CN104178733B - Lepidopterous insects wing is carried out to the method for full finned surface, high true to nature, large area microstructure replication - Google Patents
Lepidopterous insects wing is carried out to the method for full finned surface, high true to nature, large area microstructure replication Download PDFInfo
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Abstract
本发明涉及一种对鳞翅目昆虫翅膀进行全翅面、高逼真、大面积微结构复制的方法，包括多角度旋转蒸镀覆形金属膜、选择性化学厚镀制阴模、阴模表面等离子体灰化清除、高精度塑铸复型制阳模等步骤。有益之处：（1）本发明采用多角度旋转蒸镀方法在完整鳞翅目昆虫翅膀表面沉积一层覆形金属膜以便对斜楔形、小倾角鳞翅微结构进行捕捉与固定，充分利用了其晶粒细腻、填充性好、易于覆形等优势，有利于保证后续化学厚镀的高逼真度；（2）本发明采用先捕捉固定微结构再进行化学厚镀的方法，避免了现有电铸制模方法存在的诸多问题，可实现复型阴模板的全翅面、大面积制作。
The invention relates to a method for duplicating the full-wing, high-fidelity, and large-area microstructure of the wings of Lepidoptera insects, including multi-angle rotary evaporation coating metal film, selective chemical thick plating to form a female mold, and the surface of the female mold Plasma ashing and cleaning, high-precision plastic casting replicas and positive mold making steps. Benefits: (1) The present invention uses a multi-angle rotary evaporation method to deposit a layer of metal film on the surface of complete Lepidoptera insect wings so as to capture and fix the oblique wedge-shaped and small-angle scale wing microstructures, making full use of Its advantages such as fine grain, good filling, and easy coating are beneficial to ensure the high fidelity of the subsequent chemical thick plating; (2) the present invention adopts the method of first capturing and fixing the microstructure and then performing chemical thick plating, which avoids the existing There are many problems in the electroforming method, and the full-wing and large-area production of the replica negative template can be realized.
Description
技术领域 technical field
本发明涉及一种对昆虫翅膀复杂微细结构进行大面积、高逼真复制的方法，更特别地说，是指对鳞翅目昆虫翅膀进行全翅面、高逼真、大面积微结构复制的方法，属于仿生制造技术领域。 The invention relates to a method for large-area and high-fidelity replication of the complex microstructure of insect wings, more particularly, a method for replicating the full-surface, high-fidelity, and large-area microstructure of the wings of Lepidoptera insects. It belongs to the technical field of bionic manufacturing.
背景技术 Background technique
鳞翅目是昆虫纲中仅次于鞘翅目的第二大目，包括各种蝴蝶和蛾类，有约40个以上的总科、120个以上的科及超过18万种的种类。鳞翅目昆虫翅膀上的颜色分为化学色和物理色，其中物理色亦称结构色，是指由微结构本身的光特性所呈现出的带有各向异性的色彩。大多数鳞翅目昆虫的翅膀均由半透明的膜和覆于其上的若干细小鳞片构成，鳞片表面由微米及亚微米级的沟槽、肋片及孔洞等微结构构成。当前，对具有化学色或物理色的鳞翅目昆虫翅膀进行微结构复制在光子器件制造、吸波吸声材料制造、光伪装材料制造等领域具有重要的潜在应用价值。例如，申请号为20121024412.1的中国专利公开了一种基于蝴蝶翅膀单个鳞片生物模板制备磁性光子晶体的方法，申请号为201410127205.6的中国专利公开了一种直接由薄脆型生物表面反向电铸出仿生复型表面的方法。 Lepidoptera is the second largest order in Insecta after Coleoptera, including various butterflies and moths, with more than 40 superfamilies, more than 120 families and more than 180,000 species. The colors on the wings of Lepidoptera insects are divided into chemical colors and physical colors. Physical colors are also called structural colors, which refer to the anisotropic colors presented by the light characteristics of the microstructure itself. The wings of most Lepidoptera insects are composed of a translucent membrane and a number of tiny scales covering it. The surface of the scales is composed of microstructures such as micron and submicron grooves, ribs and holes. At present, the microstructure replication of Lepidoptera insect wings with chemical or physical colors has important potential application value in the fields of photonic device manufacturing, wave-absorbing and sound-absorbing materials manufacturing, and optical camouflage materials manufacturing. For example, the Chinese patent application number 20121024412.1 discloses a method for preparing magnetic photonic crystals based on a single scale biotemplate of a butterfly wing, and the Chinese patent application number 201410127205.6 discloses a method of reverse electroforming bionic crystals directly from a thin and brittle biological surface. Methods for replicating surfaces.
