking elongation of 18%, and a breaking energy of 60 J/g. After removing the sericin, the high-performance silk has no obvious loss of breaking strength after being irradiated with ultraviolet light with a light intensity of 1245 μW/cm2 and a wavelength of 390 nm for 3 hours, and the inhibition zone against Escherichia coli is greater than 10 mm.
由高性能蚕丝经编织而成蚕丝制品。Silk products are woven from high-performance silk.
实验用蚕饲料的组成如下：The composition of the silkworm feed used in the experiment is as follows:
实施例4Example 4
一种制备高性能蚕丝的纳米氧化锌添食育蚕法，首先制备复合饲料，具体为：A kind of method for raising silkworms by adding food to nano-zinc oxide for preparing high-performance silk, at first preparing compound feed, specifically:
(1)将尺寸范围为40～200nm的纳米氧化锌溶于水中，制成纳米氧化锌溶液；(1) dissolving nano-zinc oxide with a size range of 40 to 200nm in water to make a nano-zinc oxide solution;
(2)先将纳米氧化锌溶液超声18min，使纳米粒子分散均匀，将纳米氧化锌溶液与蚕饲料搅拌均匀，然后放入微波炉中加热5min，微波炉的输出功率为900W，冷却后即制成复合饲料；其中，水的质量为蚕饲料的2倍；(2) Ultrasonic the nano-zinc oxide solution for 18 minutes to disperse the nanoparticles evenly, stir the nano-zinc oxide solution and silkworm feed evenly, then put it into a microwave oven and heat it for 5 minutes. Feed; Wherein, the quality of water is 2 times of silkworm feed;
然后在家蚕人工饲料即蚕饲料中添加纳米氧化锌并喂养蚕，由蚕吸收纳米氧化锌进入丝腺并最终在纺丝过程中将纳米氧化锌结合进入蚕丝，即获得高性能蚕丝；Then add nano-zinc oxide to silkworm artificial feed, that is, silkworm feed, and feed silkworms. The silkworm absorbs nano-zinc oxide and enters the silk gland, and finally combines nano-zinc oxide into silk during the spinning process to obtain high-performance silk;
具体为：蚕在一龄到四龄喂食未添加纳米氧化锌的蚕饲料，五龄第二天开始喂食添加了质量百分数为0.8％纳米氧化锌的复合饲料，直至上蔟结茧，同一批蚕从五龄第二天到上蔟结茧期间，所述复合饲料中，纳米氧化锌的添食浓度保持不变。Specifically: the silkworms were fed the silkworm feed without adding nano-zinc oxide from the first to the fourth instar, and fed the compound feed added with 0.8% nano-zinc oxide on the second day of the fifth instar until the upper cocoons were cocooned. From the second day of the fifth instar to the period of cocooning in the upper bundle, in the compound feed, the concentration of nano-zinc oxide added remained unchanged.
一种制备高性能蚕丝的纳米氧化锌添食育蚕法所获得的高性能蚕丝，将高性能蚕丝进行脱除丝胶，脱除丝胶的具体过程包括以下步骤：A high-performance silk obtained by adding food to silkworms with nano-zinc oxide for preparing high-performance silk. The high-performance 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) cutting the silkworm cocoon to remove the inner silkworm chrysalis;
(2)将蚕茧置于质量百分数为0.8％的Na2CO3水溶液中，煮沸22min，然后用去离子水清洗；(2) Put silkworm cocoons in 0.8% Na2 CO3 aqueous solution, boil them for 22 minutes, and then wash them with deionized water;
(3)重复第(2)步3次，将脱胶完成的蚕丝悬挂于室内自然风干。高性能蚕丝在脱除丝胶之后单丝的断裂强度为400MPa，断裂伸长率为16％，断裂能为37J/g。高性能蚕丝脱除丝胶之后经光强为1245μW/cm2且波长为390nm的紫外光照射3h后断裂强度无明显损失，对大肠杆菌的抑菌圈大于10mm。(3) Repeat step (2) for 3 times, and hang the degummed silk in the room to dry naturally. After removing the sericin, the high-performance silk has a breaking strength of 400 MPa, a breaking elongation of 16%, and a breaking energy of 37 J/g. After removing the sericin, the high-performance silk has no obvious loss of breaking strength after being irradiated with ultraviolet light with a light intensity of 1245 μW/cm2 and a wavelength of 390 nm for 3 hours, and the inhibition zone against Escherichia coli is greater than 10 mm.
由高性能蚕丝经编织而成蚕丝制品。Silk products are woven from high-performance silk.
