WO2023217065A1 - 电热刺激形状记忆fpc电磁屏蔽膜的制备方法 - Google Patents

电热刺激形状记忆fpc电磁屏蔽膜的制备方法 Download PDF

Info

Publication number
WO2023217065A1
WO2023217065A1 PCT/CN2023/092678 CN2023092678W WO2023217065A1 WO 2023217065 A1 WO2023217065 A1 WO 2023217065A1 CN 2023092678 W CN2023092678 W CN 2023092678W WO 2023217065 A1 WO2023217065 A1 WO 2023217065A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
electromagnetic shielding
shape memory
fiber membrane
shielding film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2023/092678
Other languages
English (en)
French (fr)
Inventor
李文兵
魏婉婷
刘均澔
曹丰
钱坤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangnan University
Original Assignee
Jiangnan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangnan University filed Critical Jiangnan University
Publication of WO2023217065A1 publication Critical patent/WO2023217065A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]

Definitions

  • the invention relates to a preparation method of electrothermal stimulation shape memory FPC electromagnetic shielding film, and belongs to the field of polymer science and technology.
  • 5G foldable mobile phones have ultra-high data transmission rates, large portable screens and expensive prices, and deserve to be the leader in smartphones.
  • FPC flexible circuit boards
  • electromagnetic shielding film provides a solution for electromagnetic shielding of FPC and has good application effects.
  • the polymer-based conductive composite fiber membrane has outstanding advantages such as thinness, high flexibility, strong durability, high conductivity, high electromagnetic interference shielding efficiency and wide shielding band, and is expected to become a new generation of high-performance electromagnetic interference (EMI) shielding materials.
  • EMI electromagnetic interference
  • the flexible composite electromagnetic shielding film constructed of conductive nanofibers in the patent CN113265908 achieves the shielding of electromagnetic waves by the flexible self-supporting conductive nanofiber film.
  • it requires subsequent processing to fit FPCs of various sizes, and when the mobile phone is scrapped When recycled, the shielding film will inevitably be scrapped.
  • the first object of the present invention is to provide a method for preparing an electrothermal stimulation shape memory FPC electromagnetic shielding film. The steps are:
  • EVA ethylene-vinyl acetate copolymer
  • the electrospinning of step (1) prepares an EVA fiber membrane by mixing ethylene-vinyl acetate copolymer (EVA) particles, benzophenone (BP) powder and triallyl isocyanate Urea ester (TAIC) is mixed and dissolved in a mixed solvent of toluene and N,N-dimethylformamide (DMF) to obtain a uniform spinning liquid, and then the uniform spinning liquid is transferred to a syringe for electrostatic spinning to prepare electrostatic Spun EVA fiber membrane.
  • EVA ethylene-vinyl acetate copolymer
  • BP benzophenone
  • TAIC triallyl isocyanate Urea ester
  • the ultraviolet light curing in step (1) is to place the electrospun EVA fiber membrane under 365nm ultraviolet light for 1 hour.
  • the mass ratio of EVA particles, BP powder and TAIC in the electrospinning solution of step (1) is 100:2-5:1-3, and the preferred mass ratio is 100: 3:1.
  • the VA of the EVA particles accounts for 20wt% to 30wt%, and preferably the VA of the EVA particles accounts for 25wt%.
  • the volume ratio of toluene and DMF in the electrospinning spinning solution of step (1) is 2 to 3:1, and the preferred volume ratio is 7:3.
  • the mass concentration of EVA in the electrospinning solution of step (1) is 8wt% ⁇ 15wt%, and the preferred mass concentration of EVA in the spinning solution is 10wt% ⁇ 12wt%.
  • the optimal mass concentration of EVA in the spinning solution is 10wt%.
  • the voltage of electrospinning in step (1) is 15-18kV, the preferred voltage is 16 ⁇ 0.5kV, and the optimal voltage is 16kV.
  • step (1) the specific steps of preparing EVA fiber membrane by electrospinning in step (1) are:
  • the dopamine solution in step (2) is a mixture of dopamine hydrochloride and trishydroxymethylcarbamate.
  • Alkane (Tris) was mixed and dissolved in deionized water.
  • the dopamine solution in step (2) is prepared by dissolving dopamine hydrochloride in deionized water to form a dopamine solution, and adding Tris to adjust the pH to 8.5-9.5.
  • the dopamine concentration in the dopamine solution of step (2) is 2-5g/L, the preferred dopamine concentration is 2-3g/L, and the optimal dopamine concentration is 2g/L.
  • the time for the EVA fiber membrane to be immersed in the dopamine solution in step (2) is 20 to 25 hours.
  • step (2) the reacted fiber membrane also needs to be moved to deionized water and ultrasonicated for 1 to 5 minutes.
  • the silver ammonia solution in step (3) is obtained by dissolving AgNO 3 crystals in water to obtain an AgNO 3 solution. Under continuous stirring, ammonia water is slowly dripped into the AgNO 3 solution until the solution becomes clear. .
  • the AgNO 3 solution concentration in step (3) is 9 to 11 g/L, and the preferred AgNO 3 solution concentration is 9 to 10 g/L.
  • the silver ammonia solution in step (3) is specifically to dissolve 1gAgNO 3 crystals in 100 ml of deionized water to obtain a homogeneous AgNO 3 solution. Under continuous stirring, add AgNO 3 with a concentration of 10g/L. Slowly drip ammonia solution with a concentration of 25% into the solution until the solution becomes clear.
  • the reaction temperature in step (3) is 30-50°C.
  • the stirring time in step (3) is 20 to 40 minutes, and the optimal stirring time is 30 minutes.
  • the concentration of the glucose solution in step (3) is 15-25g/L.
  • the concentration ratio of the AgNO 3 solution and the glucose solution in step (3) is 1:1 to 2, and the volume ratio is 1:1.
  • the reaction of step (3) is to slowly drop the glucose solution into the silver ammonia solution, conduct it in an ultrasonic environment for 3 minutes, and then conduct it with magnetic stirring at 40°C for 2 hours.
