TWI445018B - Electromagnetic shielding composition, electromagnetic shielding device, anti-electrostatic device and method of manufacturing electromagnetic shielding structure - Google Patents
Electromagnetic shielding composition, electromagnetic shielding device, anti-electrostatic device and method of manufacturing electromagnetic shielding structure Download PDFInfo
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Description
本揭露係關於一種用於電磁屏蔽之組合物,尤指一種具奈米線材與奈米粒子之組合物。The present disclosure relates to a composition for electromagnetic shielding, and more particularly to a composition having a nanowire and a nanoparticle.
隨著無線通訊科技的進步,無線通訊裝置例如手機等被廣泛地使用。由於無線通訊裝置及其基地台均會產生電磁波,因此容易造成環境中充斥著電磁波。此外,許多日常使用之電子產品,例如:電腦或微波爐等,也都會產生微量之電磁波。With the advancement of wireless communication technology, wireless communication devices such as mobile phones and the like are widely used. Since the wireless communication device and its base station generate electromagnetic waves, it is easy to cause electromagnetic waves in the environment. In addition, many everyday electronic products, such as computers or microwave ovens, also generate trace amounts of electromagnetic waves.
根據1998年世界衛生組織所發表的報告,長期暴露在高於電磁波標準值的人,容易罹患心血管疾病、糖尿病或癌症等疾病,或容易導致生殖系統、免疫系統、神經系統等之病變,或造成孕婦流產、畸胎或不孕等。長期暴露在高於電磁波標準值的兒童易出現骨骼發育緩慢、肝臟造血功能下降、視力衰落甚至視網膜脫落等症狀。由此可知,電磁波對人體之健康影響甚鉅。According to a report published by the World Health Organization in 1998, people who have been exposed to higher than the standard value of electromagnetic waves for a long time are prone to diseases such as cardiovascular disease, diabetes or cancer, or are prone to diseases of the reproductive system, immune system, nervous system, etc., or Cause abortion, abortion or infertility in pregnant women. Long-term exposure to children above the standard value of electromagnetic waves is prone to symptoms such as slow bone development, decreased hematopoietic function, visual decline, and even retinal detachment. It can be seen that electromagnetic waves have a great impact on the health of the human body.
目前傳統遮蔽電磁波之方法是使用金屬塊材或金屬外殼遮蔽電磁波源,但由於其重量重、不易配合所需之形狀來製作,以及在長期使用下,易氧化毀損等,因而無法方便地使用在各類電子產品上。At present, the conventional method of shielding electromagnetic waves is to shield the electromagnetic wave source by using a metal block or a metal casing, but it is not easy to use because it is heavy in weight, difficult to fit with the desired shape, and easily oxidized and damaged under long-term use. All kinds of electronic products.
另一種遮蔽電磁波之方法係將金屬顆粒混合於膠體或漆類中,以塗佈之方式在本體上形成電磁波遮蔽層。電磁波遮蔽層質輕,並可配合各種外形來製作。但為達到一定程度的電磁波遮蔽效果,膠體或漆類中需添加高濃度之金屬顆粒。高濃度之金屬顆粒雖會提高屏蔽效果,但會降低混合材料之可塑性及強度,而失去易加工、重量輕及低成本的優點。此外,電磁波遮蔽層一般僅具有單一外形結構之金屬顆粒,為提高屏蔽效果而增加金屬顆粒之含量,通常其電磁遮蔽效率(Shielding Effectiveness;S.E.)之改善有限。Another method of shielding electromagnetic waves is to mix metal particles in a colloid or lacquer to form an electromagnetic wave shielding layer on the body in a coating manner. The electromagnetic wave shielding layer is light in weight and can be produced in various shapes. However, in order to achieve a certain degree of electromagnetic wave shielding effect, a high concentration of metal particles needs to be added to the colloid or lacquer. High concentration of metal particles will improve the shielding effect, but will reduce the plasticity and strength of the mixed material, and lose the advantages of easy processing, light weight and low cost. In addition, the electromagnetic wave shielding layer generally only has metal particles of a single outer shape structure, and the content of the metal particles is increased in order to improve the shielding effect, and the improvement of the Shielding Effectiveness (S.E.) is generally limited.
此外,傳統的電磁波遮蔽層通常需製備至250微米以上的厚度,方可具有顯著的電磁波遮蔽效果。然而,製備厚的電磁波遮蔽層均勻度不佳,且會浪費較多材料。In addition, the conventional electromagnetic wave shielding layer usually needs to be prepared to a thickness of 250 micrometers or more in order to have a significant electromagnetic wave shielding effect. However, the preparation of a thick electromagnetic wave shielding layer is not uniform and wastes a lot of material.
有鑑於傳統遮蔽電磁波之方法之不足,因此有必要發展一種具高電磁波遮蔽率、成本低且容易使用等優點之電磁波遮蔽材料。In view of the deficiencies of the conventional method of shielding electromagnetic waves, it is necessary to develop an electromagnetic wave shielding material having the advantages of high electromagnetic shielding rate, low cost, and ease of use.
本揭露之一實施範例揭示一種用於電磁屏蔽之組合物,其包含一載體、複數根奈米金屬線材及複數個奈米粒子。複數根奈米金屬線材散佈於該載體中,其中以該組合物為100重量份計,該些奈米金屬線材介於1重量份至95重量份。複數個奈米粒子散佈於該載體中,其中以該組合物為100重量份計,該些奈米粒子介於0.1重量份至60重量份。One embodiment of the present disclosure discloses a composition for electromagnetic shielding comprising a carrier, a plurality of nanowires, and a plurality of nanoparticles. A plurality of nanowires are interspersed in the carrier, wherein the nanowires are between 1 and 95 parts by weight based on 100 parts by weight of the composition. A plurality of nanoparticles are dispersed in the carrier, wherein the nanoparticles are present in an amount of from 0.1 part by weight to 60 parts by weight based on 100 parts by weight of the composition.
本揭露另一實施範例揭示一種用於電磁屏蔽之組合物,其包含一載體、複數根奈米金屬線材,以及複數個奈米粒子。複數根奈米金屬線材散佈於該載體中。該些奈米金屬線材之長徑比大於10。該奈米金屬線材係金、銀、銅、銦、鈀、鋁、鐵、鈷、鎳或前述金屬之混合物、合金或氧化物,其中以該組合物為100重量份計,該些奈米金屬線材介於1重量份至95重量份。複數個奈米粒子散佈於該載體中。該些奈米粒子小於1000奈米。該奈米粒子為金、銀、銅、銦、鈀、鋁、鐵、鈷、鎳或前述金屬之混合物、合金或氧化物,其中以該組合物為100重量份計,該些奈米粒子介於0.1重量份至60重量份。Another embodiment of the present disclosure discloses a composition for electromagnetic shielding comprising a carrier, a plurality of nanowires, and a plurality of nanoparticles. A plurality of nanowires are interspersed in the carrier. The nano metal wires have an aspect ratio greater than 10. The nano metal wire is a mixture, alloy or oxide of gold, silver, copper, indium, palladium, aluminum, iron, cobalt, nickel or the foregoing metal, wherein the nano metal is 100 parts by weight of the composition. The wire is between 1 part by weight and 95 parts by weight. A plurality of nanoparticles are interspersed in the carrier. The nanoparticles are less than 1000 nm. The nanoparticle is gold, silver, copper, indium, palladium, aluminum, iron, cobalt, nickel or a mixture, alloy or oxide of the foregoing metals, wherein the nanoparticle is based on 100 parts by weight of the composition. It is from 0.1 part by weight to 60 parts by weight.
本揭露另一實施範例揭示一種用於電磁屏蔽之組合物,其包含一載體、複數根奈米金屬線材,以及複數個奈米粒子。複數根奈米金屬線材散佈於該載體中。該些奈米金屬線材之長徑比大於10。該奈米金屬線材係金、銀、銅、銦、鈀、鋁、鐵、鈷、鎳或前述金屬之混合物、合金或氧化物。複數個奈米粒子散佈於該載體中。該些奈米粒子小於1000奈米。該奈米粒子為金、銀、銅、銦、鈀、鋁、鐵、鈷、鎳或前述金屬之混合物、合金或氧化物。以該組合物為100重量份計,該些奈米金屬線材介於1重量份至11重量份,而該些奈米粒子介於0.5重量份至4重量份,如此使用於電磁屏蔽之該組合物具有大於10dB之電磁波遮蔽效率值。Another embodiment of the present disclosure discloses a composition for electromagnetic shielding comprising a carrier, a plurality of nanowires, and a plurality of nanoparticles. A plurality of nanowires are interspersed in the carrier. The nano metal wires have an aspect ratio greater than 10. The nanowire is a mixture, alloy or oxide of gold, silver, copper, indium, palladium, aluminum, iron, cobalt, nickel or the foregoing metals. A plurality of nanoparticles are interspersed in the carrier. The nanoparticles are less than 1000 nm. The nanoparticles are gold, silver, copper, indium, palladium, aluminum, iron, cobalt, nickel or a mixture, alloy or oxide of the foregoing metals. The nano metal wires are between 1 part by weight and 11 parts by weight based on 100 parts by weight of the composition, and the nano particles are between 0.5 parts by weight and 4 parts by weight, so that the combination is used for electromagnetic shielding. The object has an electromagnetic wave shielding efficiency value greater than 10 dB.
本揭露另一實施範例揭示一種用於電磁屏蔽之組合物,其包含一載體、複數根奈米金屬線材,以及複數個奈米粒子。複數根奈米金屬線材散佈於該載體中。該些奈米金屬線材之長徑比為20到500。該奈米金屬線材係金、銀、銅、銦、鈀、鋁、鐵、鈷、鎳或前述金屬之混合物、合金或氧化物。複數個奈米粒子散佈於該載體中。該些奈米粒子粒徑為30到1000奈米。該奈米粒子為金、銀、銅、銦、鈀、鋁、鐵、鈷、鎳或前述金屬之混合物、合金或氧化物。其中以該組合物為100重量份計,該些奈米金屬線材介於1重量份至3重量份,該些奈米粒子佔該組合物之總重量為0.5重量份至4重量份,如此使用於電磁屏蔽之該組合物具有大於10dB之電磁波遮蔽效率值。Another embodiment of the present disclosure discloses a composition for electromagnetic shielding comprising a carrier, a plurality of nanowires, and a plurality of nanoparticles. A plurality of nanowires are interspersed in the carrier. The nano metal wires have an aspect ratio of 20 to 500. The nanowire is a mixture, alloy or oxide of gold, silver, copper, indium, palladium, aluminum, iron, cobalt, nickel or the foregoing metals. A plurality of nanoparticles are interspersed in the carrier. The nanoparticles have a particle size of 30 to 1000 nm. The nanoparticles are gold, silver, copper, indium, palladium, aluminum, iron, cobalt, nickel or a mixture, alloy or oxide of the foregoing metals. Wherein the nano metal wire is from 1 part by weight to 3 parts by weight based on 100 parts by weight of the composition, and the nano particles are from 0.5 part by weight to 4 parts by weight based on the total weight of the composition, and thus used The composition for electromagnetic shielding has an electromagnetic wave shielding efficiency value greater than 10 dB.
本揭露一實施範例揭示一種電磁屏蔽裝置,其包含一本體及一薄膜,其中薄膜形成於該本體上,以遮蔽電磁波。薄膜包含複數根奈米金屬線材及複數個奈米粒子,其中複數根奈米金屬線材與複數個奈米粒子分別散佈於該薄膜中,而且以該薄膜為100重量份,該些奈米金屬線材介於1重量份至95重量份;該些奈米粒子介於0.5重量份至60重量份。An embodiment of the present disclosure discloses an electromagnetic shielding device including a body and a film, wherein a film is formed on the body to shield electromagnetic waves. The film comprises a plurality of nanowires and a plurality of nanoparticles, wherein a plurality of nanowires and a plurality of nanoparticles are respectively dispersed in the film, and the nanowires are 100 parts by weight of the film. It is between 1 part by weight and 95 parts by weight; the nano particles are between 0.5 parts by weight and 60 parts by weight.
本揭露之一實施範例揭示一種抗靜電裝置,其包含一基板及一薄膜,其中薄膜形成於該基板上。薄膜包含複數根奈米金屬線材及複數個奈米粒子,其中複數根奈米金屬線材與複數個奈米粒子分別散佈於該薄膜中,而且以該薄膜為100重量份,該些奈米金屬線材介於1重量份至95重量份;該些奈米粒子介於0.1重量份至60重量份。One embodiment of the present disclosure discloses an antistatic device comprising a substrate and a film, wherein a film is formed on the substrate. The film comprises a plurality of nanowires and a plurality of nanoparticles, wherein a plurality of nanowires and a plurality of nanoparticles are respectively dispersed in the film, and the nanowires are 100 parts by weight of the film. Between 1 part by weight and 95 parts by weight; the nanoparticles are between 0.1 part by weight and 60 parts by weight.