然而，上述专利成果尽管在蝴蝶翅膀微结构复制方面提供了一定的参考价值，但仅限于对单个蝴蝶鳞片或小面积生物样本进行微结构复制，并未解决全翅面、高逼真、大面积微结构复制的问题，而上述问题的解决将有助于推动与鳞翅目昆虫翅膀相关的仿生器件或功能材料实现规模化、工业化生产制造。 However, although the above-mentioned patent achievements provide a certain reference value in the microstructure replication of butterfly wings, they are only limited to the microstructure replication of a single butterfly scale or small-area biological samples, and do not solve the problem of full-wing, high-fidelity, large-area microstructure. The problem of structural replication, and the solution of the above problems will help to promote the large-scale and industrial production of bionic devices or functional materials related to the wings of Lepidoptera insects.
发明内容 Contents of the invention
本发明的目的在于，提供一种对鳞翅目昆虫翅膀进行全翅面、高逼真、大面积微结构复制的方法，以解决上述技术问题。 The object of the present invention is to provide a method for duplicating the full wing surface, high fidelity and large-area microstructure of the wings of Lepidoptera insects, so as to solve the above technical problems.
本发明所解决的技术问题采用以下技术方案来实现：对鳞翅目昆虫翅膀进行全翅面、高逼真、大面积微结构复制的方法，包括如下步骤。 The technical problem solved by the present invention is realized by the following technical solutions: the method for duplicating the full-wing, high-fidelity, and large-area microstructure of the wings of Lepidoptera insects includes the following steps.
第一步：鳞翅目昆虫翅膀气吹清洁及全翅面粘贴固定 Step 1: Air-blow cleaning of Lepidoptera insect wings and pasting and fixing of the whole wing surface
裁选翅面完整、无破损的新鲜鳞翅目成虫翅膀作为复制用生物模板，先用气吹球轻轻吹去其表面浮尘，再用防水胶带沿翅膀外缘轮廓将其粘贴固定于玻璃基片上，制得全翅面粘固生物模板。 Fresh adult Lepidoptera wings with complete and undamaged wings were selected as biological templates for replication, and the floating dust on the surface was gently blown off with an air blower, and then pasted and fixed on the glass substrate along the outer edge of the wings with waterproof tape. On the chip, a full-wing surface-bonded biological template was prepared.
第二步：全翅面粘固生物模板多角度旋转蒸镀覆形金属膜 The second step: multi-angle rotary evaporation coating metal film on the whole wing surface of the cemented biological template
（A）将第一步制得的全翅面粘固生物模板固定于真空蒸镀室内的基片夹具上，调整样品转轴与水平面的初始夹角处于小角度范围，以细晶粒金属作为蒸发源并保持2rps的样品转速在全翅面粘固生物模板表面蒸镀一层厚度为250nm～300nm的覆形金属膜； (A) Fix the full-winged biological template prepared in the first step on the substrate fixture in the vacuum evaporation chamber, adjust the initial angle between the sample rotation axis and the horizontal plane in a small angle range, and use fine-grained metal as the evaporation Source and maintain the sample rotation speed of 2rps to vapor-deposit a layer of metal film with a thickness of 250nm to 300nm on the surface of the full-wing cemented biological template;
（B）进一步调整样品转轴与水平面的二次夹角处于15°～20°范围内，保持2rps的样品转速在经（A）步骤蒸镀后的全翅面粘固生物模板表面再蒸镀一层厚度为300nm～350nm的同质覆形金属膜。 (B) Further adjust the secondary angle between the sample rotation axis and the horizontal plane within the range of 15° to 20°, and keep the sample rotation speed of 2rps on the surface of the full-winged biological template after evaporation in (A) and then vapor-deposit one Homogeneous covering metal film with a layer thickness of 300nm-350nm.