  • the present invention uses the above method to prepare an electrical/thermal stimulation shape memory FPC electromagnetic shielding film.
  • the second object of the present invention is to apply the above-mentioned electrical/thermal stimulation shape memory FPC electromagnetic shielding film to the field of electronic equipment manufacturing.
  • the shape memory polymer fiber membrane prepared by electrospinning also has high porosity and large specific surface area, which can provide enough space for multiple reflections of incident electromagnetic waves and is flexible.
  • Ideal matrix for EMI shielding materials
  • the chemical silver plating process can be used to firmly modify the dense and uniform silver layer on the surface of the polymer fiber, giving the composite fiber high electrical conductivity and strong EMI shielding ability;
  • the FPC electromagnetic shielding film prepared by the present invention can not only deform freely according to the size of the FPC, but also can completely adhere to the densely arranged uneven or staggered electronic components on the FPC. At the same time, its Electromagnetic interference shielding effectiveness remains at a relatively high level;
  • thermal stimulation of the fiber membrane can restore its shape and electromagnetic interference shielding effectiveness, making it highly recyclable.
  • Figure 1 is a schematic diagram of the preparation method of the FPC electromagnetic shielding film with electrical/thermal stimulation shape memory effect of the present invention.
  • Figure 2 shows the thermally induced shape memory effect of EVA fiber membrane.
  • Figure 3 shows the thermally induced shape memory effect of the FPC electromagnetic shielding film prepared in Example 1.
  • Figure 4 is the electromagnetic shape memory effect of the FPC electromagnetic shielding film prepared in Example 1.
  • a is the shape fixation rate (R f ) and shape recovery of the FPC electromagnetic shielding film prepared in Example 1 in the electric response stretching shape memory behavior.
  • b is the electrical response stretching shape memory behavior of the FPC electromagnetic shielding film prepared in Example 1;
  • c is the R f and R in the electrical response pressing shape memory behavior of the FPC electromagnetic shielding film prepared in Example 1 r ;
  • d is the electrical response to pressing shape memory behavior of the FPC electromagnetic shielding film prepared in Example 1.
  • Figure 5 is the conductivity of the FPC electromagnetic shielding film prepared in Example 1 during the shape memory process.
  • FIG 6 shows the electromagnetic interference shielding effectiveness (EMI SE) of the FPC electromagnetic shielding film prepared in Example 1 during the shape memory process.
  • EMI SE electromagnetic interference shielding effectiveness
  • Figure 7 is a schematic diagram of the EMI shielding mechanism of FPC electromagnetic shielding film.
  • Figure 8 is a schematic diagram of the practical application of FPC electromagnetic shielding film.
  • the original electrothermal stimulation shape memory FPC electromagnetic shielding film is stretched to the size of FPC at 0.55V.
  • the stretched electrothermal stimulation shape memory FPC electromagnetic shielding film is stretched at 0.55V.
  • the shape memory FPC electromagnetic shielding film is driven to return to its original shape at 80°C by the cooled electrothermal stimulus that is pressed to closely adhere to the densely laid out electronic components.
  • the electrical/thermal stimulation shape memory process of FPC electromagnetic shielding film is as follows: (1) Test the conductivity and EMI SE of the initial FPC electromagnetic shielding film. (2) Apply a voltage of 0.55V to the initial sample, stretch the sample, turn off the power, and remove the external force. The deformed sample can be obtained and its conductivity and EMI SE can be tested. (3) Under stress-free conditions, apply a high temperature of 80°C to the deformed sample to obtain a recovered sample, and test its conductivity and EMI SE.
  • EMI SE Measurement of electrothermal stimulation shape memory FPC electromagnetic shielding film using vector network analyzer.
  • the EVA particles used in the following examples were purchased from Aladdin, with a VA content of 25wt% and a melt index of 19g/10min.
  • Figure 1 is a schematic diagram of the preparation method of the FPC electromagnetic shielding film of the present invention.
  • the sequence of preparation process steps includes:
  • the prepared electrothermal stimulation shape memory FPC electromagnetic shielding film has excellent shape memory effect, R f is 99%, R r is 97%, and electromagnetic shielding performance is also excellent, with EMI SE of 87.71dB.
  • Example 1 only the spinning voltage of 4 in step (1) was changed to 16kV, 17kV and 18kV, and the other conditions remained unchanged, to prepare an electrothermal stimulation shape memory FPC electromagnetic shielding film.
  • Example 1 change the concentrations of the AgNO 3 solution and glucose solution in step (3) according to Table 2, and keep the other conditions unchanged, to prepare an electrothermal stimulation shape memory FPC electromagnetic shielding film.
  • Table 3 Performance comparison table of electrothermal stimulation shape memory FPC electromagnetic shielding films prepared using different hot pressing temperatures.
  • step (1) the ultraviolet curing in step (5) in step (1) is omitted, and the other conditions remain unchanged, to prepare an electrothermal stimulation shape memory FPC electromagnetic shielding film.
  • the electromagnetic shielding performance of the prepared electrothermal stimulation shape memory FPC electromagnetic shielding film was not affected, but the shape memory effect decreased, with R f being 92% and R r being 80%.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