本揭露另提出一種電磁屏蔽結構之製備方法,其包含下列步驟:提供一目標物;提供一混合材料,該混合材料包含複數根奈米金屬線材,其中該些奈米金屬線材之長徑比大於50;利用該混合材料,在該目標物之一表面上,形成一第一薄膜;以及加熱該第一薄膜至攝氏50度至攝氏250度之間之一溫度。The present disclosure further provides a method for preparing an electromagnetic shielding structure, comprising the steps of: providing a target; providing a mixed material, the mixed material comprising a plurality of nanowires, wherein the nanowires have an aspect ratio greater than 50: using the mixed material, forming a first film on one surface of the target; and heating the first film to a temperature between 50 degrees Celsius and 250 degrees Celsius.
本揭露之一實施範例揭示一種用於電磁屏蔽之組合物,其包含一載體、複數根奈米金屬線材及複數個奈米粒子。複數根奈米金屬線材係分散在載體內;複數個奈米粒子係分散在載體內;而複數根奈米金屬線材與複數個奈米粒子則彼此相混合。One embodiment of the present disclosure discloses a composition for electromagnetic shielding comprising a carrier, a plurality of nanowires, and a plurality of nanoparticles. The plurality of nanowires are dispersed in the carrier; the plurality of nanoparticles are dispersed in the carrier; and the plurality of nanowires and the plurality of nanoparticles are mixed with each other.
在一實施例中,以該組合物為100重量份計,複數根奈米金屬線材的含量為1重量份至95重量份之間,而以該組合物為100重量份計,複數個奈米粒子的含量為0.1重量份至60重量份。在另一實施例中,奈米粒子的含量為0.3重量份至40重量份。在另一實施例中,奈米粒子的含量為0.5重量份至20重量份。在另一實施例中,奈米粒子的含量為0.5重量份至10重量份。在另一實施例中,奈米粒子的含量為0.5重量份至4重量份。在另一實施例中,奈米粒子的含量為0.5重量份至2重量份。In one embodiment, the content of the plurality of nanowires is between 1 part by weight and 95 parts by weight based on 100 parts by weight of the composition, and the plurality of nanoparticles is 100 parts by weight of the composition. The content of the particles is from 0.1 part by weight to 60 parts by weight. In another embodiment, the content of the nanoparticles is from 0.3 parts by weight to 40 parts by weight. In another embodiment, the content of the nanoparticles is from 0.5 parts by weight to 20 parts by weight. In another embodiment, the content of the nanoparticles is from 0.5 part by weight to 10 parts by weight. In another embodiment, the content of the nanoparticles is from 0.5 parts by weight to 4 parts by weight. In another embodiment, the content of the nanoparticles is from 0.5 parts by weight to 2 parts by weight.
在一實施例中,以該組合物為100重量份計,複數根奈米金屬線材之含量為1重量份至95重量份之間,而以該組合物為100重量份計,複數個奈米粒子之含量為0.5重量份至60重量份之間。In one embodiment, the content of the plurality of nanowires is between 1 part by weight and 95 parts by weight based on 100 parts by weight of the composition, and the plurality of nanoparticles is 100 parts by weight of the composition. The content of the particles is between 0.5 parts by weight and 60 parts by weight.
在一實施例中,複數根奈米金屬線材與複數個奈米粒子之含量比可大於0.1。In one embodiment, the ratio of the plurality of nanowires to the plurality of nanoparticles may be greater than 0.1.
本揭露之一實施範例揭示一種固化體,其係由前述之組合物固化而成。在一實施例中,前述之固化體可為在電磁屏蔽裝置上之一薄膜或在抗靜電裝置中之一薄膜。奈米金屬線材可形成一導電結構,使固化體可實質地導電。One embodiment of the present disclosure discloses a cured body formed by curing the aforementioned composition. In one embodiment, the aforementioned cured body may be a film on one of the electromagnetic shielding devices or one of the antistatic devices. The nanowire can form a conductive structure such that the cured body can be substantially electrically conductive.
根據推論,加入奈米粒子可改變電磁波光程差,因此其在該固化體內可損耗電磁波能量,所以將奈米粒子混入奈米金屬線材,可明顯提高固化體之電磁遮蔽效率(Shielding Effectiveness;S.E.)。According to the inference, the addition of nano particles can change the optical path difference of the electromagnetic wave, so that the electromagnetic wave energy can be lost in the solidified body, so the mixing of the nano particles into the nano metal wire can significantly improve the electromagnetic shielding efficiency of the solidified body (Shielding Effectiveness; SE ).
本發明公開的複數個奈米粒子之粒徑可小於1000奈米。The plurality of nano particles disclosed in the present invention may have a particle diameter of less than 1000 nm.
在一實施例中,奈米粒子可為導電粒子。在另一實施例中,奈米粒子可為奈米金屬粒子,其材料可為金、銀、銅、銦、鈀、鋁、鐵、鈷、鎳或前述金屬之混合物或前述金屬之合金或前述金屬之氧化物,其中以該組合物為100重量份計,奈米金屬粒子佔該組合物之總重量為0.5重量份至2重量份之間。在又一實施例中,奈米粒子可為金包覆銀奈米粒子、銀包覆金奈米粒子、金包覆銅奈米粒子、銅包覆金奈米粒子、銀包覆銅奈米粒子、銅包覆銀奈米粒子或前述之組合。In an embodiment, the nanoparticles can be electrically conductive particles. In another embodiment, the nano particles may be nano metal particles, and the material thereof may be gold, silver, copper, indium, palladium, aluminum, iron, cobalt, nickel or a mixture of the foregoing metals or an alloy of the foregoing or the foregoing An oxide of a metal wherein the nano metal particles are present in an amount of from 0.5 part by weight to 2 parts by weight based on the total weight of the composition. In still another embodiment, the nanoparticles may be gold-coated silver nanoparticles, silver-coated gold nanoparticles, gold-coated copper nanoparticles, copper-coated gold nanoparticles, and silver-coated copper nanoparticles. Particles, copper coated silver nanoparticles or a combination of the foregoing.
在一實施例中,奈米粒子可為導磁粒子,且其可包含鐵磁性元素。在另一實施例中,奈米粒子可為絕緣導磁粒子,其材料可包含四氧化三鐵,其中以該組合物為100重量份計,該奈米粒子可為0.5重量份至4重量份之間或0.5重量份至2重量份之間。In an embodiment, the nanoparticles may be magnetically permeable particles and they may comprise ferromagnetic elements. In another embodiment, the nano particles may be insulating magnetic conductive particles, and the material thereof may include triiron tetroxide, wherein the nano particles may be 0.5 parts by weight to 4 parts by weight based on 100 parts by weight of the composition. Between 0.5 parts by weight and 2 parts by weight.
在一實施例中,奈米粒子可為奈米銀粒子、奈米四氧化三鐵粒子或前述粒子之混合,其中以該組合物為100重量份計,該些奈米粒子可為0.5重量份至4重量份之間或0.5重量份至2重量份之間。In one embodiment, the nano particles may be nano silver particles, nano-iron trioxide particles or a mixture of the foregoing particles, wherein the nano particles may be 0.5 parts by weight based on 100 parts by weight of the composition. Between 4 parts by weight or between 0.5 parts by weight and 2 parts by weight.
在一實施例中,奈米粒子為導電粒子、導磁粒子、絕緣導磁粒子,或上述之組合,且該些奈米粒子介於0.5重量份至2重量份。In one embodiment, the nanoparticles are conductive particles, magnetically permeable particles, insulated magnetically permeable particles, or a combination thereof, and the nanoparticles are between 0.5 parts by weight and 2 parts by weight.
在一實施例中,奈米粒子之粒徑可大於10奈米,或例如介於30奈米至1000奈米之間。在一實施例中,奈米粒子之粒徑可介於30奈米至500奈米之間。In one embodiment, the nanoparticles may have a particle size greater than 10 nanometers, or such as between 30 nanometers and 1000 nanometers. In one embodiment, the nanoparticles may have a particle size between 30 nanometers and 500 nanometers.
組合物固化成固化體,複數根奈米金屬線材可均勻地分佈在固化體中。在一實施例中,複數根奈米金屬線材可在固化體內形成一網絡結構,使固化體具低的表面電阻率(surface resistivity),例如小於10歐姆/平方(Ω/sqr)。The composition is cured into a solidified body, and the plurality of nanowires are uniformly distributed in the solidified body. In one embodiment, the plurality of nanowires can form a network structure within the cured body such that the cured body has a low surface resistivity, such as less than 10 ohms/square (Ω/sqr).
在另一實施例中,組合物包含少量之奈米金屬線材,且當組合物固化成固化體後,複數根奈米金屬線材可在固化體內形成一網絡結構或類網絡結構,其中該網絡結構或類網絡結構讓固化體具較高的表面電阻率(surface resistivity)值,例如介於10至106 歐姆/平方(Ω/sqr)之間。In another embodiment, the composition comprises a small amount of nanowire metal, and after the composition is cured into a cured body, the plurality of nanowires can form a network structure or a network-like structure in the cured body, wherein the network structure Or a network structure allows the cured body to have a higher surface resistivity value, for example between 10 and 10 6 ohms/square (Ω/sqr).
在又一實施例中,組合物包含少量之奈米金屬線材,且當組合物固化成固化體後,複數根奈米金屬線材可在固化體內形成一網絡結構或類網絡結構,其中該網絡結構或類網絡結構讓固化體具較高的表面電阻率(surface resistivity)值,例如介於104 至1012 歐姆/平方(Ω/sqr)之間,使得該固化體可應用在抗靜電之場合。In still another embodiment, the composition comprises a small amount of nanowires, and after the composition is cured into a cured body, the plurality of nanowires can form a network structure or a network-like structure in the cured body, wherein the network structure Or a network structure allows the cured body to have a high surface resistivity value, for example, between 10 4 and 10 12 ohms/square (Ω/sqr), so that the cured body can be used in an antistatic environment. .
組合物可包含具高長徑比(high aspect ratio)之奈米金屬線材。使用高長徑比之奈米金屬線材可大幅提高固化體之電磁遮蔽效率。此外,使用高長徑比之奈米金屬線材可進一步減少奈米金屬線材之使用量。The composition may comprise a nano metal wire having a high aspect ratio. The use of high aspect ratio nanowires can greatly increase the electromagnetic shielding efficiency of the cured body. In addition, the use of nanometer metal wires with a high aspect ratio can further reduce the amount of nanowires used.
在一實施例中,奈米金屬線材之長徑比可大於10,或例如介於20至500之間,或例如介於50至300之間。In an embodiment, the nano metal wires may have an aspect ratio greater than 10, or such as between 20 and 500, or such as between 50 and 300.
在一實施例中,該奈米金屬線材可為金、銀、銅、銦、鈀、鋁、鐵、鈷、鎳或前述金屬之混合物、合金或氧化物。在另一實施例中,奈米金屬線材可為金包覆銀奈米線材、銀包覆金奈米線材、金包覆銅奈米線材、銅包覆金奈米線材、銀包覆銅奈米線材、銅包覆銀奈米線材或前述之組合。In one embodiment, the nanowire may be gold, silver, copper, indium, palladium, aluminum, iron, cobalt, nickel, or a mixture, alloy or oxide of the foregoing. In another embodiment, the nano metal wire may be a gold-coated silver nanowire, a silver-coated gold nanowire, a gold-coated copper nanowire, a copper-coated gold nanowire, or a silver-coated copper nano. Rice wire, copper coated silver nanowire or a combination of the foregoing.
載體可包含高分子材料。高分子材料可包含熱塑性塑膠,例如:壓克力樹脂;或者包含熱固性塑膠,例如:環氧樹脂。在一實施例中,載體亦可為光交聯(photo-crosslinking)或熱交聯(thermally crosslinking polymer)高分子材料。The carrier may comprise a polymeric material. The polymer material may comprise a thermoplastic plastic such as an acrylic resin or a thermosetting plastic such as an epoxy resin. In one embodiment, the carrier may also be a photo-crosslinking or thermally crosslinking polymer material.