第三步：全翅面粘固生物模板选择性化学厚镀制阴模 Step 3: Selective electroless thick plating of biological templates on the whole wing surface to make negative molds
（A）将质量分数为10％的硫化纳水溶液混合到普通绝缘漆中制得具有催化毒性的绝缘漆，然后用该漆对第二步蒸镀有覆形金属膜的全翅面粘固生物模板进行局部绝缘涂覆，以保证除完整翅面之外的其他部位不能发生后续化学镀过程； (A) Mix the aqueous solution of sodium sulfide with a mass fraction of 10% into ordinary insulating varnish to prepare a catalytically toxic insulating varnish, and then use this varnish to treat the whole wing surface of the second-step vapor-deposited metal film. Partial insulation coating is carried out on the template to ensure that the subsequent electroless plating process cannot occur on other parts except the complete fin surface;
（B）对经（A）步骤局部绝缘后的全翅面粘固生物模板进行活化预处理，并按所述覆形金属膜的同质金属体系配置化学镀液，然后在一定温度及酸碱度条件下对活化后全翅面粘固生物模板进行化学厚镀； (B) Activation pretreatment is performed on the full-wing surface-bonded biological template after partial insulation in step (A), and the electroless plating solution is configured according to the homogeneous metal system of the covered metal film, and then under certain temperature and pH conditions Under the following conditions, chemical thick plating is performed on the activated full-wing surface-bonded biological template;
（C）当经（B）步骤在全翅面粘固生物模板上覆形金属膜外表面沉积一定厚度的同质金属镀层后停止化学厚镀，取出镀件并用去离子水冲洗4～7次，进而揭除防水胶带和玻璃基片，制得全翅面复型阴模。 (C) After step (B) deposits a certain thickness of homogeneous metal coating on the outer surface of the overlying metal film on the full-winged biological template, stop the chemical thick plating, take out the plated part and rinse it with deionized water for 4 to 7 times , and then remove the waterproof tape and the glass substrate, and make the negative mold of the full wing surface replica.
第四步：阴模表面鳞翅目昆虫翅膀等离子体灰化清除 Step 4: Plasma ashing and cleaning of Lepidoptera insect wings on the surface of the female mold
以氧气作为工艺气体，利用等离子体清洗机对第三步制得的全翅面复型阴模进行若干时间的氧等离子体低温灰化处理，以清除全翅面复型阴模上粘连的生物原型组织，进而完整地暴露出阴模微结构。 Using oxygen as the process gas, use a plasma cleaning machine to perform oxygen plasma low-temperature ashing treatment on the full-wing surface replica negative mold prepared in the third step for a certain period of time, so as to remove the sticky organisms on the full-wing surface replica negative mold. Prototype tissue, and then fully expose the microstructure of the female mold.
第五步：高分子预聚体高精度塑铸复型制阳模 Step 5: High-precision plastic casting of polymer prepolymer to make positive mold
选择具有较高复型精度的复型高聚物作为复型材料，先按比例配置其高分子预聚体，进而在浇铸型腔内对第四步灰化处理后的全翅面复型阴模进行塑铸复型，经除气、固化后脱模便制得全翅面复型阳模，最终完成对鳞翅目昆虫翅膀的全翅面、高逼真、大面积微结构复制。 Select the replica high polymer with high replica precision as the replica material, first configure its polymer prepolymer in proportion, and then in the casting cavity, the full-fin replica after the fourth step of ashing treatment is cast. After degassing and curing, the full-wing surface replica positive mold is obtained after demoulding, and finally completes the full-wing surface, high-fidelity, and large-area microstructure replication of Lepidoptera insect wings.
所述样品转轴与水平面的初始夹角为5°～10°。 The initial included angle between the sample rotation axis and the horizontal plane is 5°-10°.
所述细晶粒金属是镍、铝、铜、铬。 The fine grained metals are nickel, aluminum, copper, chromium.
所述复型高聚物是聚二甲基硅氧烷、聚乙烯醇。 The complex polymer is polydimethylsiloxane and polyvinyl alcohol.