一种电热刺激形状记忆FPC电磁屏蔽膜的制备方法，属于高分子科学技术领域。先利用静电纺丝和紫外光固化制备EVA纤维膜，固化后浸入多巴胺溶液，表面沉积聚多巴胺薄膜的纤维膜放入银氨溶液，再加入葡萄糖溶液反应，反应结束后干燥即得电热刺激形状记忆FPC电磁屏蔽膜。所制备的FPC电磁屏蔽膜具有超高电导率、超强EMI SE以及电/热刺激形状记忆效应。综合表现为FPC电磁屏蔽膜可在电刺激下根据FPC的大小自由变形并完全贴紧稠密布局的电子元器件，与此同时，仍可保持稳定的高EMI SE；当手机废弃回收时，通过热刺激驱动形状记忆聚合物基导电复合纤维膜的形状回复以及EMI SE恢复，具有较强回收再利用性。

Description

一种电热刺激形状记忆FPC电磁屏蔽膜的制备方法 技术领域
本发明涉及一种电热刺激形状记忆FPC电磁屏蔽膜的制备方法，属于高分子科学技术领域。
背景技术
目前我国3C数码类产品回收市场规模已经突破了千亿元，有些废旧手机损坏严重，失去了维修价值，但手机当中的零件还有拆解的必要，他们会被拆解成主板、屏幕、电池、摄像头、内存等等。现阶段我国每年电子废物处理量已经达到但8000万吨左右，但规范回收率还不到20％，而欧洲已经达到了42.5％，而在手机这个分类上，回收率更是骤降到2％。
报废手机的低成本循环利用，是目前尚未解决的难题，影响了行业整体发展，提升手机零件的可回收再利用性能，不仅促进回收行业的发展，还避免了资源浪费和环境破坏。
5G折叠手机拥有超高的数据传输速率、超大的便携屏幕和昂贵的价格，当之无愧地成为智能手机的领头者。然而当其处于复杂的电磁环境时，不可避免地会受到内部及外部柔性电路板(FPC)上电子元器件的电磁干扰，造成信号衰减，使得信号传输不完整。
电磁屏蔽膜的出现，为FPC的电磁屏蔽提供了解决方案，具有良好的应用效果。聚合物基导电复合纤维膜具有轻薄化、高柔韧性、强耐久性、高导电性、高电磁干扰屏蔽效能和宽屏蔽带等突出优势，有望成为新一代高性能电磁干扰(EMI)屏蔽材料。比如，专利CN113265908中利用导电纳米纤维构筑的柔性复合电磁屏蔽薄膜，实现了柔性自支撑导电纳米纤维薄膜对电磁波的屏蔽，但其还需要后续加工才能贴合各种大小的FPC，而且当手机报废回收时，该屏蔽膜会不可避免地产生报废。
现有的FPC电磁屏蔽膜设计之初，只考虑到生产和应用，并没有考虑到回收环节，例如容易拆解和循环利用，以实现电子垃圾的低成本循环利用。
发明内容
为了解决上述问题，本发明第一个目的是提供了一种电热刺激形状记忆FPC电磁屏蔽膜的制备方法，步骤为：
(1)静电纺丝和紫外光固化制备乙烯-醋酸乙烯共聚物(EVA)纤维膜；
(2)将EVA纤维膜浸入多巴胺溶液反应，反应结束后，去除EVA纤维膜表面过量的聚多巴胺微球，得到表面沉积聚多巴胺薄膜的EVA纤维膜；
(3)表面沉积聚多巴胺薄膜的纤维膜浸入银氨溶液，搅拌，并滴加葡萄糖溶液反应，反 应结束后，洗涤干燥，即得到具有电热刺激形状记忆效应的FPC电磁屏蔽膜。
在本发明一种实施方式中，步骤(1)的静电纺丝制备EVA纤维膜，是将乙烯-醋酸乙烯共聚物(EVA)颗粒、二苯甲酮(BP)粉末和三烯丙基异氰脲酸酯(TAIC)混合溶解在甲苯和N,N-二甲基甲酰胺(DMF)混合溶剂中，得到均匀纺丝液，然后将均匀纺丝液转移至注射器内进行静电纺丝制备得到静电纺EVA纤维膜。
在本发明一种实施方式中，步骤(1)的紫外光固化是将静电纺EVA纤维膜置于365nm紫外光下固化1h。
在本发明一种实施方式中，步骤(1)的静电纺丝的纺丝液中EVA颗粒、BP粉末和TAIC的质量比为100:2～5:1～3，优选的质量比为100:3:1。