使用具金屬或導磁性奈米材料的混合材料,在一目標物(target)上形成薄膜,可使該目標物具電磁遮蔽效果。若對該薄膜施以光能或熱能,可進一步提高薄膜的電磁遮蔽效率。由於薄膜的電磁遮蔽效率提昇,因此在不減損所需的電磁波遮蔽效果的情況下,可降低薄膜的厚度。厚度降低可使薄膜更為均勻,並減少使用材料。薄膜可加熱至攝氏50度至攝氏250度之間之一溫度。混合材料可包含奈米材料及一載體,其中載體可為高分子材料,而奈米材料可為奈米金屬線材,而該些奈米金屬線材之長徑比可大於50。在一實施例中,載體亦可為光交聯(photo-crosslinking)或熱交聯(thermally crosslinking polymer)高分子材料。The use of a mixed material of a metal or magnetically conductive nanomaterial to form a film on a target allows the target to have an electromagnetic shielding effect. If the film is applied with light energy or heat energy, the electromagnetic shielding efficiency of the film can be further improved. Since the electromagnetic shielding efficiency of the film is improved, the thickness of the film can be reduced without detracting from the shielding effect of the electromagnetic wave required. The reduced thickness allows for a more uniform film and reduces the amount of material used. The film can be heated to a temperature between 50 degrees Celsius and 250 degrees Celsius. The hybrid material may comprise a nano material and a carrier, wherein the carrier may be a polymer material, and the nano material may be a nano metal wire, and the nano metal wires may have an aspect ratio of greater than 50. In one embodiment, the carrier may also be a photo-crosslinking or thermally crosslinking polymer material.
薄膜可被加熱至攝氏50度至攝氏250度之間之一溫度,並維持一段時間(至少5分鐘以上),可使薄膜在頻率30M至16G之間之電磁遮蔽效率提昇至少5dB。在一實施例中,薄膜在攝氏60度至攝氏250度之間之一溫度上,加熱至少5分鐘以上。在一實施例中,加熱至少1小時以上。在一實施例中,薄膜在攝氏60度至攝氏200度之間之一溫度,加熱5分鐘至2小時以上。The film can be heated to a temperature between 50 degrees Celsius and 250 degrees Celsius for a period of time (at least 5 minutes or more) to increase the electromagnetic shielding efficiency of the film between 30M and 16G by at least 5dB. In one embodiment, the film is heated for at least 5 minutes at a temperature between 60 degrees Celsius and 250 degrees Celsius. In one embodiment, the heating is for at least 1 hour. In one embodiment, the film is heated at a temperature between 60 degrees Celsius and 200 degrees Celsius for 5 minutes to over 2 hours.
奈米金屬線材的材料可為金、銀、銅、銦、鈀、鋁、鐵、鈷或鎳。奈米金屬線材的材料亦可為金、銀、銅、銦、鈀、鋁、鐵、鈷、鎳或前述金屬的混合物,或者為金、銀、銅、銦、鈀、鋁、鐵、鈷、鎳或前述金屬的氧化物。The material of the nano metal wire may be gold, silver, copper, indium, palladium, aluminum, iron, cobalt or nickel. The material of the nano metal wire may also be gold, silver, copper, indium, palladium, aluminum, iron, cobalt, nickel or a mixture of the foregoing metals, or gold, silver, copper, indium, palladium, aluminum, iron, cobalt, Nickel or an oxide of the foregoing metal.
在一實施例中,薄膜可另包含複數個奈米粒子,其中奈米粒子為金屬奈米粒子、導磁性奈米粒子或其混合物。金屬奈米粒子可為銀粒子。導磁性奈米粒子可為四氧化三鐵粒子。奈米粒子小於1000奈米(例如:介於30奈米至1000奈米之間或介於30奈米至500奈米之間)。以該薄膜為100重量份,奈米粒子之含量可為0.1至60重量份之間、0.3至40重量份之間、0.5至20重量份之間、0.5至4重量份之間或0.5至2重量份之間。In an embodiment, the film may further comprise a plurality of nano particles, wherein the nano particles are metal nanoparticles, magnetic nanoparticles or a mixture thereof. The metal nanoparticles can be silver particles. The magnetically conductive nanoparticle may be a triiron tetroxide particle. Nanoparticles are less than 1000 nanometers (eg, between 30 nanometers and 1000 nanometers or between 30 nanometers and 500 nanometers). The content of the nanoparticles may be from 0.1 to 60 parts by weight, from 0.3 to 40 parts by weight, from 0.5 to 20 parts by weight, from 0.5 to 4 parts by weight or from 0.5 to 2, based on 100 parts by weight of the film. Between parts by weight.
目標物上可形成相疊設置之兩薄膜,其中一薄膜包含奈米金屬線材,而另一薄膜包含金屬或導磁性奈米粒子。Two films may be formed on the target, one of which comprises a nanowire and the other film comprises a metal or magnetically conductive nanoparticle.
目標物可視應用而定。例如:應用於電子裝置上時,目標物可為電子裝置之殼體、電子裝置上之電路板或電子裝置上需電磁遮蔽的部件。此外,目標物亦可為承載薄膜之基板。The target can be determined by the application. For example, when applied to an electronic device, the target may be a housing of the electronic device, a circuit board on the electronic device, or a component on the electronic device that needs electromagnetic shielding. In addition, the target may also be a substrate carrying a film.
以下列舉數個實例,以對本揭露做更加詳細之說明。Several examples are listed below to explain the disclosure in more detail.
實驗範例1Experimental example 1
以下描述之製備方法可用於調配不同奈米金屬線材與奈米粒子之組合物。在每一樣本中,首先,合成長徑比大於20之奈米銀線。奈米銀線之製備方法可為雷射消溶法(laser ablation method)、金屬氣相合成法(metal vapor synthesis method)、化學還原法(chemical reduction method)或多元醇法(polyol method)。前述之製備方法為相關技藝者所熟知,故不再於此贅述。The preparation methods described below can be used to formulate combinations of different nanowires and nanoparticles. In each sample, first, a nanowire with a length to diameter ratio greater than 20 was synthesized. The preparation method of the nano silver wire may be a laser ablation method, a metal vapor synthesis method, a chemical reduction method or a polyol method. The foregoing preparation methods are well known to those skilled in the art and will not be described again.
其次,將合成後之奈米銀線與奈米粒子加入一高分子材料內,以獲得一組合物。組合物可利用超音波震盪裝置與公/自轉攪拌機(planetary centrifugal mixer),將奈米銀線與奈米粒子均勻分散於高分子材料中。然後,將組合物適當成形固化後,獲得一固化體。最後,測試固化體之電磁波遮蔽效率值。電磁波遮蔽效率值之測試可利用標準電磁波測試方法,例如:ASTM D4935-99等。通常,電磁波遮蔽效率值(S.E.)可以下列公式表示。Next, the synthesized nano silver wire and the nanoparticle are added to a polymer material to obtain a composition. The composition can uniformly disperse the nano silver wire and the nano particles in the polymer material by means of an ultrasonic oscillating device and a planetary centrifugal mixer. Then, after the composition is appropriately shaped and cured, a cured body is obtained. Finally, the electromagnetic wave shielding efficiency value of the cured body was tested. The electromagnetic wave shielding efficiency value can be tested by a standard electromagnetic wave testing method, for example, ASTM D4935-99. Generally, the electromagnetic wave shielding efficiency value (S.E.) can be expressed by the following formula.
其中,Iin 為入射測試樣品電磁波強度;Iout 為通過測試樣品之電磁波強度。Wherein, I in is the electromagnetic wave intensity of the incident test sample; I out is the electromagnetic wave intensity of the test sample.
表1例示6種不同濃度之組合物。組合物(樣本1至樣本5)係將相同重量份之奈米銀線(Ag nanowire;AgNW)但不同重量份之四氧化三鐵奈米粒子(Fe3 O4 nano particle;Fe3 O4 NP)混入高分子溶液中製備而成,其中以組合物為100重量份計,奈米銀線之含量為1.22重量份,而四氧化三鐵奈米粒子之含量在0~1.88重量份之間,而前述之高分子材料為ETERSOL 6515不飽和聚酯樹脂(來源:長興化學工業股份有限公司(ETERNAL CHEMICAL CO.,LTD),台灣)。高分子材料包含聚甲基丙烯酸甲酯水溶液。Table 1 illustrates six different concentrations of the composition. The composition (sample 1 to sample 5) is the same weight part of nano silver wire (Ag nanowire; AgNW) but different parts by weight of ferroferric oxide particles (Fe 3 O 4 nano particle; Fe 3 O 4 NP Prepared by mixing into a polymer solution, wherein the content of the nano silver wire is 1.22 parts by weight, and the content of the ferroferric oxide particles is between 0 and 1.88 parts by weight, based on 100 parts by weight of the composition, The above polymer material is ETERSOL 6515 unsaturated polyester resin (Source: ETERNAL CHEMICAL CO., LTD, Taiwan). The polymer material contains a polymethyl methacrylate aqueous solution.
若以高分子材料為100重量份計,甲基丙烯酸甲酯之含量約為45~55重量份,而水約為55~45重量份。又,前述之奈米銀線之長徑比(aspect ratio)為250,而四氧化三鐵奈米粒子之粒徑為100奈米。樣本6則僅將四氧化三鐵粒子混入高分子溶液中,其中四氧化三鐵奈米粒子之含量為9.09重量份。樣本1~6混合均勻後,再分別以其製備成50微米厚之薄膜,最後再測試這些薄膜之電磁波遮蔽率。The methyl methacrylate content is about 45 to 55 parts by weight, and the water is about 55 to 45 parts by weight, based on 100 parts by weight of the polymer material. Further, the aforementioned nano silver wire has an aspect ratio of 250, and the ferroferric oxide nanoparticle has a particle diameter of 100 nm. In the sample 6, only the ferroferric oxide particles were mixed into the polymer solution, and the content of the triiron tetroxide particles was 9.09 parts by weight. After the samples 1 to 6 were uniformly mixed, they were respectively prepared into films of 50 μm thickness, and finally the electromagnetic wave shielding ratios of the films were tested.
如圖1與圖2所示,從樣本1~5之測試結果可發現,大致上隨著四氧化三鐵奈米粒子的含量增加,薄膜遮蔽電磁波的效率亦增加。四氧化三鐵奈米粒子的含量在0.1~3重量份之間時,尤其是在0.5~2重量份之間時,會有不錯的電磁波遮蔽效率值。As shown in Fig. 1 and Fig. 2, it can be found from the test results of the samples 1 to 5 that the efficiency of shielding the electromagnetic wave by the film is also increased substantially as the content of the ferroferric oxide particles increases. When the content of the ferric oxide nanoparticles is between 0.1 and 3 parts by weight, especially between 0.5 and 2 parts by weight, there is a good electromagnetic shielding efficiency value.
由此可知,適量地添加導磁性粒子於混有奈米金屬線材之薄膜內,可明顯地改善其電磁波遮蔽效率,但是當添加過多的導磁性粒子於混有奈米金屬線材之薄膜內時,結果和習知技術所推測的導磁性粒子越多效果會越好相反。因此,當四氧化三鐵奈米粒子粒徑為80~120奈米,而奈米銀線長徑比為200~300的情況下,四氧化三鐵奈米粒子的含量可介於0.1~3重量份或介於0.5~2重量份。Therefore, it can be seen that an appropriate amount of the magnetic conductive particles is added to the film in which the nano metal wire is mixed, and the electromagnetic wave shielding efficiency can be remarkably improved, but when too much magnetic conductive particles are added to the film in which the nano metal wire is mixed, As a result, the more magnetic conductive particles speculated by the prior art, the better the opposite effect. Therefore, when the particle size of the ferroferric oxide nanoparticle is 80 to 120 nm, and the aspect ratio of the nano silver wire is 200 to 300, the content of the triiron tetroxide particles may be between 0.1 and 3 Parts by weight or between 0.5 and 2 parts by weight.
另,從樣本6之測試結果可看出,雖四氧化三鐵奈米粒子為導磁粒子,但僅混有9.09重量份之四氧化三鐵奈米粒子之薄膜,其幾無電磁波遮蔽效果。若依據樣本6之測試結果推論,將含量低於9.09重量份之四氧化三鐵奈米粒子混入具奈米金屬線材之薄膜內,理應不會改善其電磁波遮蔽效果。Further, it can be seen from the test results of the sample 6 that although the ferroferric oxide particles are magnetically conductive particles, only a film of 9.09 parts by weight of the ferroferric oxide particles is mixed, and there is little electromagnetic wave shielding effect. According to the test result of the sample 6, it is inferred that the content of less than 9.09 parts by weight of the ferroferric oxide particles in the film with the nanowire metal wire should not improve the electromagnetic wave shielding effect.