实验用蚕饲料的组成如下：The composition of the silkworm feed used in the experiment is as follows:
实施例5Example 5
一种制备高性能蚕丝的纳米氧化锌添食育蚕法，首先制备复合饲料，具体为：A kind of method for raising silkworms by adding food to nano-zinc oxide for preparing high-performance silk, at first preparing compound feed, specifically:
(1)将尺寸范围为40～200nm的纳米氧化锌溶于水中，制成纳米氧化锌溶液；(1) dissolving nano-zinc oxide with a size range of 40 to 200nm in water to make a nano-zinc oxide solution;
(2)先将纳米氧化锌溶液超声20min，使纳米粒子分散均匀，将纳米氧化锌溶液与蚕饲料搅拌均匀，然后放入微波炉中加热5min，微波炉的输出功率为900W，冷却后即制成复合饲料；其中，水的质量为蚕饲料的2倍；(2) Ultrasonic the nano-zinc oxide solution for 20 minutes to disperse the nanoparticles evenly, stir the nano-zinc oxide solution and silkworm feed evenly, then put it into a microwave oven and heat it for 5 minutes. Feed; Wherein, the quality of water is 2 times of silkworm feed;
然后在家蚕人工饲料即蚕饲料中添加纳米氧化锌并喂养蚕，由蚕吸收纳米氧化锌进入丝腺并最终在纺丝过程中将纳米氧化锌结合进入蚕丝，即获得高性能蚕丝；Then add nano-zinc oxide to silkworm artificial feed, that is, silkworm feed, and feed silkworms. The silkworm absorbs nano-zinc oxide and enters the silk gland, and finally combines nano-zinc oxide into silk during the spinning process to obtain high-performance silk;
具体为：蚕在一龄到四龄喂食未添加纳米氧化锌的蚕饲料，五龄第二天开始喂食添加了质量百分数为0.9％纳米氧化锌的复合饲料，直至上蔟结茧，同一批蚕从五龄第二天到上蔟结茧期间，所述复合饲料中，纳米氧化锌的添食浓度保持不变。Specifically: the silkworms were fed the silkworm feed without adding nano-zinc oxide from the first to the fourth instar, and fed the compound feed added with 0.9% nano-zinc oxide on the second day of the fifth instar until the upper cocoons were cocooned. From the second day of the fifth instar to the period of cocooning in the upper bundle, in the compound feed, the concentration of nano-zinc oxide added remained unchanged.
一种制备高性能蚕丝的纳米氧化锌添食育蚕法所获得的高性能蚕丝，将高性能蚕丝进行脱除丝胶，脱除丝胶的具体过程包括以下步骤：A high-performance silk obtained by adding food to silkworms with nano-zinc oxide for preparing high-performance silk. The high-performance 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) cutting the silkworm cocoon to remove the inner silkworm chrysalis;
(2)将蚕茧置于质量百分数为0.6％的Na2CO3水溶液中，煮沸21min，然后用去离子水清洗；(2) Put silkworm cocoons in a 0.6% Na2 CO3 aqueous solution by mass, boil them for 21 minutes, and then wash them with deionized water;
(3)重复第(2)步2次，将脱胶完成的蚕丝悬挂于室内自然风干。高性能蚕丝在脱除丝胶之后单丝的断裂强度为420MPa，断裂伸长率为18％，断裂能为43J/g。高性能蚕丝脱除丝胶之后经光强为1245μW/cm2且波长为390nm的紫外光照射3h后断裂强度无明显损失，对大肠杆菌的抑菌圈大于10mm。(3) Repeat step (2) twice, and hang the degummed silk in the room to dry naturally. After removing the sericin, the high-performance silk has a breaking strength of 420 MPa, a breaking elongation of 18%, and a breaking energy of 43 J/g. After removing the sericin, the high-performance silk has no obvious loss of breaking strength after being irradiated with ultraviolet light with a light intensity of 1245 μW/cm2 and a wavelength of 390 nm for 3 hours, and the inhibition zone against Escherichia coli is greater than 10 mm.
由高性能蚕丝经纺织而成蚕丝制品。Silk products are made of high-performance silk by weaving.