本发明的有益之处：（1）本发明采用多角度旋转蒸镀方法在完整鳞翅目昆虫翅膀表面沉积一层覆形金属膜以便对斜楔形、小倾角鳞翅微结构进行捕捉与固定，充分利用了其晶粒细腻、填充性好、易于覆形等优势，有利于保证后续化学厚镀的高逼真度；（2）本发明采用先捕捉固定微结构再进行化学厚镀以制作复型阴模板的方法，有效避免了现有电铸制模方法存在的电铸液易扰动破坏镀膜鳞翅导电性进而导致不能大面积制模甚至电铸失败的问题，可以实现复型阴模板的全翅面、大面积制作。 The benefits of the present invention: (1) The present invention uses a multi-angle rotary evaporation method to deposit a layer of metal film on the surface of the complete Lepidoptera insect wings so as to capture and fix the oblique wedge-shaped and small-angle scale wing microstructures, It makes full use of the advantages of its fine grain, good filling, and easy coating, which is beneficial to ensure the high fidelity of the subsequent chemical thick plating; (2) the present invention first captures and fixes the microstructure and then performs chemical thick plating to make replicas The method of the negative template effectively avoids the problem that the electroforming liquid is easily disturbed and destroys the conductivity of the coating fins in the existing electroforming method, which leads to the failure of large-area molding or even the failure of electroforming, and can realize the full replica of the negative template. Wing surface, large area production.
附图说明 Description of drawings
图1为本发明的对鳞翅目昆虫翅膀进行全翅面、高逼真、大面积微结构复制的方法 Fig. 1 is the method for carrying out whole wing surface, high fidelity, large area microstructure replication to Lepidoptera insect wing of the present invention
流程图。 flow chart.
图2为本发明实施例提供的蓝凤蝶翅膀鳞片微结构扫描电镜照片（放大1000倍）。 Fig. 2 is a scanning electron micrograph (1000 times magnification) of the microstructure of the wing scales of the blue swallowtail butterfly provided by the embodiment of the present invention.
图3为全翅面粘固生物模板在真空蒸镀室内的安装示意图。 Fig. 3 is a schematic diagram of the installation of the full-wing surface-bonded biological template in the vacuum evaporation chamber.
图4为多角度旋转真空蒸镀覆形金属膜后生物模板上各微结构示意图。 Fig. 4 is a schematic diagram of microstructures on the bio-template after multi-angle rotation and vacuum evaporation of the metal film.
图5为对全翅面粘固生物模板进行镀前局部绝缘涂覆的示意图。 Fig. 5 is a schematic diagram of partial insulation coating before plating on the whole wing-fixed biological template.
图6为结束化学厚镀并揭除防水胶带和玻璃基片后生物模板上各微结构示意图。 Fig. 6 is a schematic diagram of each microstructure on the biological template after the chemical thick plating is finished and the waterproof tape and the glass substrate are removed.
图7为等离子体灰化清除生物模板后所得全翅面复型阴模上各微结构示意图。 Fig. 7 is a schematic diagram of the microstructures on the full-wing replica negative mold obtained after plasma ashing to remove the biological template.
图中：1、真空蒸镀室2、样品转轴3、基片夹具4、全翅面粘固生物模板5、金属蒸气6、蒸发源7、翅膜8、鳞片9、覆形金属膜10、玻璃基片11、生物模板12、防水胶带13、绝缘漆面14、化学厚镀层15、鳞片阴模。 In the figure: 1. Vacuum evaporation chamber 2. Sample shaft 3. Substrate fixture 4. Biological template glued to the whole wing surface 5. Metal vapor 6. Evaporation source 7. Wing film 8. Scales 9. Metal film covering 10. Glass substrate 11, biological template 12, waterproof tape 13, insulating paint surface 14, chemical thick coating 15, scale negative mold.
具体实施方式 detailed description
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合附图和具体实施例进一步阐述本发明。 In order to make the technical means, creative features, goals and effects achieved by the present invention easy to understand, the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
按照图1所示流程对美洲蓝凤蝶（pipevineswallowtail）翅膀进行全翅面、高逼真、大面积微结构复制。参照图2，蓝凤蝶翅膀上具有规则排列的细小鳞片，且每个鳞片上具有沟槽状微结构。 According to the process shown in Figure 1, the full-wing, high-fidelity, and large-area microstructure replication of the American blue swallowtail butterfly ( pipevine swallowtail ) wing was carried out. Referring to Figure 2, there are regularly arranged fine scales on the wings of the blue swallowtail butterfly, and each scale has a groove-like microstructure.