然而,本揭露之實驗卻發現,在具奈米金屬線材之薄膜內,摻入低含量之四氧化三鐵奈米粒子,卻可使該薄膜具有不可預期之電磁波遮蔽效率值之改善結果。However, the experiments of the present disclosure have found that the incorporation of a low content of ferroferric oxide nanoparticles in a film having a nanowire can impart an unexpected result of an unexpected electromagnetic wave shielding efficiency.
實驗範例2Experimental example 2
以組合物為100重量份計,表2之組合物(樣本7至樣本9)係混入1.22重量份之奈米銀線以及分別混入0~1.24重量份之四氧化三鐵奈米粒子,其中奈米銀線之長徑比為80,而四氧化三鐵奈米粒子之粒徑為100奈米。混合完成後之樣本7至樣本9分別製作成厚度50微米之薄膜,以測試電磁波遮蔽效率值。組合物包含高分子材料,而高分子材料包含聚甲基丙烯酸甲酯水溶液。若以高分子材料為100重量份計,甲基丙烯酸甲酯之含量約為45~55重量份,而水約為55~45重量份。The composition of Table 2 (samples 7 to 9) was mixed with 1.22 parts by weight of nano silver wire and mixed with 0 to 1.24 parts by weight of ferroferric oxide particles, respectively, based on 100 parts by weight of the composition. The length-to-diameter ratio of the rice-silver wire is 80, and the particle size of the ferro-oxide-semiconductor particles is 100 nm. Samples 7 to 9 after the completion of the mixing were respectively made into a film having a thickness of 50 μm to test the electromagnetic wave shielding efficiency value. The composition comprises a polymeric material and the polymeric material comprises a polymethyl methacrylate aqueous solution. The methyl methacrylate content is about 45 to 55 parts by weight, and the water is about 55 to 45 parts by weight, based on 100 parts by weight of the polymer material.
參照圖2與圖3所示,相較於四氧化三鐵粒子與奈米銀線含量相近之樣本1、4與5之結果,樣本7至樣本9製作之薄膜具較低之電磁遮蔽效率。而由圖11顯示之模擬的結果可推知,電磁遮蔽效率隨著奈米銀線之長徑比之降低而降低,而樣本7至樣本9可能因使用長徑比較低之奈米銀線之緣故,而使其電磁遮蔽效率較低。Referring to Figures 2 and 3, the films produced in Samples 7 through 9 have lower electromagnetic shielding efficiency than the results of Samples 1, 4 and 5 in which the content of ferroferric oxide particles and nano silver wires are similar. From the results of the simulation shown in Fig. 11, it can be inferred that the electromagnetic shielding efficiency decreases as the aspect ratio of the nano silver wire decreases, and the samples 7 to 9 may be due to the use of a relatively low diameter nano silver wire. , making its electromagnetic shielding less efficient.
以例言,以樣本4製作之薄膜,其在2~16GHz頻率間之電磁遮蔽效率介於38~58dB之間,而相較地,樣本8位於相同頻率範圍之電磁遮蔽效率則介於可接受之20~27dB之間。For example, the film produced in sample 4 has an electromagnetic shielding efficiency between 38 and 58 dB at frequencies between 2 and 16 GHz. In contrast, the electromagnetic shielding efficiency of sample 8 in the same frequency range is acceptable. Between 20~27dB.
除奈米銀線的長徑比的影響外,與前述實驗相似,以樣本7至樣本9所製作之薄膜,四氧化三鐵奈米粒子含量越高者,其電磁遮蔽效率越高。Except for the influence of the aspect ratio of the nano silver wire, similar to the foregoing experiment, the film made from the samples 7 to 9 has a higher electromagnetic shielding efficiency as the content of the ferroferric oxide particles is higher.
再者,以樣本4製作的薄膜在2~16GHz頻率間的電磁遮蔽效率介於38~58dB之間。相較地,從圖3可得知,即便四氧化三鐵奈米粒子含量增加至1.2重量份(樣本9)後,薄膜的電磁遮蔽效率仍小於35dB。由此可得知,調整薄膜內之奈米銀線的長徑比對薄膜的電磁遮蔽效率的影響會較調整薄膜內之奈米粒子為大。一般而言,奈米銀線的長徑比可為10以上、80以上或100~300。Furthermore, the electromagnetic shielding efficiency of the film prepared in sample 4 between 2 and 16 GHz is between 38 and 58 dB. In comparison, it can be seen from Fig. 3 that even if the content of the ferroferric oxide particles is increased to 1.2 parts by weight (sample 9), the electromagnetic shielding efficiency of the film is still less than 35 dB. From this, it can be seen that the effect of adjusting the aspect ratio of the nanowires in the film on the electromagnetic shielding efficiency of the film is greater than that of the nanoparticles in the film. In general, the aspect ratio of the nano silver wire can be 10 or more, 80 or more, or 100 to 300.
實驗範例3Experimental example 3
以組合物為100重量份計,表3之組合物(樣本10至樣本13)係包含1.14重量份之奈米銀線以及分別包含含量在0~1.99重量份之四氧化三鐵奈米粒子,其中奈米銀線之長徑比為250,而四氧化三鐵奈米粒子之粒徑為100奈米。混合完成後之樣本10至樣本13分別製作成厚度50微米之薄膜,以測試電磁波遮蔽效率值。組合物包含高分子材料,而高分子材料包含聚甲基丙烯酸甲酯水溶液。若以高分子材料為100重量份計,甲基丙烯酸甲酯之含量約為45~55重量份,而水約為55~45重量份。The composition of Table 3 (samples 10 to 13) comprises 1.14 parts by weight of nano silver wire and respectively containing lanthanum tetraoxide nanoparticles in an amount of 0 to 1.99 parts by weight, based on 100 parts by weight of the composition. The nano silver wire has a length to diameter ratio of 250, and the ferroferric oxide nanoparticle has a particle size of 100 nm. Samples 10 to 13 after the completion of the mixing were each formed into a film having a thickness of 50 μm to test the electromagnetic wave shielding efficiency value. The composition comprises a polymeric material and the polymeric material comprises a polymethyl methacrylate aqueous solution. The methyl methacrylate content is about 45 to 55 parts by weight, and the water is about 55 to 45 parts by weight, based on 100 parts by weight of the polymer material.
參照圖2與圖4所示,相較於圖2中具相似四氧化三鐵奈米粒子含量之薄膜之實驗結果,由於樣本10至樣本13內具較低含量之奈米銀線,因此以樣本10至樣本13製作之薄膜具較低之電磁波遮蔽效率值。舉例言,比較樣本4和5之結果與樣本12之結果,以樣本4和5製成之薄膜在7~16GHz頻率間之電磁遮蔽效率介於36~58dB之間,而樣本12位於相同頻率範圍之電磁遮蔽效率則介於較低之22~27dB之範圍。Referring to FIG. 2 and FIG. 4, compared with the experimental results of the film having the similar content of the ferroferric oxide nanoparticle in FIG. 2, since the sample 10 to the sample 13 have a lower content of the nano silver wire, Films made from Samples 10 through 13 have lower electromagnetic wave shielding efficiency values. For example, comparing the results of samples 4 and 5 with the results of sample 12, the films produced in samples 4 and 5 have electromagnetic shielding efficiencies between 36 and 58 dB at frequencies between 7 and 16 GHz, while sample 12 is in the same frequency range. The electromagnetic shielding efficiency is in the range of 22 to 27 dB lower.
另,從實驗範例3之實驗結果可看出,相較於未添加四氧化三鐵奈米粒子之薄膜而言,薄膜添加1.33重量份之四氧化三鐵奈米粒子後,可大幅改善薄膜之電磁遮蔽效率。相同地,當添加過多、如樣本13之1.99重量份之四氧化三鐵奈米粒子時,電磁遮蔽效率則會降低。In addition, it can be seen from the experimental results of Experimental Example 3 that the film can be greatly improved by adding 1.33 parts by weight of the ferroferric oxide particles after adding the film to the film without the addition of the ferroferric oxide particles. Electromagnetic shielding efficiency. Similarly, when too much, such as 1.99 parts by weight of the ferroferric oxide particles of the sample 13, is added, the electromagnetic shielding efficiency is lowered.
由上述結果可得知,從圖2中之樣本4與樣本5及圖4中之樣本11、樣本12與樣本13等樣本之實驗結果來看,當薄膜材料中之線材的重量份在3%以下時,若添加超過2重量份的粒子,對其電磁遮蔽率的提升影響不大。因此,當四氧化三鐵奈米粒子粒徑為80~120奈米,奈米銀線長徑比為200~300,而且薄膜材料中的線材為1.0~1.3重量份時,四氧化三鐵奈米粒子的含量可介於0.1~3重量份、介於0.2~2重量份或介於1~2重量份。From the above results, it can be seen from the experimental results of the sample 4 and the sample 5 in FIG. 2 and the sample 11, the sample 12 and the sample 13 in FIG. 4, when the weight of the wire in the film material is 3%. In the following, when more than 2 parts by weight of particles are added, there is little influence on the improvement of the electromagnetic shielding rate. Therefore, when the particle size of the ferroferric oxide nanoparticle is 80 to 120 nm, the aspect ratio of the nano silver wire is 200 to 300, and the wire material in the film material is 1.0 to 1.3 parts by weight, the triiron telecommunications The content of the rice particles may be 0.1 to 3 parts by weight, 0.2 to 2 parts by weight or 1 to 2 parts by weight.
實驗範例4Experimental example 4
以組合物為100重量份計,表4之組合物(樣本14至樣本17)包含3重量份之奈米銀線以及分別包含含量介於0~1.79重量份之四氧化三鐵奈米粒子,其中奈米銀線之長徑比為250,而四氧化三鐵奈米粒子之粒徑為0.5微米。混合完成後之樣本14至樣本17分別製作成厚度50微米之薄膜,以測試電磁波遮蔽效率值。組合物包含高分子材料,而高分子材料包含聚甲基丙烯酸甲酯水溶液。若以高分子材料為100重量份計,甲基丙烯酸甲酯之含量約為45~55重量份,而水約為55~45重量份。The composition of Table 4 (samples 14 to 17) contained 3 parts by weight of nano silver wire and contained ferrotitanium tetraoxide particles in an amount of 0 to 1.79 parts by weight, respectively, based on 100 parts by weight of the composition. The nano silver wire has an aspect ratio of 250, and the ferroferric oxide nanoparticle has a particle size of 0.5 μm. The sample 14 to the sample 17 after the completion of the mixing were respectively formed into a film having a thickness of 50 μm to test the electromagnetic wave shielding efficiency value. The composition comprises a polymeric material and the polymeric material comprises a polymethyl methacrylate aqueous solution. The methyl methacrylate content is about 45 to 55 parts by weight, and the water is about 55 to 45 parts by weight, based on 100 parts by weight of the polymer material.
參照圖2與圖5所示,相較於圖2之實驗,樣本14至樣本17內因具較高含量之奈米銀線,故以樣本14至樣本17製作而成之薄膜可具有更低之表面電阻率。但比較圖2與圖5之實驗結果可發現,樣本14至樣本17製作而成之薄膜不因具有較低之表面電阻率而明顯改善其電磁遮蔽效率。Referring to FIG. 2 and FIG. 5, compared with the experiment of FIG. 2, since the sample 14 to the sample 17 have a relatively high content of nano silver wire, the film prepared from the sample 14 to the sample 17 can have a lower film. Surface resistivity. However, comparing the experimental results of FIG. 2 and FIG. 5, it can be found that the films prepared from the samples 14 to 17 do not significantly improve the electromagnetic shielding efficiency due to the lower surface resistivity.
例如,比較樣本5與樣本17,以樣本5製作之薄膜在頻率6~16GHz之間之電磁遮蔽效率約在36~53dB之間,而以樣本17製作之薄膜在相同頻率範圍內,其電磁遮蔽效率約在較低之9~52dB之範圍。由此隨著線材濃度的增加,粒子在相近的濃度下增大其粒徑,似乎對高頻的影響越顯著。For example, comparing sample 5 with sample 17, the film produced by sample 5 has an electromagnetic shielding efficiency between 36 and 53 dB at a frequency of 6 to 16 GHz, and the film produced with sample 17 is in the same frequency range with electromagnetic shielding. The efficiency is about the lower 9~52dB range. As the concentration of the wire increases, the particles increase their particle size at similar concentrations, and the effect on the high frequency appears to be more pronounced.