在本发明一种实施方式中，EVA颗粒的VA占20wt％～30wt％，优选的EVA颗粒的VA占25wt％。
在本发明一种实施方式中，步骤(1)的静电纺丝的纺丝液中甲苯和DMF体积比为2～3:1，优选的体积比为7:3。
在本发明一种实施方式中，步骤(1)的静电纺丝的纺丝液中EVA的质量浓度为8wt％～15wt％，优选的纺丝液中EVA的质量浓度为10wt％～12wt％，最佳的纺丝液中EVA的质量浓度为10wt％。
在本发明一种实施方式中，步骤(1)的静电纺丝的电压为15～18kV，优选的电压为16±0.5kV，最佳的电压为16kV。
在本发明一种实施方式中，步骤(1)的静电纺丝制备EVA纤维膜具体步骤是：
①在50℃磁力搅拌下，将5g的EVA颗粒、BP粉末和TAIC按100:3:1的质量比溶解在50ml的甲苯和DMF以7:3体积比配置的混合溶剂中5h，得到均匀纺丝液；
②将20ml的均匀纺丝液转移至配备加热套(温度保持50℃)和金属针的塑料注射器内，并将高压电源的正极与金属针相连；
③打开红外灯(温度保持50℃)和距注射泵20cm、转速为100r/min的收集滚筒，并将高压电源的负极与收集滚筒相连；
④在环境温度为30±2℃，相对湿度为45±5％条件下，依次打开进料速率为2ml/h的注射泵和电压为16kV的高压电源，8h后可收集到静电纺EVA纤维膜；
⑤静电纺EVA纤维膜在通风处静止24h后，将其从致密的不锈钢网上剥离，并置于紫外固化机内处理1h；
⑥采用乙醇溶液超声清洗，去除表面的杂质，得到EVA纤维膜。
在本发明一种实施方式中，步骤(2)的多巴胺溶液是将多巴胺盐酸盐和三羟甲基氨基甲 烷(Tris)混合溶解在去离子水中。
在本发明一种实施方式中，步骤(2)的多巴胺溶液是将多巴胺盐酸盐溶解在去离子水中，配置成多巴胺溶液，加入Tris调节pH至8.5～9.5。
在本发明一种实施方式中，步骤(2)的多巴胺溶液中多巴胺浓度为2～5g/L，优选的多巴胺浓度为2～3g/L，最佳的多巴胺浓度为2g/L。
在本发明一种实施方式中，步骤(2)中EVA纤维膜浸入多巴胺溶液反应的时间为20～25h。
在本发明一种实施方式中，步骤(2)中还需将反应后的纤维膜迁移至去离子水中超声1～5min。
在本发明一种实施方式中，步骤(3)银氨溶液是将AgNO3晶体溶解在水中，得AgNO3溶液，在持续搅拌下，向AgNO3溶液中缓慢滴入氨水，直至溶液变为澄清。
在本发明一种实施方式中，步骤(3)中AgNO3溶液浓度为9～11g/L，优选的AgNO3溶液浓度为9～10g/L。
在本发明一种实施方式中，步骤(3)银氨溶液具体是将1gAgNO3晶体溶解在100ml去离子水中，得到均质AgNO3溶液，在持续搅拌下，向浓度为10g/L的AgNO3溶液中缓慢滴入浓度为25％的氨水，直至溶液变为澄清。
在本发明一种实施方式中，步骤(3)的反应温度30-50℃。
在本发明一种实施方式中，步骤(3)搅拌的时间为20～40min，最佳搅拌的时间为30min。
在本发明一种实施方式中，步骤(3)的葡萄糖溶液浓度为15～25g/L。
在本发明一种实施方式中，步骤(3)AgNO3溶液和葡萄糖溶液浓度比为1:1～2，体积比为1:1。
在本发明一种实施方式中，步骤(3)反应是将葡萄糖溶液缓慢滴入银氨溶液中，在超声环境下进行3min，然后在40℃下磁力搅拌进行2h。
本发明利用上述方法制得一种电/热刺激形状记忆FPC电磁屏蔽膜。
本发明第二个目的是将上述电/热刺激形状记忆FPC电磁屏蔽膜应用到电子设备制造领域。
有益效果：