实施例6Example 6
一种制备高性能蚕丝的纳米氧化锌添食育蚕法，首先制备复合饲料，具体为：A kind of method for raising silkworms by adding food to nano-zinc oxide for preparing high-performance silk, at first preparing compound feed, specifically:
(1)将尺寸范围为40～200nm的纳米氧化锌溶于水中，制成纳米氧化锌溶液；(1) dissolving nano-zinc oxide with a size range of 40 to 200nm in water to make a nano-zinc oxide solution;
(2)先将纳米氧化锌溶液超声25min，使纳米粒子分散均匀，将纳米氧化锌溶液与蚕饲料搅拌均匀，然后放入微波炉中加热4min，微波炉的输出功率为900W，冷却后即制成复合饲料；其中，水的质量为蚕饲料的2倍；(2) Ultrasonic the nano-zinc oxide solution for 25 minutes to disperse the nanoparticles evenly, stir the nano-zinc oxide solution and silkworm feed evenly, then put it into a microwave oven and heat it for 4 minutes. Feed; Wherein, the quality of water is 2 times of silkworm feed;
然后在家蚕人工饲料即蚕饲料中添加纳米氧化锌并喂养蚕，由蚕吸收纳米氧化锌进入丝腺并最终在纺丝过程中将纳米氧化锌结合进入蚕丝，即获得高性能蚕丝；Then add nano-zinc oxide to silkworm artificial feed, that is, silkworm feed, and feed silkworms. The silkworm absorbs nano-zinc oxide and enters the silk gland, and finally combines nano-zinc oxide into silk during the spinning process to obtain high-performance silk;
具体为：蚕在一龄到四龄喂食未添加纳米氧化锌的蚕饲料，五龄第二天开始喂食添加了质量百分数为1％纳米氧化锌的复合饲料，直至上蔟结茧，同一批蚕从五龄第二天到上蔟结茧期间，所述复合饲料中，纳米氧化锌的添食浓度保持不变。Specifically: the silkworms were fed the silkworm feed without adding nano-zinc oxide from the first to the fourth instar, and fed the compound feed added with 1% nano-zinc oxide on the second day of the fifth instar until the upper cocoons were cocooned. From the second day of the fifth instar to the period of cocooning in the upper bundle, in the compound feed, the concentration of nano-zinc oxide added remained unchanged.
一种制备高性能蚕丝的纳米氧化锌添食育蚕法所获得的高性能蚕丝，将高性能蚕丝进行脱除丝胶，脱除丝胶的具体过程包括以下步骤：A high-performance silk obtained by adding food to silkworms with nano-zinc oxide for preparing high-performance silk. The high-performance 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) cutting the silkworm cocoon to remove the inner silkworm chrysalis;
(2)将蚕茧置于质量百分数为0.5％的Na2CO3水溶液中，煮沸30min，然后用去离子水清洗；(2) Put silkworm cocoons in a 0.5% Na2 CO3 aqueous solution by mass, boil them for 30 minutes, and then wash them with deionized water;
(3)重复第(2)步3次，将脱胶完成的蚕丝悬挂于室内自然风干。高性能蚕丝在脱除丝胶之后单丝的断裂强度为450MPa，断裂伸长率为18％，断裂能为55J/g。高性能蚕丝脱除丝胶之后经光强为1245μW/cm2且波长为390nm的紫外光照射3h后断裂强度无明显损失，对大肠杆菌的抑菌圈大于10mm。(3) Repeat step (2) for 3 times, and hang the degummed silk in the room to dry naturally. After removing the sericin, the high-performance silk has a single filament breaking strength of 450 MPa, a breaking elongation of 18%, and a breaking energy of 55 J/g. After removing the sericin, the high-performance silk has no obvious loss of breaking strength after being irradiated with ultraviolet light with a light intensity of 1245 μW/cm2 and a wavelength of 390 nm for 3 hours, and the inhibition zone against Escherichia coli is greater than 10 mm.
由高性能蚕丝经编织而成蚕丝制品。Silk products are woven from high-performance silk.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510214727.4ACN104872082B (en) | 2015-04-29 | 2015-04-29 | A kind of nano zine oxide for preparing high-performance silk freshens food and educates silkworm method and its product |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510214727.4ACN104872082B (en) | 2015-04-29 | 2015-04-29 | A kind of nano zine oxide for preparing high-performance silk freshens food and educates silkworm method and its product |
| Publication Number | Publication Date |
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| CN104872082Atrue CN104872082A (en) | 2015-09-02 |
| CN104872082B CN104872082B (en) | 2018-05-25 |
| Application Number | Title | Priority Date | Filing Date |
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| CN201510214727.4AActiveCN104872082B (en) | 2015-04-29 | 2015-04-29 | A kind of nano zine oxide for preparing high-performance silk freshens food and educates silkworm method and its product |
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