又,參照圖5所示,比較樣本14至樣本16製作而成之薄膜之電磁遮蔽效率,在大部分頻率範圍中,電磁遮蔽效率隨著四氧化三鐵奈米粒子之含量增加而改進,其中相較於未添加四氧化三鐵奈米粒子之薄膜而言,薄膜添加1.2重量份之四氧化三鐵奈米粒子後,電磁遮蔽效率有較明顯之改善。同樣地,當添加更多的四氧化三鐵奈米粒子,如樣本17之1.79重量份之四氧化三鐵奈米粒子時,電磁遮蔽效率則反而降低。因此,當四氧化三鐵奈米粒子粒徑為300~700奈米,奈米銀線長徑比為200~300,薄膜材料中之奈米線材增加至3重量份以上時,四氧化三鐵奈米粒子的含量可介於0.1~3重量份、介於0.2~2重量份或介於0.3~2重量份。Further, referring to FIG. 5, the electromagnetic shielding efficiency of the film prepared from the sample 14 to the sample 16 is compared, and in most of the frequency range, the electromagnetic shielding efficiency is improved as the content of the ferroferric oxide particles increases. Compared with the film in which the Fe3O4 nanoparticles are not added, the electromagnetic shielding efficiency is significantly improved after the film is added with 1.2 parts by weight of the ferroferric oxide particles. Similarly, when more ferroferric oxide nanoparticles, such as 1.79 parts by weight of ferrotitanium tetraoxide particles of sample 17, are added, the electromagnetic shielding efficiency is instead reduced. Therefore, when the particle diameter of the ferroferric oxide nanoparticle is 300 to 700 nm, the aspect ratio of the nano silver wire is 200 to 300, and the thickness of the nanowire in the film material is increased to more than 3 parts by weight, the ferroferric oxide The content of the nanoparticles may be 0.1 to 3 parts by weight, 0.2 to 2 parts by weight or 0.3 to 2 parts by weight.
此外,從圖2與圖3的實驗比較可以得知,使用高長徑比之奈米線材有助於薄膜之電磁遮蔽效率的提升。又,再參照圖10所示,若將薄膜材料中之奈米線材增加至3重量份以上時,無法明顯提昇其電磁遮蔽效率;反而,若在薄膜材料中添加不同尺寸的奈米的金屬或導磁粒子,則可以改變薄膜材料在高頻頻段上電磁波的光程差,而可有效提升遮蔽率。In addition, it can be seen from the comparison of the experiments of FIG. 2 and FIG. 3 that the use of a nanometer wire having a high aspect ratio contributes to an improvement in the electromagnetic shielding efficiency of the film. Moreover, referring to FIG. 10, if the nanowire in the film material is increased to more than 3 parts by weight, the electromagnetic shielding efficiency cannot be significantly improved; instead, if a different size of nano metal is added to the film material or The magnetically permeable particles can change the optical path difference of the electromagnetic wave of the film material in the high frequency band, and can effectively improve the shielding rate.
實驗範例5Experimental example 5
以組合物為100重量份計,表5之組合物(樣本18至樣本21)包含10.45重量份之奈米銀線以及分別包含含量介於0~1.87重量份之四氧化三鐵奈米粒子,其中奈米銀線之長徑比為250,而四氧化三鐵奈米粒子之粒徑為30奈米。混合完成後之樣本18至樣本21分別製作成厚度50微米之薄膜,以測試電磁波遮蔽效率值。組合物包含高分子材料,而高分子材料包含聚甲基丙烯酸甲酯水溶液。若以高分子材料為100重量份計,甲基丙烯酸甲酯之含量約為45~55重量份,而水約為55~45重量份。The composition of Table 5 (Sample 18 to Sample 21) contained 10.45 parts by weight of nano silver wire and contained ferrotitanium tetraoxide particles each having a content of 0 to 1.87 parts by weight, based on 100 parts by weight of the composition. The nano silver wire has a length to diameter ratio of 250, and the ferroferric oxide nanoparticle has a particle size of 30 nm. The sample 18 to the sample 21 after the completion of the mixing were respectively formed into a film having a thickness of 50 μm to test the electromagnetic wave shielding efficiency value. The composition comprises a polymeric material and the polymeric material comprises a polymethyl methacrylate aqueous solution. The methyl methacrylate content is about 45 to 55 parts by weight, and the water is about 55 to 45 parts by weight, based on 100 parts by weight of the polymer material.
參照圖2與圖6所示,相較於圖2之實驗,樣本18至樣本21內具較高含量之奈米銀線,故以樣本18至樣本21製作而成之薄膜可具有更低之表面電阻率。但比較圖2與圖5之實驗結果可發現,樣本18至樣本21製作而成之薄膜不因具有較低之表面電阻率而明顯改善其電磁遮蔽效率。以例言,比較樣本5與樣本21,以樣本5製作之薄膜在頻率4~16GHz之間之電磁遮蔽效率約在36~48dB之間,而樣本21製作之薄膜在相同頻率範圍內,其電磁波效率約在較低之25~37dB之範圍間。Referring to FIG. 2 and FIG. 6, compared with the experiment of FIG. 2, the sample 18 to the sample 21 have a higher content of nano silver wire, so the film made from the sample 18 to the sample 21 can have a lower film. Surface resistivity. Comparing the experimental results of FIG. 2 and FIG. 5, it can be found that the films prepared from the samples 18 to 21 do not significantly improve the electromagnetic shielding efficiency due to the lower surface resistivity. By way of example, comparing sample 5 with sample 21, the electromagnetic shielding efficiency of the film made with sample 5 at a frequency between 4 and 16 GHz is between 36 and 48 dB, while the film produced by sample 21 is in the same frequency range, and the electromagnetic wave is Efficiency is around the lower 25 to 37 dB range.
另,比較樣本18至樣本21製作而成之薄膜之電磁遮蔽效率,電磁遮蔽效率隨著四氧化三鐵奈米粒子之含量增加而改進,其中相較於未添加四氧化三鐵奈米粒子之薄膜而言,添加1.87重量份之四氧化三鐵奈米粒子之薄膜大體上具有較佳之電磁遮蔽效率。因此,當四氧化三鐵奈米粒子粒徑為10~50奈米,奈米銀線長徑比為200~300,薄膜材料中之奈米線材增加至10.45重量份時,四氧化三鐵奈米粒子的含量可介於0.4~2.6重量份、介於0.6~2.4重量份或介於1~2重量份之間。In addition, comparing the electromagnetic shielding efficiency of the film prepared from sample 18 to sample 21, the electromagnetic shielding efficiency is improved as the content of the ferroferric oxide nanoparticle increases, which is compared with the addition of the ferroferric oxide nanoparticle. In the case of a film, a film in which 1.87 parts by weight of triiron tetroxide particles are added generally has a better electromagnetic shielding efficiency. Therefore, when the particle diameter of the ferroferric oxide nanoparticle is 10 to 50 nm, the aspect ratio of the nano silver wire is 200 to 300, and the nanowire of the film material is increased to 10.45 parts by weight, the triiron tetanate The content of the rice particles may be between 0.4 and 2.6 parts by weight, between 0.6 and 2.4 parts by weight or between 1 and 2 parts by weight.
故,從圖5與圖6可以得知,當銀線的添加到達一定的程度(可再參照圖8~10),增加銀線的添加量對於薄膜材料之電磁遮蔽效率的提升有限,反而是藉由添加特定的濃度下之奈米粒子,會使薄膜材料對高頻的遮蔽率有預期外的提升。Therefore, it can be seen from FIG. 5 and FIG. 6 that when the addition of the silver wire reaches a certain degree (refer to FIGS. 8 to 10 again), increasing the addition amount of the silver wire has a limited improvement in the electromagnetic shielding efficiency of the film material, but instead By adding nanoparticles at specific concentrations, the masking rate of the film material to the high frequency is expected to increase.
實驗範例6Experimental example 6
以組合物為100重量份計,表6之組合物(樣本22至樣本25)均包含1.14重量份之奈米銀線以及分別包含含量介於0~1.99重量份之銀奈米粒子;而樣本26則僅包含7.65重量份之銀奈米粒子,但未包含奈米銀線,其中奈米銀線之長徑比為250,而銀奈米粒子之粒徑為100奈米。混合完成後之樣本22至樣本26分別製作成厚度50微米之薄膜,以測試電磁波遮蔽效率值。組合物包含高分子材料,而高分子材料包含聚甲基丙烯酸甲酯水溶液。若以高分子材料為100重量份計,甲基丙烯酸甲酯之含量約為45~55重量份,而水約為55~45重量份。The composition of Table 6 (sample 22 to sample 25) contained 1.14 parts by weight of nano silver wire and silver nanoparticles containing content of 0 to 1.99 parts by weight, respectively, based on 100 parts by weight of the composition; 26 contains only 7.65 parts by weight of silver nanoparticles, but does not contain nano silver wires, wherein the nano silver wire has an aspect ratio of 250, and the silver nanoparticles have a particle diameter of 100 nm. The sample 22 to the sample 26 after the completion of the mixing were respectively formed into a film having a thickness of 50 μm to test the electromagnetic wave shielding efficiency value. The composition comprises a polymeric material and the polymeric material comprises a polymethyl methacrylate aqueous solution. The methyl methacrylate content is about 45 to 55 parts by weight, and the water is about 55 to 45 parts by weight, based on 100 parts by weight of the polymer material.
參照圖7所示,相較於圖4之實驗,樣本23至樣本26內具導電之銀奈米粒子,故以樣本23至樣本26製作而成之薄膜可具有更低之表面電阻率。但比較圖4與圖7之實驗結果可發現,樣本23至樣本26製作而成之薄膜不因具有較低之表面電阻率而具較佳之電磁遮蔽效率。舉例而言,比較樣本12與樣本24,除在頻率4.8GHz所發生之共振模態(resonant mode)外,樣本12在所示頻段間之電磁遮蔽效率係介於18至29 dB之間,而樣本24之電磁遮蔽效率係介於19至30 dB之間,兩者幾無差異。從前述實驗結果可知,對薄膜的而言,添加銀奈米粒子的薄膜與添加導磁粒子的薄膜,兩者的電磁遮蔽效率無明顯的差異。Referring to FIG. 7, compared to the experiment of FIG. 4, the sample 23 to the sample 26 have conductive silver nanoparticles, so that the film prepared from the sample 23 to the sample 26 can have a lower surface resistivity. However, comparing the experimental results of FIG. 4 and FIG. 7, it can be found that the films prepared from the samples 23 to 26 do not have better electromagnetic shielding efficiency due to the lower surface resistivity. For example, comparing sample 12 to sample 24, the electromagnetic shielding efficiency of sample 12 between the indicated bands is between 18 and 29 dB, except for the resonant mode occurring at a frequency of 4.8 GHz. The electromagnetic shielding efficiency of sample 24 is between 19 and 30 dB, with no difference. From the above experimental results, it is understood that there is no significant difference in electromagnetic shielding efficiency between the film in which the silver nanoparticles are added and the film in which the magnetic particles are added.
因此,當銀奈米粒子粒徑為80~120奈米,奈米銀線長徑比為200~300的情況下,銀奈米粒子的含量可介於0.5~2.5重量份或介於0.7~2重量份。Therefore, when the silver nanoparticles have a particle diameter of 80 to 120 nm and the nano silver wire has a length to diameter ratio of 200 to 300, the content of the silver nanoparticles may be 0.5 to 2.5 parts by weight or 0.7 to 0.7. 2 parts by weight.