(1)由静电纺丝制备的形状记忆聚合物纤维膜除了具备轻薄化和高柔韧性的特点，还具有高孔隙率和大比表面积，可为入射电磁波的多重反射提供足够的空间，是柔性EMI屏蔽材料的理想基体；
(2)采用化学镀银工艺可将致密且均匀的银层稳固地修饰在聚合物纤维表面，赋予复合纤维较高的导电性能以及较强的EMI屏蔽能力；
(3)在电刺激下，本发明制备的FPC电磁屏蔽膜不仅可根据FPC的大小自由变形，而且可完全贴紧FPC上稠密布局的凹凸或错层排列的电子元器件，与此同时，其电磁干扰屏蔽效能仍保持在相对较高的水平；
(4)当电子设备废弃回收时，对纤维膜施加热刺激即可令其形状回复以及电磁干扰屏蔽效能恢复，具有较强的回收再利用性。
附图说明
图1是本发明具有电/热刺激形状记忆效应的FPC电磁屏蔽膜制备方法示意图。
图2是EVA纤维膜的热致形状记忆效应。
图3是实施例1制备的FPC电磁屏蔽膜的热致形状记忆效应。
图4是实施例1制备的FPC电磁屏蔽膜的电致形状记忆效应，a为实施例1制备的FPC电磁屏蔽膜在电响应拉伸形状记忆行为中的形状固定率(Rf)和形状回复率(Rr)；b为实施例1制备的FPC电磁屏蔽膜的电响应拉伸形状记忆行为；c为实施例1制备的FPC电磁屏蔽膜在电响应按压形状记忆行为中的Rf和Rr；d为实施例1制备的FPC电磁屏蔽膜的电响应按压形状记忆行为。
图5是实施例1制备的FPC电磁屏蔽膜在形状记忆过程中的电导率。
图6是实施例1制备的FPC电磁屏蔽膜在形状记忆过程中的电磁干扰屏蔽效能(EMI SE)。
图7是FPC电磁屏蔽膜的EMI屏蔽机理示意图。
图8是FPC电磁屏蔽膜的实际应用示意图，原始的电热刺激形状记忆FPC电磁屏蔽膜在0.55V下被拉伸成FPC的大小，拉伸后的电热刺激形状记忆FPC电磁屏蔽膜在0.55V下被按压至紧密贴附稠密布局的电子元器件，冷却的电热刺激形状记忆FPC电磁屏蔽膜在80℃下被驱动回复至初始形状。
具体实施方式
FPC电磁屏蔽膜的电/热刺激形状记忆过程如下：(1)测试初始FPC电磁屏蔽膜的电导率及EMI SE。(2)对初始样品依次采取施加0.55V电压、拉伸样品、关闭电源、移除外力操作，可得到变形样品，测试其电导率及EMI SE。(3)在无应力条件下，对变形样品施加80℃的高温，可得到回复样品，测试其电导率及EMI SE。
电导率：使用四探针方阻仪对电热刺激形状记忆FPC电磁屏蔽膜测量。
EMI SE:使用矢量网络分析仪对电热刺激形状记忆FPC电磁屏蔽膜测量。
下列实施例使用的EVA颗粒购自于阿拉丁，其中VA含量为25wt％，熔融指数为19g/10min。
实施例1：
一种电热刺激形状记忆效应的FPC电磁屏蔽膜的制备方法，图1是本发明的FPC电磁屏蔽膜制备方法示意图，制备的工艺步骤顺序包括：
(1)静电纺丝和紫外光固化制备EVA纤维膜：
①在50℃磁力搅拌下，将5g EVA颗粒、0.15g BP粉末和0.05g TAIC溶解在50ml的甲苯和DMF以7:3体积比配置的混合溶剂中5h，得到均匀纺丝液；
②将20ml的均匀纺丝液转移至配备加热套(温度保持50℃)和金属针的塑料注射器内，并将高压电源的正极与金属针相连；
③打开红外灯(温度保持50℃)和距注射泵20cm、转速为100r/min的收集滚筒，并将高压电源的负极与收集滚筒相连；
④在环境温度为30℃，相对湿度为50％条件下，依次打开进料速率为2ml/h的注射泵和电压为16kV的高压电源，8h后可收集到静电纺EVA纤维膜；
⑤静电纺EVA纤维膜在通风处静止24h后，将其从致密的不锈钢网上剥离，并置于紫外固化机内处理1h；
⑥采用乙醇溶液超声清洗，去除表面的杂质，得到EVA纤维膜。