第一步：蓝凤蝶翅膀气吹清洁及全翅面粘贴固定 Step 1: Cleaning the wings of the blue swallowtail butterfly with air blowing and pasting and fixing the whole wing surface
参照图5，裁选翅面完整、无破损的新鲜蓝凤蝶成虫翅膀作为复制用生物模板11，先用气吹球轻轻吹去其表面浮尘，再用防水胶带12沿翅膀外缘轮廓将其粘贴固定于玻璃基片10上，使翅面无皱褶并尽量贴合玻璃基片10，制得全翅面粘固生物模板4。 With reference to Fig. 5, the fresh blue swallowtail butterfly adult wing with complete wing surface and no damage is selected as the biological template 11 for replication, and the floating dust on its surface is gently blown off with an air blowing ball first, and then the waterproof tape 12 is used to wrap the wing along the outer edge of the wing. It is pasted and fixed on the glass substrate 10, so that the wing surface has no wrinkles and fits the glass substrate 10 as much as possible, and the biological template 4 is obtained by sticking the whole wing surface.
第二步：全翅面粘固生物模板多角度旋转蒸镀覆形金属膜 The second step: multi-angle rotary evaporation coating metal film on the whole wing surface of the cemented biological template
（A）参照图3、图4、图5，将第一步制得的全翅面粘固生物模板4固定于真空蒸镀室1内的基片夹具3上，考虑到美洲蓝凤蝶翅膀上鳞片8的倾角约为5°，为保证蒸镀过程中由下部蒸发源6发出的金属蒸气5能尽可能多的进入到鳞片8底部并兼顾鳞上镀膜，可调整样品转轴2与水平面的初始夹角为9°；以细晶粒金属镍丝作为蒸发源6并保持2rps的样品转速在全翅面粘固生物模板4表面蒸镀一层厚度为300nm的覆形金属膜9； (A) Referring to Fig. 3, Fig. 4, and Fig. 5, the full-wing surface-bonded biological template 4 prepared in the first step is fixed on the substrate holder 3 in the vacuum evaporation chamber 1, considering that the wings of the American blue swallowtail butterfly The inclination angle of the upper scale 8 is about 5°. In order to ensure that the metal vapor 5 emitted by the lower evaporation source 6 can enter the bottom of the scale 8 as much as possible during the evaporation process and take into account the coating on the scale, the distance between the sample rotating shaft 2 and the horizontal plane can be adjusted. The initial included angle is 9°; fine-grain metal nickel wire is used as the evaporation source 6 and a sample rotation speed of 2rps is maintained to vapor-deposit a layer of 300nm-thick metal film 9 on the surface of the bio-template 4 with a thickness of 300nm;
（B）参照图3、图4，进一步调整样品转轴2与水平面的二次夹角为20°，保持2rps的样品转速在经（A）步骤蒸镀后的全翅面粘固生物模板4表面再蒸镀一层厚度为300nm的镍质覆形金属膜9。 (B) Referring to Figure 3 and Figure 4, further adjust the secondary angle between the sample rotating shaft 2 and the horizontal plane to be 20°, and keep the sample rotation speed of 2rps on the surface of the full-winged bio-template 4 after evaporation in step (A) A layer of nickel clad metal film 9 with a thickness of 300nm is vapor-deposited.