除此之外,比較樣本22至樣本25製作而成之薄膜之電磁遮蔽效率,薄膜中單純加入線材的電磁遮蔽效率較薄膜中只有加入粒子的效果好,電磁遮蔽效率隨著銀奈米粒子之含量增加而改進,而若將導磁粒子改為導電粒子時,似乎都具有一定的電磁波遮避率。圖12顯示兩薄膜之電磁遮蔽效率之測試結果圖,其中該兩薄膜係以雙酚A環氧樹脂BE188(來源:長春人造樹酯公司(Chang Chun Plastics Co.,Ltd),台灣)為載體所製備。兩薄膜係分別以兩組合物所製成,其中兩組合物包含長徑比為80且濃度為2.06重量份之奈米線材,以及包含粒徑為50奈米而濃度分別為0重量份及0.65重量份之奈米粒子。經實驗後發現,即便將載體之材料由壓克力樹脂改為雙酚A環氧樹脂(bisphenol A type epoxy,) BE188(來源:長春人造樹酯公司(Chang Chun Plastics Co.,Ltd),台灣),載體中添加奈米粒子後,以其製成之薄膜之電磁遮蔽效率仍可提升。因此加入特定比例的奈米粒子所造成預期外的效應,並不會受到使用不同之高分子材料而受影響。In addition, comparing the electromagnetic shielding efficiency of the film made from sample 22 to sample 25, the electromagnetic shielding efficiency of simply adding the wire in the film is better than that of adding only particles in the film, and the electromagnetic shielding efficiency is the same as that of the silver nanoparticle. The content is improved and improved, and if the magnetic conductive particles are changed to conductive particles, it seems to have a certain electromagnetic wave avoidance rate. Figure 12 is a graph showing the results of the electromagnetic shielding efficiency of the two films, wherein the two films are based on bisphenol A epoxy resin BE188 (source: Changchun Plastics Co., Ltd., Taiwan). preparation. The two film systems are respectively prepared as a two-component compound, wherein the two components comprise a nanowire having an aspect ratio of 80 and a concentration of 2.06 parts by weight, and a particle diameter of 50 nm and a concentration of 0 parts by weight and 0.65, respectively. Parts by weight of nanoparticles. After the experiment, it was found that even the material of the carrier was changed from acrylic resin to bisphenol A type epoxy (BE188) (Source: Changchun Plastics Co., Ltd., Taiwan) After the addition of the nanoparticles to the carrier, the electromagnetic shielding efficiency of the film made therefrom can be improved. Therefore, the addition of a specific proportion of nanoparticles causes an unexpected effect and is not affected by the use of different polymeric materials.
利用本揭露具有奈米線材與奈米粒子之組合物所製成之薄膜具有優異之電磁波遮蔽效果。The film made of the composition having a nanowire and a nanoparticle has an excellent electromagnetic wave shielding effect.
表7Table 7
由表7與圖13之結果可以得知,利用樣本4製成之具奈米結構之電磁波遮蔽材料,較使用傳統金屬圓形粒子之習知產品(B及C)所製成之薄膜有較佳之EMI防護效果。而且,相較於市售具高含量之粒子之相關產品,本揭露之組合物A中僅需添加低含量之奈米材料,即可有更高電磁波遮蔽值。From the results of Table 7 and Figure 13, it can be seen that the electromagnetic wave shielding material having the nano structure made of the sample 4 is more than the film made by the conventional products (B and C) of the conventional metal circular particles. Good EMI protection. Moreover, in the composition A of the present disclosure, only a low content of the nano material is required to have a higher electromagnetic wave shielding value than a commercially available product having a high content of particles.
參照圖14所示,本揭露另揭示一種電磁屏蔽裝置10。電磁屏蔽裝置10包含一本體11以及一薄膜12,其中本體11具一表面13,而薄膜12形成於該表面13上,以提供電磁波遮蔽。薄膜12可包含複數根奈米金屬線材及複數個奈米粒子。複數根奈米金屬線材與複數個奈米粒子分別均勻散佈於薄膜12中且彼此混合,其中以該薄膜12為100重量份計,該些奈米金屬線材介於1重量份至95重量份;以該薄膜12為100重量份計,該些奈米粒子介於0.5重量份至60重量份。本體11可為任意需塗佈薄膜12,以遮蔽電磁波之對象,例如:本體11可為線材、板材、高分子膜或機殼等。Referring to FIG. 14, the present disclosure further discloses an electromagnetic shielding device 10. The electromagnetic shielding device 10 includes a body 11 and a film 12, wherein the body 11 has a surface 13 on which the film 12 is formed to provide electromagnetic wave shielding. The film 12 can comprise a plurality of nanowires and a plurality of nanoparticles. a plurality of nanowires and a plurality of nanoparticles are uniformly dispersed in the film 12 and mixed with each other, wherein the nanowires are between 1 part by weight and 95 parts by weight based on 100 parts by weight of the film 12; The nanoparticles are contained in an amount of from 0.5 part by weight to 60 parts by weight based on 100 parts by weight of the film. The body 11 can be any object that needs to be coated with the film 12 to shield electromagnetic waves. For example, the body 11 can be a wire, a plate, a polymer film or a casing.
參照圖15所示,本揭露另揭示一種抗靜電裝置20。抗靜電裝置20包含一基板21以及一薄膜22,其中基板21具一表面23,而薄膜22形成於該表面23上,以提供電磁波遮蔽。薄膜22可包含複數根奈米金屬線材及複數個奈米粒子。複數根奈米金屬線材與複數個奈米粒子分別均勻散佈於薄膜22中且彼此混合,其中以該薄膜為100重量份計,該些奈米金屬線材佔薄膜22之總重量為1重量份至95重量份;該些奈米粒子佔薄膜22之總重量為0.5重量份至60重量份。Referring to Figure 15, the present disclosure further discloses an antistatic device 20. The antistatic device 20 includes a substrate 21 and a film 22, wherein the substrate 21 has a surface 23 on which the film 22 is formed to provide electromagnetic wave shielding. The film 22 can comprise a plurality of nanowires and a plurality of nanoparticles. The plurality of nanowires and the plurality of nanoparticles are uniformly dispersed in the film 22 and mixed with each other, wherein the nanowires comprise 1 part by weight of the total weight of the film 22, based on 100 parts by weight of the film. 95 parts by weight; the nanoparticles are from 0.5 part by weight to 60 parts by weight based on the total weight of the film 22.
綜合上述,在含有奈米金屬線材之組合物內添加適量的導磁或金屬奈米粒子,可改善以該組合物所製成之薄膜之電磁遮蔽效率。根據前述諸實施範例之結果,以組合物為100重量份,奈米金屬線材之含量可介於1重量份至95重量份、介於1重量份至11重量份或介於1重量份至3重量份。又,導磁或金屬奈米粒子之含量可介於0.1重量份至60重量份、介於0.1重量份至10重量份、介於0.5重量份至10重量份或介於0.5重量份至2重量份。In summary, by adding an appropriate amount of magnetic conductive or metallic nanoparticles to the composition containing the nanowire, the electromagnetic shielding efficiency of the film made of the composition can be improved. According to the results of the foregoing embodiments, the content of the nano metal wire may be from 1 part by weight to 95 parts by weight, from 1 part by weight to 11 parts by weight or from 1 part by weight to 3 parts by weight of the composition. Parts by weight. Further, the content of the magnetic conductive or metallic nanoparticles may be from 0.1 part by weight to 60 parts by weight, from 0.1 part by weight to 10 parts by weight, from 0.5 part by weight to 10 parts by weight, or from 0.5 part by weight to 2 parts by weight. Share.
此外,在含有奈米金屬線材之組合物內添加大量的導磁或金屬奈米粒子,其電磁遮蔽效率無明顯地提昇。另,在薄膜內添加絕緣導磁奈米粒子,較以提高導電性而增加奈米金屬線材或添加金屬奈米顆粒之薄膜,其電磁遮蔽效率之改善更為明顯。Further, by adding a large amount of magnetic conductive or metallic nanoparticles to the composition containing the nanowire, the electromagnetic shielding efficiency is not significantly improved. In addition, the addition of the insulating magnetic nanoparticles to the film increases the electromagnetic shielding efficiency of the nanowire or the metal nanoparticle by increasing the conductivity.
圖16顯示本揭露一實施例之電磁屏蔽結構30之示意圖。電磁屏蔽結構30包含一目標物31及一薄膜32。電磁屏蔽結構30之製備方法包含下列步驟:提供目標物31;以塗佈或噴塗等方式,在目標物31上形成薄膜32;以及利用光照或烘箱加熱薄膜32至一溫度,其中該溫度介於攝氏50度至攝氏250度之間。薄膜32之組成如表8所列示。組合物被配置以供塗佈或噴塗。組合物可包含奈米銀線和高分子材料。在一些實施例中,組合物更包含奈米顆粒。高分子材料可包含聚胺甲酸酯(polyurethane)和水,其中以高分子材料為100重量份計,聚胺甲酸酯之含量約為45~55重量份,而水約為55~45重量份。FIG. 16 shows a schematic diagram of an electromagnetic shielding structure 30 in accordance with an embodiment of the present disclosure. The electromagnetic shielding structure 30 includes a target 31 and a film 32. The method for preparing the electromagnetic shielding structure 30 comprises the steps of: providing a target 31; forming a film 32 on the target 31 by coating or spraying; and heating the film 32 to a temperature by illumination or an oven, wherein the temperature is between 50 degrees Celsius to 250 degrees Celsius. The composition of film 32 is as listed in Table 8. The composition is configured for coating or spraying. The composition may comprise nano silver wires and polymeric materials. In some embodiments, the composition further comprises nanoparticle. The polymer material may comprise polyurethane and water, wherein the content of the polyurethane is about 45 to 55 parts by weight, and the water is about 55 to 45 weights, based on 100 parts by weight of the polymer material. Share.
圖17顯示在本發明一實施例中以具有2.43重量份的銀奈米線和1.45重量份的四氧化三鐵粒子的混合材料所製作的薄膜,在頻率0~1800MHz間之電磁波遮蔽效率值之量測圖。圖18顯示在本發明一實施例中以具有2.43重量份的銀奈米線和1.45重量份的四氧化三鐵粒子的混合材料所製作的薄膜,在頻率1~18GHz間之電磁波遮蔽效率值之量測圖。塗佈樣本27於一目標物上,然後再將以攝氏80度加熱5分鐘,以製作成厚度50微米之薄膜。之後,量測該薄膜之電磁波遮蔽效率值。從圖17與18之量測結果可得知,薄膜以攝氏80度加熱5分鐘後,在頻率介於1至1800MHz之間,其電磁波遮蔽效率有顯著的提升;而在高頻範圍平均,其電磁波遮蔽效率值可高於40dB。Figure 17 is a view showing an electromagnetic wave shielding efficiency value at a frequency of 0 to 1800 MHz, which is a film made of a mixed material of 2.43 parts by weight of silver nanowires and 1.45 parts by weight of ferroferric oxide particles in an embodiment of the present invention. Measurement chart. Figure 18 is a view showing an electromagnetic wave shielding efficiency value at a frequency of 1 to 18 GHz in a film made of a mixed material of 2.43 parts by weight of silver nanowires and 1.45 parts by weight of ferroferric oxide particles in an embodiment of the present invention. Measurement chart. The sample 27 was coated on a target and then heated at 80 degrees Celsius for 5 minutes to form a film having a thickness of 50 μm. Thereafter, the electromagnetic wave shielding efficiency value of the film was measured. From the measurement results of Figs. 17 and 18, it can be seen that after the film is heated at 80 degrees Celsius for 5 minutes, the electromagnetic wave shielding efficiency is significantly improved at a frequency between 1 and 1800 MHz; and in the high frequency range, it is averaged. The electromagnetic wave shielding efficiency value can be higher than 40 dB.
圖19顯示以具有2.43重量份的銀奈米線和1.45重量份的四氧化三鐵粒子的混合材料所製作的薄膜,其電磁波遮蔽效率值與加熱時間之關係圖。將樣本27塗佈在一目標物上,再以攝氏80度加熱5分鐘,以製作出厚度30微米之薄膜。薄膜再以攝氏150度,經不同的加熱時間烘烤。然後,量測經不同加熱時間烘烤之薄膜之電磁波遮蔽效率值,可得到如圖19所示之結果。從圖19顯示的結果可看出,當薄膜加熱1小時以上,其電磁波遮蔽效率值可提高10dB以上。若在攝氏150度,經72小時烘烤,其電磁波遮蔽效率值更可達到40dB以上。Fig. 19 is a graph showing the relationship between the electromagnetic wave shielding efficiency value and the heating time of a film made of a mixed material of 2.43 parts by weight of silver nanowires and 1.45 parts by weight of triiron tetroxide particles. The sample 27 was coated on a target and heated at 80 ° C for 5 minutes to produce a film having a thickness of 30 μm. The film is then baked at 150 degrees Celsius and heated for different heating times. Then, the electromagnetic wave shielding efficiency values of the films baked at different heating times were measured, and the results shown in Fig. 19 were obtained. As can be seen from the results shown in Fig. 19, when the film is heated for more than 1 hour, the electromagnetic wave shielding efficiency value can be increased by 10 dB or more. If it is baked at 150 degrees Celsius for 72 hours, the electromagnetic wave shielding efficiency value can reach more than 40dB.