(2)将多巴胺盐酸盐溶解在去离子水中，配置成浓度为2g/L的多巴胺溶液，加入Tris调节pH至8.5；将清洗后的EVA纤维膜浸入多巴胺溶液中并持续搅拌反应24h，将反应后的EVA纤维膜迁移至去离子水中超声5min，得到表面沉积聚多巴胺薄膜的EVA纤维膜；
(3)将1gAgNO3晶体溶解在100ml去离子水中，得到均质AgNO3溶液；在持续搅拌下，向浓度为10g/L的AgNO3溶液中缓慢滴入浓度为25％的氨水，直至溶液变为澄清，配置成银氨溶液；将表面沉积聚多巴胺薄膜的EVA纤维膜放入银氨溶液中磁力搅拌30min；将浓度为20g/L的100ml葡萄糖溶液缓慢滴入浸有表面沉积聚多巴胺薄膜的EVA纤维膜的银氨溶液中，在超声环境下进行3min，然后在40℃下磁力搅拌进行2h，将反应后的纤维膜在去离子水中洗涤并在室温下干燥，即得到电热刺激形状记忆FPC电磁屏蔽膜。
制得的电热刺激形状记忆FPC电磁屏蔽膜形状记忆效应优秀，Rf为99％，Rr为97％，电磁屏蔽性能也很优秀，EMI SE为87.71dB。
实施例2：
参照实施例1，仅改变步骤(1)中④的纺丝电压为16kV、17kV和18kV，其余条件不变，制得电热刺激形状记忆FPC电磁屏蔽膜。
表1不同纺丝电压制得电热刺激形状记忆FPC电磁屏蔽膜性能对照表
实施例3：
参照实施例1，按表2改变步骤(3)中的AgNO3溶液和葡萄糖溶液的浓度，其余条件不变，制得电热刺激形状记忆FPC电磁屏蔽膜。
表2不同AgNO3溶液和葡萄糖溶液制得电热刺激形状记忆FPC电磁屏蔽膜性能对照表
实施例4
(1)热压法制备乙烯-醋酸乙烯共聚物(EVA)纤维膜：
①将5g EVA颗粒和0.15g过氧化异丙苯(DCP)溶解在50ml甲苯溶剂中，得到均匀的EVA溶液；
②将混合溶液先置于室温干燥后置于真空干燥箱中干燥，以充分去除甲苯。
③将干燥后的基体材料剪碎并均匀铺于热压模具上，在140℃、150℃、160℃下固化3h。
④在25℃下将固化完成的EVA膜从热压模具上取出。
(2)将多巴胺盐酸盐和Tris混合物溶解在去离子水中，得到pH为8.5，浓度为2g/L的多巴胺溶液；将清洗后的EVA纤维膜浸入多巴胺溶液中并持续搅拌24h，将反应后的EVA纤维膜迁移至去离子水中超声5min，得到表面沉积聚多巴胺薄膜的EVA纤维膜；
(3)表面沉积聚多巴胺薄膜的纤维膜浸入银氨溶液，搅拌，并滴加葡萄糖溶液反应，反应结束后，洗涤干燥，即得到具有电热刺激形状记忆效应的FPC电磁屏蔽膜。将1gAgNO3晶体溶解在100ml去离子水中，得到均质AgNO3溶液；在持续搅拌下，向浓度为10g/L的AgNO3溶液中缓慢滴入浓度为25％的氨水，直至溶液变为澄清，配置成银氨溶液；将表面沉积聚多巴胺薄膜的EVA纤维膜放入银氨溶液中磁力搅拌30min；将浓度为20g/L的100ml葡萄糖溶液缓慢滴入浸有表面沉积聚多巴胺薄膜的EVA纤维膜的银氨溶液中，在超声环境下进行3min，然后在40℃下磁力搅拌进行2h，将反应后的纤维膜在去离子水中洗涤并在室温下干燥，即得到电热刺激形状记忆FPC电磁屏蔽膜。
表3使用热压法不同热压温度制备的电热刺激形状记忆FPC电磁屏蔽膜性能对照表
实施例5
参照实施例1，省略步骤(1)中⑤的紫外光固化，其余条件不变，制得电热刺激形状记忆FPC电磁屏蔽膜。
制得的电热刺激形状记忆FPC电磁屏蔽膜的电磁屏蔽性能未受到影响，但是形状记忆效应下降，Rf为92％，Rr为80％。
虽然本发明已以较佳实例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权力要求书所界定的为准。