第三步：全翅面粘固生物模板选择性化学厚镀制阴模 Step 3: Selective electroless thick plating of biological templates on the whole wing surface to make negative molds
（A）参照图5，将质量分数为10％的硫化纳水溶液混合到普通绝缘漆中制得具有催化毒性的绝缘漆，然后用该漆对第二步蒸镀有覆形金属膜9的全翅面粘固生物模板4局部涂覆绝缘漆面13，以保证除完整翅面之外的其他部位不能发生后续化学镀过程； (A) Referring to Figure 5, mix the aqueous solution of sodium sulfide with a mass fraction of 10% into ordinary insulating varnish to prepare a catalytically toxic insulating varnish, and then use this varnish to coat the entire surface with the metal film 9 vapor-deposited in the second step. Wing surface sticking biological template 4 is partially coated with insulating paint surface 13, so as to ensure that the subsequent electroless plating process cannot occur on other parts except the complete wing surface;
（B）对经（A）步骤局部绝缘后的全翅面粘固生物模板4进行活化预处理，并按标准酸性镀镍配方配置化学镀镍溶液，然后在温度为85℃、pH值为4.5条件下对活化后全翅面粘固生物模板4进行化学厚镀； (B) Pre-activate the whole-wing surface-bonded bio-template 4 after partial insulation in step (A), and prepare an electroless nickel plating solution according to the standard acidic nickel plating formula, and then heat it at a temperature of 85°C and a pH value of 4.5 Perform chemical thick plating on the bio-template 4 bonded to the whole wing surface after activation under certain conditions;
（C）参照图6，当经（B）步骤在全翅面粘固生物模板4上覆形金属膜9的外表面沉积出厚度为0.2mm的镍质化学厚镀层14后停止化学厚镀，取出镀件并用去离子水冲洗7次，进而揭除防水胶带12和玻璃基片10，制得全翅面复型阴模。 (C) Referring to FIG. 6 , stop electroless thick plating after depositing a nickel chemical thick plating layer 14 with a thickness of 0.2 mm on the outer surface of the overlying metal film 9 on the full-wing surface of the biological template 4 through the step (B), The plated part was taken out and rinsed 7 times with deionized water, and then the waterproof adhesive tape 12 and the glass substrate 10 were removed to obtain a full-wing replica negative mold.
第四步：阴模表面鳞翅目昆虫翅膀等离子体灰化清除 Step 4: Plasma ashing and cleaning of Lepidoptera insect wings on the surface of the female mold
参照图7，以氧气作为工艺气体，在氧气流量为300sccm、功率为350W条件下利用等离子体清洗机对第三步制得的全翅面复型阴模进行40min的氧等离子体低温灰化处理，以清除全翅面复型阴模上粘连的翅膜7、鳞片8等生物原型组织，进而完整地暴露出鳞片阴模15等微结构。 Referring to Fig. 7, with oxygen as the process gas, under the conditions of oxygen flow rate of 300 sccm and power of 350 W, the full fin surface replica negative mold obtained in the third step is subjected to oxygen plasma low-temperature ashing treatment for 40 minutes by using a plasma cleaning machine , to remove the biological prototype tissues such as wing membrane 7 and scales 8 adhered on the full-wing surface replica female model, and then completely expose the microstructures such as the scale female model 15 .
第五步：高分子预聚体高精度塑铸复型制阳模 Step 5: High-precision plastic casting of polymer prepolymer to make positive mold
选择具有较高复型精度的复型高聚物聚二甲基硅氧烷作为复型材料，先将预聚物Sylgard184与固化剂按10:1的比例配置其高分子预聚体，进而在浇铸型腔内对第四步灰化处理后的全翅面复型阴模进行塑铸复型，经真空除气3min、常温固化24h后脱模便制得全翅面复型阳模，最终完成对蓝凤蝶翅膀的全翅面、高逼真、大面积微结构复制。 Select the replicating polymer polydimethylsiloxane with high replicating precision as the replicating material. In the casting cavity, the full-wing surface replica negative mold after the fourth step of ashing treatment is plastic-cast and replicated. After vacuum degassing for 3 minutes and room temperature curing for 24 hours, the full-wing surface replica male mold is obtained after demoulding. Finally, Complete the full-wing, high-fidelity, large-area microstructure replication of the blue swallowtail butterfly's wings.
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。 The basic principles and main features of the present invention and the advantages of the present invention have been shown and described above. Those skilled in the industry should understand that the present invention is not limited by the above-mentioned embodiments. What are described in the above-mentioned embodiments and the description only illustrate the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will also have Variations and improvements all fall within the scope of the claimed invention. The protection scope of the present invention is defined by the appended claims and their equivalents.
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