圖20顯示以具有2.43重量份的銀奈米線和1.45重量份的四氧化三鐵粒子的混合材料所製作的薄膜,其電磁波遮蔽效率值與加熱溫度間之關係圖。將樣本27塗佈在一目標物上,再以攝氏80度加熱5分鐘,以製作出厚度20微米之薄膜。薄膜再以固定1小時的時間,在不同的加熱溫度下加熱。然後,量測在不同溫度下加熱之薄膜之電磁波遮蔽效率值,可得到如圖20所示之結果。從圖20顯示的結果可得知,薄膜之電磁波遮蔽效率值隨加熱溫度的增加而增加。因此,薄膜可利用調整加熱溫度,來獲得所需之電磁波遮蔽效率值。此外,經過圖20顯示之溫度加熱之薄膜均可通過鉛筆硬度B及附著度4B等的測試。Fig. 20 is a graph showing the relationship between the electromagnetic wave shielding efficiency value and the heating temperature of a film made of a mixed material of 2.43 parts by weight of silver nanowires and 1.45 parts by weight of ferroferric oxide particles. The sample 27 was coated on a target and heated at 80 ° C for 5 minutes to produce a film having a thickness of 20 μm. The film was then heated at different heating temperatures for a fixed period of 1 hour. Then, the electromagnetic wave shielding efficiency values of the films heated at different temperatures were measured, and the results shown in Fig. 20 were obtained. As can be seen from the results shown in Fig. 20, the electromagnetic wave shielding efficiency value of the film increases as the heating temperature increases. Therefore, the film can be adjusted to the heating temperature to obtain the desired electromagnetic wave shielding efficiency value. Further, the film heated at the temperature shown in Fig. 20 can be tested by pencil hardness B and adhesion degree 4B.
圖21顯示在本發明一實施例中以具3.49重量份之銀奈米線和2.18重量份之四氧化三鐵粒子之混合材料所製作之薄膜,在頻率0~1800MHz間之電磁波遮蔽效率值之量測圖。圖22顯示在本發明一實施例中以具3.49重量份之銀奈米線和2.18重量份之四氧化三鐵粒子之混合材料所製作之薄膜,在頻率1~18GHz間之電磁波遮蔽效率值之量測圖。塗佈樣本28於一目標物上,然後再將以攝氏80度加熱5分鐘,以製作成厚度80微米之薄膜。之後,量測該薄膜之電磁波遮蔽效率值。從圖21與22之量測結果可得知,薄膜以攝氏80度加熱5分鐘後,其電磁波遮蔽效率值可高於40dB。再者,由於混合四氧化三鐵粒子與銀奈米線,因此使薄膜可產生多重散射與吸收效應,故可得到較佳的電磁波遮蔽效率。Figure 21 is a view showing an electromagnetic wave shielding efficiency value at a frequency of 0 to 1800 MHz in a film made of a mixed material of 3.49 parts by weight of silver nanowires and 2.18 parts by weight of ferroferric oxide particles in an embodiment of the present invention. Measurement chart. Figure 22 is a view showing an electromagnetic wave shielding efficiency value at a frequency of 1 to 18 GHz in a film made of a mixed material of 3.49 parts by weight of silver nanowires and 2.18 parts by weight of ferroferric oxide particles in an embodiment of the present invention. Measurement chart. The sample 28 was coated on a target and then heated at 80 degrees Celsius for 5 minutes to form a film having a thickness of 80 μm. Thereafter, the electromagnetic wave shielding efficiency value of the film was measured. From the measurement results of Figs. 21 and 22, it can be known that after the film is heated at 80 degrees Celsius for 5 minutes, the electromagnetic wave shielding efficiency value can be higher than 40 dB. Furthermore, since the ferroferric oxide particles and the silver nanowire are mixed, the film can generate multiple scattering and absorption effects, so that better electromagnetic wave shielding efficiency can be obtained.
圖23顯示在本發明一實施例中以具有2.1重量份的銀奈米線和0.55重量份的四氧化三鐵粒子的混合材料所製作的薄膜,經不同加熱時間與加熱溫度後,其在頻率0~1800MHz間之電磁波遮蔽效率值之量測圖。塗佈樣本29於一目標物上,然後再將以攝氏80度加熱5分鐘,以製作成厚度70微米之薄膜。量測該薄膜之電磁波遮蔽效率可得如圖23顯示之結果。又,將薄膜放置於烘箱中,以攝氏150度、24小時再次烘烤,接著測試其電磁波遮蔽效率,可得如圖23顯示之結果。比較圖23顯示之結果可知,薄膜若再24小時、攝氏150度的烘烤,其電磁波遮蔽效率值可提昇10dB。Figure 23 is a view showing a film made of a mixed material of 2.1 parts by weight of silver nanowires and 0.55 parts by weight of triiron tetroxide particles in an embodiment of the present invention, after different heating times and heating temperatures, at a frequency Measure the electromagnetic wave shielding efficiency value between 0 and 1800 MHz. The sample 29 was coated on a target and then heated at 80 degrees Celsius for 5 minutes to form a film having a thickness of 70 μm. Measuring the electromagnetic wave shielding efficiency of the film can be as shown in Fig. 23. Further, the film was placed in an oven and baked again at 150 ° C for 24 hours, and then the electromagnetic wave shielding efficiency was tested, and the results as shown in Fig. 23 were obtained. Comparing the results shown in Fig. 23, it can be seen that if the film is baked for another 24 hours and 150 degrees Celsius, the electromagnetic wave shielding efficiency value can be increased by 10 dB.
圖24顯示在本發明一實施例中以具1.09重量份之銀奈米粒子和3.69重量份之四氧化三鐵粒子之混合材料所製作之薄膜,經不同加熱時間後,其在頻率100~1800MHz間之電磁波遮蔽效率值之量測圖。塗佈樣本30於一目標物上,然後再將以攝氏80度加熱5分鐘,以製作成厚度30微米之薄膜。之後,薄膜在不同的溫度下,加熱1小時。然後,量測薄膜之電磁波遮蔽效率,其結果如圖24所顯示。從圖24顯示的結果可看出,加熱攝氏80度以上,可使薄膜的電磁波遮蔽效率值提昇超過40dB。Figure 24 is a view showing a film made of a mixed material of 1.09 parts by weight of silver nanoparticles and 3.69 parts by weight of ferroferric oxide particles in an embodiment of the present invention, which has a frequency of 100 to 1800 MHz after different heating times. A measure of the electromagnetic wave shielding efficiency value between. The sample 30 was coated on a target and then heated at 80 degrees Celsius for 5 minutes to form a film having a thickness of 30 μm. Thereafter, the film was heated at different temperatures for 1 hour. Then, the electromagnetic wave shielding efficiency of the film was measured, and the results are shown in Fig. 24. It can be seen from the results shown in Fig. 24 that by heating above 80 degrees Celsius, the electromagnetic wave shielding efficiency value of the film can be increased by more than 40 dB.
復參圖16所示,電磁屏蔽結構30可包含目標物31、薄膜32和一黏膠層33,薄膜32設置於目標物31上,粘膠層33設置於薄膜32上。在一實施例中,黏膠層33包含感壓型黏著劑(pressure sensitive adhesive)。此外,在另一實施例中,電磁屏蔽結構30可另包含至少一第二薄膜(未繪示),其中該第二薄膜與薄膜32相疊置,可位於黏膠層33與薄膜32之間,而且薄膜32與第二薄膜可分別具有奈米粒子與奈米金屬線材。Referring to FIG. 16, the electromagnetic shielding structure 30 may include a target 31, a film 32, and an adhesive layer 33. The film 32 is disposed on the target 31, and the adhesive layer 33 is disposed on the film 32. In one embodiment, the adhesive layer 33 comprises a pressure sensitive adhesive. In addition, in another embodiment, the electromagnetic shielding structure 30 may further include at least one second film (not shown), wherein the second film overlaps the film 32 and may be located between the adhesive layer 33 and the film 32. And the film 32 and the second film may have nano particles and a nano metal wire, respectively.
圖25顯示量測未具有抗電磁干擾之薄膜之硬碟所得之電磁強度與頻率間之關係圖。圖26顯示量測具有抗電磁干擾之薄膜(樣本31)之硬碟所得之電磁場強度與頻率間之關係圖。圖25之結果為一硬碟根據歐盟電磁相容性指引標準(EU-EMC Directive(2004/108/EC) EN 55022 class B)測試而產生,其中在頻率377、486及593MHz處(數字4、5、6標示處)超過標準。將樣本31塗佈在該硬碟上,在形成厚度小於50微米之一薄膜,待薄膜乾燥後,可發現硬碟在30MHz至1.8GHz的頻率範圍符合歐盟電磁相容性指引標準。因此,以本揭露之樣本31所製作之薄膜可降低電磁干擾的產生。樣本31-32使用的高分子材料包含聚氨酯水溶液(包含45~55重量份之聚氨酯以及55~45重量份之水)。Figure 25 is a graph showing the relationship between electromagnetic strength and frequency obtained by measuring a hard disk having no anti-electromagnetic interference film. Fig. 26 is a graph showing the relationship between the electromagnetic field strength and the frequency obtained by measuring a hard disk having an electromagnetic interference resistant film (sample 31). The result of Figure 25 is that a hard disk is produced according to the EU Electromagnetic Compatibility Directive (EU-EMC Directive (2004/108/EC) EN 55022 class B), which is at frequencies 377, 486 and 593 MHz (number 4, 5, 6 marked) exceeds the standard. The sample 31 was coated on the hard disk to form a film having a thickness of less than 50 μm. After the film was dried, the hard disk was found to meet the EU electromagnetic compatibility guidelines in the frequency range of 30 MHz to 1.8 GHz. Therefore, the film produced by the sample 31 of the present disclosure can reduce the generation of electromagnetic interference. The polymer materials used in the samples 31-32 contained an aqueous polyurethane solution (containing 45 to 55 parts by weight of polyurethane and 55 to 45 parts by weight of water).
圖27顯示未具有抗電磁干擾之薄膜之錄放影機,在水平方向上對其進行量測,所得之電磁場強度與頻率間之關係圖。圖29顯示未具有抗電磁干擾之薄膜之錄放影機,在垂直方向上對其進行量測,所得之電磁場強度與頻率間之關係圖。圖28顯示具有抗電磁干擾之薄膜(樣本32)之錄放影機,在水平方向上對其進行量測,所得之電磁場強度與頻率間之關係圖。圖30顯示具有抗電磁干擾之薄膜(樣本32)之錄放影機,在垂直方向上對其進行量測,所得之電磁場強度與頻率間之關係圖。根據歐盟電磁相容性指引標準對未具有抗電磁干擾之薄膜之錄放影機進行水平方向及垂直方向上電磁波干擾之量測,可發現分別在15個頻率與17個頻率上不符合標準。而,以樣本32在該錄放影機上形成抗電磁干擾之薄膜(厚度小於50微米),待薄膜乾燥後,發現該錄放影機可符合歐盟電磁相容性指引標準。因此,以本揭露樣本32所製作之薄膜具大頻寬的電磁遮蔽效果。Figure 27 is a graph showing the relationship between the intensity of the electromagnetic field and the frequency obtained by measuring the film in a horizontal direction without a film having an anti-electromagnetic interference film. Figure 29 is a graph showing the relationship between the intensity of the electromagnetic field and the frequency obtained by measuring the film in a vertical direction without a film having an anti-electromagnetic interference film. Fig. 28 is a view showing the relationship between the intensity of the electromagnetic field and the frequency obtained by measuring the recording and reproducing machine of the film having the electromagnetic interference resistance (sample 32) in the horizontal direction. Figure 30 is a graph showing the relationship between the intensity of the electromagnetic field and the frequency obtained by measuring the film in a vertical direction with a film with anti-electromagnetic interference (sample 32). According to the EU Electromagnetic Compatibility Guidelines, the electromagnetic wave interference in the horizontal and vertical directions of the video recorders without anti-electromagnetic interference film can be found to be inconsistent with the standard at 15 frequencies and 17 frequencies. However, the film 32 was formed on the recording and reproducing machine with an electromagnetic interference resistant film (thickness less than 50 micrometers). After the film was dried, the video recorder was found to comply with the EU electromagnetic compatibility guidelines. Therefore, the film produced by the present disclosure 32 has a large bandwidth electromagnetic shielding effect.
習知電磁波的遮蔽率通常會與導電度的關係成正相關,不過,由以樣本31、32所做的實驗結果可知,當導電的金屬材料加至某一程度時,對遮蔽率的影響有限。The shielding rate of conventional electromagnetic waves is usually positively correlated with the conductivity. However, from the experimental results of the samples 31 and 32, it is known that when the conductive metal material is added to a certain extent, the influence on the shielding rate is limited.