Claims (11)

  1. 一种电热刺激形状记忆FPC电磁屏蔽膜的制备方法，其特征在于，步骤为：
    (1)静电纺丝和紫外光固化制备EVA纤维膜；
    (2)将EVA纤维膜浸入多巴胺溶液反应，反应结束后，得到表面沉积聚多巴胺薄膜的EVA纤维膜；
    (3)表面沉积聚多巴胺薄膜的纤维膜浸入银氨溶液，搅拌，并滴加葡萄糖溶液反应，反应结束后，洗涤干燥，即得到电热刺激形状记忆效应的FPC电磁屏蔽膜；
    步骤(1)的紫外光固化是将静电纺EVA纤维膜置于365nm紫外光下固化1h；
    步骤(3)银氨溶液是将AgNO3晶体溶解在水中，得AgNO3溶液，在持续搅拌下，向AgNO3溶液中缓慢滴入氨水，直至溶液变为澄清；
    步骤(3)中AgNO3溶液浓度为9～10g/L；步骤(3)AgNO3溶液和葡萄糖溶液浓度比为1:1，体积比为1:1。
  2. 一种电热刺激形状记忆FPC电磁屏蔽膜的制备方法，其特征在于，步骤为：
    (1)静电纺丝和紫外光固化制备EVA纤维膜；
    (2)将EVA纤维膜浸入多巴胺溶液反应，反应结束后，得到表面沉积聚多巴胺薄膜的EVA纤维膜；
    (3)表面沉积聚多巴胺薄膜的纤维膜浸入银氨溶液，搅拌，并滴加葡萄糖溶液反应，反应结束后，洗涤干燥，即得到电热刺激形状记忆效应的FPC电磁屏蔽膜。
  3. 根据权利要求2所述方法，其特征在于，步骤(1)的静电纺丝是将EVA颗粒、二苯甲酮粉末和三烯丙基异氰脲酸酯混合溶解在甲苯和N,N-二甲基甲酰胺混合溶剂中，得到均匀纺丝液，然后将均匀纺丝液转移至注射器内通过静电纺丝制备得到静电纺EVA纤维膜。
  4. 根据权利要求2所述方法，其特征在于，步骤(1)的紫外光固化是将静电纺EVA纤维膜置于365nm紫外光下固化1h。
  5. 根据权利要求3所述方法，其特征在于，步骤(1)的静电纺丝的纺丝液中EVA颗粒、BP粉末和TAIC的质量比为100:2～5:1～3。
  6. 根据权利要求3任一项所述方法，其特征在于，步骤(1)的静电纺丝的纺丝液中甲苯和DMF体积比为2～3:1。
  7. 根据权利要求2所述方法，其特征在于，步骤(1)的静电纺丝的电压为15～18kV。
  8. 根据权利要求2所述方法，其特征在于，步骤(2)的多巴胺溶液中多巴胺浓度为2～5g/L。
  9. 根据权利要求2～8任一项所述方法，其特征在于，步骤(2)反应后将纤维膜迁移至去离子水中超声1～5min。
  10. 权利要求2～9任一项所述方法制备得到的一种电热刺激形状记忆FPC电磁屏蔽膜。
  11. 权利要求10所述电热刺激形状记忆FPC电磁屏蔽膜在电子设备制造领域的应用。
PCT/CN2023/092678 2022-05-10 2023-05-08 电热刺激形状记忆fpc电磁屏蔽膜的制备方法 Ceased WO2023217065A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210507271.0 2022-05-10
CN202210507271.0A CN114855460B (zh) 2022-05-10 2022-05-10 一种电热刺激形状记忆fpc电磁屏蔽膜的制备方法

Publications (1)

Publication Number Publication Date
WO2023217065A1 true WO2023217065A1 (zh) 2023-11-16

Family

ID=82637386

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/092678 Ceased WO2023217065A1 (zh) 2022-05-10 2023-05-08 电热刺激形状记忆fpc电磁屏蔽膜的制备方法

Country Status (2)