樣本31和32中包含高分子材料,其可包含聚胺甲酸酯(polyurethane)和水,其中以高分子材料為100重量份計,聚胺甲酸酯之含量約為45~55重量份,而水約為55~45重量份。Samples 31 and 32 include a polymer material, which may include a polyurethane and water, wherein the content of the polyurethane is about 45 to 55 parts by weight based on 100 parts by weight of the polymer material. The water is about 55 to 45 parts by weight.
綜上所述,本揭露另揭示對具奈米材料之抗電磁干擾薄膜進行加熱處理,可有效提昇該薄膜之電磁波遮蔽效率值。因此,在不減電磁波遮蔽效果下,可降低使用薄膜的厚度。In summary, the disclosure further discloses that the anti-electromagnetic interference film with nano material is heat-treated, and the electromagnetic wave shielding efficiency value of the film can be effectively improved. Therefore, the thickness of the film to be used can be reduced without reducing the electromagnetic shielding effect.
本揭露之技術內容及技術特點已揭示如上,然而熟悉本項技術之人士仍可能基於本揭露之教示及揭示而作種種不背離本揭露精神之替換及修飾。因此,本揭露之保護範圍應不限於實施範例所揭示者,而應包括各種不背離本揭露之替換及修飾,並為以下之申請專利範圍所涵蓋。The technical content and technical features of the present disclosure have been disclosed as above, and those skilled in the art can still make various substitutions and modifications without departing from the spirit and scope of the disclosure. Therefore, the scope of the present disclosure is not to be construed as being limited by the scope of
10...電磁屏蔽裝置10. . . Electromagnetic shielding device
20...抗靜電裝置20. . . Antistatic device
30...電磁屏蔽結構30. . . Electromagnetic shielding structure
11...本體11. . . Ontology
12...薄膜12. . . film
13...表面13. . . surface
21...基板twenty one. . . Substrate
22...薄膜twenty two. . . film
23...表面twenty three. . . surface
31...目標物31. . . Target
32...薄膜32. . . film
33...黏膠層33. . . Adhesive layer
圖1與圖2顯示本揭露一實施範例之具不同四氧化三鐵奈米粒子含量之薄膜之電磁波遮蔽效率值對頻率之關係示意圖;1 and FIG. 2 are schematic diagrams showing the relationship between the electromagnetic wave shielding efficiency value and the frequency of a film having different content of ferroferric oxide nanoparticles according to an embodiment of the present disclosure;
圖3顯示本揭露一實施範例之複數個薄膜之電磁波遮蔽效率值對頻率之關係示意圖,其中該些薄膜包含長徑比為80之奈米銀線與分別包含不同含量之四氧化三鐵奈米粒子;3 is a schematic diagram showing the relationship between electromagnetic wave shielding efficiency values and frequency of a plurality of films according to an embodiment of the present invention, wherein the films comprise nano silver wires having an aspect ratio of 80 and respectively containing different contents of triiron tetroxide. particle;
圖4顯示本揭露一實施範例之複數個薄膜之電磁波遮蔽效率值對頻率之關係示意圖,其中該些薄膜係以包含1.14重量份之奈米銀線與分別包含不同含量之四氧化三鐵奈米粒子之組合物所製成;4 is a schematic diagram showing the relationship between electromagnetic wave shielding efficiency values and frequency of a plurality of films according to an embodiment of the present invention, wherein the films comprise 1.14 parts by weight of nano silver wire and respectively contain different contents of triiron tetanate. Made of a composition of particles;
圖5與圖6顯示本揭露一實施範例之具高奈米銀線含量之薄膜之電磁波遮蔽效率值對頻率之關係示意圖;5 and FIG. 6 are schematic diagrams showing the relationship between electromagnetic wave shielding efficiency values and frequencies of a film having a high nano silver content according to an embodiment of the present disclosure;
圖7顯示本揭露一實施範例之具奈米銀線與銀奈米粒子薄膜之電磁波遮蔽效率值對頻率之關係示意圖;7 is a schematic view showing the relationship between electromagnetic wave shielding efficiency values and frequency of a nano silver wire and a silver nanoparticle film according to an embodiment of the present disclosure;
圖8顯示本揭露一實施範例之表面電阻率對奈米線材濃度之關係圖;Figure 8 is a graph showing the relationship between surface resistivity and nanowire concentration in an embodiment of the present disclosure;
圖9顯示在使用長徑比為200之奈米銀線之條件下,材料之電磁波遮蔽效率值對表面電阻率之關係圖;Figure 9 is a graph showing the relationship between the electromagnetic wave shielding efficiency value of the material and the surface resistivity under the condition that a nano silver wire having a length to diameter ratio of 200 is used;
圖10本揭露一實施範例之複數個薄膜之電磁波遮蔽效率值對頻率之關係示意圖,其中該些薄膜係以包含1.14、3及10.45重量份之奈米銀線之組合物所製成;10 is a schematic diagram showing the relationship between electromagnetic wave shielding efficiency values and frequency of a plurality of films according to an embodiment, wherein the films are made of a composition comprising 1.14, 3, and 10.45 parts by weight of nano silver wire;
圖11顯示具有不同長徑比之材料,其電磁波遮蔽效率值對體積百分比之關係圖;Figure 11 is a graph showing the relationship between the electromagnetic wave shielding efficiency value and the volume percentage of materials having different aspect ratios;
圖12顯示使用環氧樹脂為載體且混入不同濃度之奈米粒子之組合物,其電磁波遮蔽效率值對頻率之關係示意圖;Figure 12 is a graph showing the relationship between electromagnetic wave shielding efficiency values and frequency using a composition in which an epoxy resin is used as a carrier and mixed with nanoparticles of different concentrations;
圖13顯示本揭露之組合物與習知產品之電磁波遮蔽效率值對頻率之關係示意圖;Figure 13 is a graph showing the relationship between the electromagnetic wave shielding efficiency value and the frequency of the composition of the present disclosure and a conventional product;
圖14顯示本揭露一實施範例之電磁屏蔽裝置之示意圖;Figure 14 is a schematic view showing an electromagnetic shielding device according to an embodiment of the present disclosure;
圖15顯示本揭露一實施範例之抗靜電裝置之示意圖;Figure 15 is a schematic view showing an antistatic device according to an embodiment of the present disclosure;
圖16顯示本揭露一實施例之電磁屏蔽結構之示意圖;Figure 16 is a schematic view showing an electromagnetic shielding structure according to an embodiment of the present disclosure;
圖17顯示在本發明一實施例中以具2.43重量份之銀奈線和1.45重量份的四氧化三鐵粒子之混合材料所製作之薄膜,在頻率0~1800MHz間之電磁波遮蔽效率值之量測圖;Figure 17 is a view showing the amount of electromagnetic wave shielding efficiency at a frequency of 0 to 1800 MHz in a film made of a mixed material of 2.43 parts by weight of a silver wire and 1.45 parts by weight of a ferroferric oxide particle in an embodiment of the present invention. Mapping
圖18顯示在本發明一實施例中以具2.43重量份之銀奈線和1.45重量份的四氧化三鐵粒子之混合材料所製作之薄膜,在頻率1~18GHz間之電磁波遮蔽效率值之量測圖;Fig. 18 is a view showing the amount of electromagnetic wave shielding efficiency at a frequency of 1 to 18 GHz in a film made of a mixed material of 2.43 parts by weight of silver nene and 1.45 parts by weight of ferroferric oxide particles in an embodiment of the present invention. Mapping
圖19顯示以具2.43重量份之銀奈線和1.45重量份的四氧化三鐵粒子之混合材料所製作之薄膜,其電磁波遮蔽效率值與加熱時間之關係圖;Figure 19 is a graph showing the relationship between the electromagnetic shielding efficiency value and the heating time of a film made of a mixed material of 2.43 parts by weight of a silver nene line and 1.45 parts by weight of a ferroferric oxide particle;
圖20顯示以具2.43重量份之銀奈線和1.45重量份的四氧化三鐵粒子之混合材料所製作之薄膜,其電磁波遮蔽效率值與加熱溫度間之關係圖;Figure 20 is a graph showing the relationship between the electromagnetic shielding efficiency value and the heating temperature of a film made of a mixed material of 2.43 parts by weight of a silver nene line and 1.45 parts by weight of a ferroferric oxide particle;
圖21顯示在本發明一實施例中以具3.49重量份之銀奈米粒子和2.18重量份之四氧化三鐵粒子之混合材料所製作之薄膜,在頻率0~1800MHz間之電磁波遮蔽效率值之量測圖;Figure 21 is a view showing an electromagnetic wave shielding efficiency value at a frequency of 0 to 1800 MHz in a film made of a mixed material of 3.49 parts by weight of silver nanoparticles and 2.18 parts by weight of ferroferric oxide particles in an embodiment of the present invention. Measurement map
圖22顯示在本發明一實施例中以具3.49重量份之銀奈米粒子和2.18重量份之四氧化三鐵粒子之混合材料所製作之薄膜,在頻率1~18GHz間之電磁波遮蔽效率值之量測圖;Figure 22 is a view showing an electromagnetic wave shielding efficiency value at a frequency of 1 to 18 GHz in a film made of a mixed material of 3.49 parts by weight of silver nanoparticles and 2.18 parts by weight of ferroferric oxide particles in an embodiment of the present invention. Measurement map
圖23顯示在本發明一實施例中以具2.1重量份之銀奈米線和0.55重量份之四氧化三鐵粒子之混合材料所製作之薄膜,經不同加熱時間與加熱溫度後,其在頻率0~1800MHz間之電磁波遮蔽效率值之量測圖;Figure 23 is a view showing a film made of a mixed material of 2.1 parts by weight of silver nanowires and 0.55 parts by weight of ferroferric oxide particles in an embodiment of the present invention, after different heating time and heating temperature, at a frequency Measure the electromagnetic wave shielding efficiency value between 0 and 1800 MHz;
圖24顯示在本發明一實施例中以具1.09重量份之銀奈米粒子和3.69重量份之四氧化三鐵粒子之混合材料所製作之薄膜,在不同的加熱溫度下,其在頻率100~1800MHz間之電磁波遮蔽效率值之量測圖;Figure 24 is a view showing a film made of a mixed material of 1.09 parts by weight of silver nanoparticles and 3.69 parts by weight of ferroferric oxide particles in an embodiment of the present invention, at a different heating temperature, at a frequency of 100~ a measurement map of electromagnetic wave shielding efficiency values between 1800 MHz;
圖25顯示量測未具有抗電磁干擾之薄膜之硬碟所得之電磁強度與頻率間之關係圖;Figure 25 is a graph showing the relationship between electromagnetic strength and frequency obtained by measuring a hard disk having no anti-electromagnetic interference film;
圖26顯示量測具有抗電磁干擾之薄膜之硬碟所得之電磁場強度與頻率間之關係圖;Figure 26 is a graph showing the relationship between the electromagnetic field strength and the frequency obtained by measuring a hard disk having a film resistant to electromagnetic interference;
圖27顯示未具有抗電磁干擾之薄膜之錄放影機,在水平方向上對其進行量測,所得之電磁場強度與頻率間之關係圖;Figure 27 is a view showing the relationship between the intensity of the electromagnetic field and the frequency obtained by measuring the film in a horizontal direction without a film having an anti-electromagnetic interference film;
圖28顯示具有抗電磁干擾之薄膜之硬碟,在水平方向上對其進行量測,所得之電磁場強度與頻率間之關係圖;Figure 28 is a graph showing the relationship between the obtained electromagnetic field strength and the frequency of a hard disk having a film resistant to electromagnetic interference, measured in a horizontal direction;
圖29顯示未具有抗電磁干擾之薄膜之錄放影機,在垂直方向上對其進行量測,所得之電磁場強度與頻率間之關係圖;及Figure 29 is a view showing the relationship between the intensity of the electromagnetic field and the frequency obtained by measuring the film in a vertical direction without a film having an anti-electromagnetic interference; and
圖30顯示具有抗電磁干擾之薄膜之硬碟,在垂直方向上對其進行量測,所得之電磁場強度與頻率間之關係圖。Figure 30 is a graph showing the relationship between the electromagnetic field strength and the frequency of a hard disk having a film resistant to electromagnetic interference measured in a vertical direction.
10...電磁屏蔽裝置10. . . Electromagnetic shielding device
11...本體11. . . Ontology
12...薄膜12. . . film
13...表面13. . . surface
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