Country Link
CN (1) CN114855460B (zh)
WO (1) WO2023217065A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118110058A (zh) * 2024-02-23 2024-05-31 安徽理工大学 纳米片复合材料及其制备方法、具有形状记忆功能的导电纳米复合纸及其应用
CN119754024A (zh) * 2024-12-27 2025-04-04 郑州大学 一种红外隐身织物的制备方法及由其制备得到的红外隐身织物和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114855460B (zh) * 2022-05-10 2023-05-16 江南大学 一种电热刺激形状记忆fpc电磁屏蔽膜的制备方法
CN118308833B (zh) * 2024-04-09 2026-07-03 江南大学 一种多功能柔性可穿戴MXene@EVA同轴纳米纤维膜及其制备方法
CN118516856B (zh) * 2024-05-21 2025-08-08 深圳市海普睿能科技有限公司 高柔韧性的透明导电屏蔽膜及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108193501A (zh) * 2018-01-24 2018-06-22 哈尔滨工业大学 一种导电形状记忆薄膜、制备方法及其电驱动方法
CN108570163A (zh) * 2018-05-15 2018-09-25 东华大学 一种基于纳米纤维素的高效电磁屏蔽多孔材料的制备方法
US20190177570A1 (en) * 2016-12-19 2019-06-13 Dalian University Of Technology Surface modification method based on polymerization and cross-linking solidification of dopamine and/or derivatives thereof
CN112376266A (zh) * 2020-09-24 2021-02-19 浙江理工大学 具备形状记忆性能和应变传感性能的复合纤维及其制备方法
CN113265908A (zh) * 2021-04-14 2021-08-17 上海大学 利用导电纳米纤维构筑的柔性复合电磁屏蔽薄膜及其制备方法
CN114855460A (zh) * 2022-05-10 2022-08-05 江南大学 一种电热刺激形状记忆fpc电磁屏蔽膜的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153864A (zh) * 2015-08-19 2015-12-16 中国科学院深圳先进技术研究院 一种光热致形状记忆复合材料及其制备方法
CN110248530B (zh) * 2019-06-29 2021-11-23 华南理工大学 一种可穿戴的透气自清洁高电磁屏蔽薄膜及其制备方法
CN110567359A (zh) * 2019-08-01 2019-12-13 广东工业大学 一种基于形状记忆的多重刺激自传感软体驱动器及其制备方法和应用
CN111188201B (zh) * 2020-01-08 2022-10-04 广东工业大学 一种高度可拉伸防水的形状记忆聚合物纤维膜及其制备方法和应用
CN113638239B (zh) * 2021-09-08 2023-07-11 北京化工大学常州先进材料研究院 一种具有电磁屏蔽功能的聚酰亚胺/银复合膜及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190177570A1 (en) * 2016-12-19 2019-06-13 Dalian University Of Technology Surface modification method based on polymerization and cross-linking solidification of dopamine and/or derivatives thereof
CN108193501A (zh) * 2018-01-24 2018-06-22 哈尔滨工业大学 一种导电形状记忆薄膜、制备方法及其电驱动方法
CN108570163A (zh) * 2018-05-15 2018-09-25 东华大学 一种基于纳米纤维素的高效电磁屏蔽多孔材料的制备方法
CN112376266A (zh) * 2020-09-24 2021-02-19 浙江理工大学 具备形状记忆性能和应变传感性能的复合纤维及其制备方法
CN113265908A (zh) * 2021-04-14 2021-08-17 上海大学 利用导电纳米纤维构筑的柔性复合电磁屏蔽薄膜及其制备方法
CN114855460A (zh) * 2022-05-10 2022-08-05 江南大学 一种电热刺激形状记忆fpc电磁屏蔽膜的制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118110058A (zh) * 2024-02-23 2024-05-31 安徽理工大学 纳米片复合材料及其制备方法、具有形状记忆功能的导电纳米复合纸及其应用
CN118110058B (zh) * 2024-02-23 2025-12-02 安徽理工大学 纳米片复合材料及其制备方法、具有形状记忆功能的导电纳米复合纸及其应用
CN119754024A (zh) * 2024-12-27 2025-04-04 郑州大学 一种红外隐身织物的制备方法及由其制备得到的红外隐身织物和应用

Also Published As

Publication number Publication date
CN114855460B (zh) 2023-05-16
CN114855460A (zh) 2022-08-05

Similar Documents

Publication Publication Date Title
CN114855460B (zh) 一种电热刺激形状记忆fpc电磁屏蔽膜的制备方法
CN106853966B (zh) 利用石墨烯掺杂聚酰胺酸树脂制备高导热石墨膜的方法
CN113638239B (zh) 一种具有电磁屏蔽功能的聚酰亚胺/银复合膜及其制备方法
CN106832279A (zh) 一种利用微波辅助亚胺化制备聚酰亚胺薄膜或纤维的方法
CN106832926A (zh) 用于导热的石墨混合物、石墨膜及其制备方法和应用
CN109972128A (zh) 喷墨打印结合无电镀工艺制备超薄金属网格柔性透明电极的方法
CN108493459B (zh) 一种纤维状空气电池
CN111171482A (zh) 碳纤维毡/银纳米线/聚偏氟乙烯复合材料的制备方法
CN105161219A (zh) 一种uv光固化银包镍导电浆料的制备方法
CN106833353B (zh) 一种触摸屏用uv固化纳米银线浆料及其制备方法
CN106298986A (zh) 阴极及其制备方法、太阳能单元、组合物、薄膜
CN108976449A (zh) 基于基底模量来调控聚苯胺/聚吡咯薄膜表面形貌的方法
CN120797412A (zh) 一种锂电池纤维素基隔膜用高强度纳米纤维的制备方法
CN114753061A (zh) 基于离子液体基的透明聚氨酯薄膜的制备方法
CN107385681B (zh) 一种静电纺丝制备均匀透明导电薄膜的方法
CN107325331A (zh) 一种柔性显示器基质材料制备方法
CN118832922A (zh) 一种柔性耐高温bt树脂基覆铜板及其制备方法
CN110444316A (zh) 一种高导电、低银含量的低温固化导电银浆及其制备方法
CN114591626A (zh) 一种抗电子辐照与应力场耦合的透明聚酰亚胺及制备方法
WO2020125377A1 (zh) 一种基于图案化层层组装自支持膜的柔性透明导电膜及其制备方法
CN116376085A (zh) 一种光/酸碱双重刺激响应刚性聚合物的制备及应用研究
CN117624493A (zh) 液态金属基高导电弹性体复合材料及3d打印成型方法
CN114591535A (zh) 一种纳米簇交联的有机无机杂化交联聚合物的回收方法
CN102504211B (zh) 热固性酰亚胺树脂改性硅氮烷及其复合材料的制备方法
CN108822493B (zh) 一种纳米陶瓷填充pcb覆铜板半固化片的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23802837

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23802837

Country of ref document: EP

Kind code of ref document: A1