TWI834001B - Composite material and method for manufacturing the same - Google Patents
Composite material and method for manufacturing the same Download PDFInfo
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Abstract
Description
本發明是有關於一種複合材料及其製造方法，且特別是有關於一種用於電磁波屏蔽或電磁波吸收的複合材料及其製造方法。The present invention relates to a composite material and a manufacturing method thereof, and in particular to a composite material used for electromagnetic wave shielding or electromagnetic wave absorption and a manufacturing method thereof.
隨著智慧型手機、平板電腦和筆記型電腦等電子裝置的操作速度不斷提高，電子裝置內之電子元件所產生的雜訊也不斷地增加。舉例來說，電子元件在工作時通常會產生電磁波，此電磁波會成為干擾電子裝置內之天線的雜訊而導致天線收發訊號能力有所降低。因此，如何有效地提高電磁波屏蔽或吸收的效果，為目前本領域研究人員亟欲解決的問題之一。As the operating speed of electronic devices such as smartphones, tablets, and notebook computers continues to increase, the noise generated by electronic components in the electronic devices also continues to increase. For example, electronic components usually generate electromagnetic waves when they are working. This electromagnetic wave can become noise that interferes with the antenna in the electronic device, resulting in a reduction in the antenna's ability to send and receive signals. Therefore, how to effectively improve the electromagnetic wave shielding or absorption effect is one of the problems that researchers in this field currently want to solve.
本發明提供一種複合材料及其製造方法，其具有良好的電磁波屏蔽或電磁波吸收的效果。The invention provides a composite material and a manufacturing method thereof, which have good electromagnetic wave shielding or electromagnetic wave absorption effects.
本發明提供一種用於電磁波屏蔽或電磁波吸收的複合材料，其包括含有二維的石墨烯片材的電磁波吸收材料。二維的石墨烯片材是藉由液相剝離法中的空穴原理來對碳原料進行破碎，並經由烘箱乾燥或冷凍乾燥製成。The present invention provides a composite material for electromagnetic wave shielding or electromagnetic wave absorption, which includes an electromagnetic wave absorbing material containing two-dimensional graphene sheets. Two-dimensional graphene sheets are made by crushing carbon raw materials using the hole principle in the liquid phase exfoliation method, and then drying them in an oven or freeze-drying them.
在本發明的一實施例中，複合材料更包括含有一維的碳材的導電材料。In an embodiment of the invention, the composite material further includes a conductive material containing one-dimensional carbon material.
在本發明的一實施例中，基於100重量份的電磁波吸收材料，導電材料的含量為1重量份至10重量份。In an embodiment of the present invention, the content of the conductive material is 1 to 10 parts by weight based on 100 parts by weight of the electromagnetic wave absorbing material.
在本發明的一實施例中，一維的碳材包括奈米碳管。In one embodiment of the invention, the one-dimensional carbon material includes carbon nanotubes.
本發明提供一種用於電磁波屏蔽或電磁波吸收的複合材料的製造方法，其包括以下步驟：藉由液相剝離法中的空穴原理來對碳原料進行破碎，以形成石墨烯懸浮液；以及對石墨烯懸浮液進行烘箱乾燥或冷凍乾燥，以形成含有二維的石墨烯片材的電磁波吸收材料。The present invention provides a method for manufacturing composite materials for electromagnetic wave shielding or electromagnetic wave absorption, which includes the following steps: crushing carbon raw materials through the hole principle in a liquid phase exfoliation method to form a graphene suspension; and The graphene suspension is oven dried or freeze dried to form an electromagnetic wave absorbing material containing two-dimensional graphene sheets.
在本發明的一實施例中，複合材料的製造方法更包括將含有一維的碳材的導電材料混合至電磁波吸收材料中。In an embodiment of the present invention, the manufacturing method of the composite material further includes mixing a conductive material containing one-dimensional carbon material into the electromagnetic wave absorbing material.
在本發明的一實施例中，基於100重量份的電磁波吸收材料，導電材料的含量為1重量份至10重量份。In an embodiment of the present invention, the content of the conductive material is 1 to 10 parts by weight based on 100 parts by weight of the electromagnetic wave absorbing material.
在本發明的一實施例中，一維的碳材包括奈米碳管。In one embodiment of the invention, the one-dimensional carbon material includes carbon nanotubes.
在本發明的一實施例中，液相剝離法中所使用的溶劑為選自以下群組中的一者或多者：水、乙醇和NMP。In one embodiment of the present invention, the solvent used in the liquid phase stripping method is one or more selected from the following groups: water, ethanol, and NMP.
在本發明的一實施例中，碳原料於溶劑中的固含量為1 wt%至10 wt%。In an embodiment of the present invention, the solid content of the carbon raw material in the solvent is 1 wt% to 10 wt%.
在本發明的一實施例中，液相剝離法的破碎次數大於1次且小於100。In an embodiment of the present invention, the number of crushing times of the liquid phase exfoliation method is greater than 1 and less than 100.
在本發明的一實施例中，烘箱乾燥的溫度為40℃至100℃。In an embodiment of the present invention, the oven drying temperature is 40°C to 100°C.
在本發明的一實施例中，冷凍乾燥的溫度為-110℃至-30℃。In an embodiment of the present invention, the freeze-drying temperature is -110°C to -30°C.
基於上述，在本發明的複合材料及其製造方法中，由於包括二維的石墨烯片材的電磁波吸收材料可在材料內部形成導電鏈或導電網絡，使得進入至複合材料的電磁波能夠因極化而產生與電場方向相同的電流，而該電流於複合材料的內部形成封閉的電流迴路以產生渦電流（eddy current），如此電能夠進一步轉化成熱能而被消耗掉，使得複合材料能夠具有良好的電磁波屏蔽或電磁波吸收的效果。Based on the above, in the composite material and its manufacturing method of the present invention, since the electromagnetic wave absorbing material including two-dimensional graphene sheets can form conductive chains or conductive networks inside the material, the electromagnetic waves entering the composite material can be polarized due to A current in the same direction as the electric field is generated, and this current forms a closed current loop inside the composite material to generate eddy current. In this way, the electricity can be further converted into heat energy and consumed, so that the composite material can have good The effect of electromagnetic wave shielding or electromagnetic wave absorption.
參照本實施例之圖式以更全面地闡述本發明。然而，本發明亦可以各種不同的形式體現，而不應限於本文中所述之實施例。圖式中的層與區域的厚度會為了清楚起見而放大。相同或相似之參考號碼表示相同或相似之元件，以下段落將不再一一贅述。The present invention will be described more fully with reference to the drawings of this embodiment. However, the present invention may also be embodied in various forms and should not be limited to the embodiments described herein. The thickness of layers and regions in the drawings are exaggerated for clarity. The same or similar reference numbers indicate the same or similar components, and will not be repeated one by one in the following paragraphs.
應當理解，當諸如元件被稱為在另一元件「上」或「連接到」另一元件時，其可以直接在另一元件上或與另一元件連接，或者也可存在中間元件。若當元件被稱為「直接在另一元件上」或「直接連接到」另一元件時，則不存在中間元件。如本文所使用的，「連接」可以指物理及/或電性連接，而「電性連接」或「耦合」可為二元件間存在其它元件。本文中所使用的「電性連接」可包括物理連接（例如有線連接）及物理斷接（例如無線連接）。It will be understood that when an element is referred to as being "on" or "connected to" another element, it can be directly on or connected to the other element or intervening elements may also be present. When an element is referred to as being "directly on" or "directly connected to" another element, there are no intervening elements present. As used herein, "connection" may refer to a physical and/or electrical connection, and "electrical connection" or "coupling" may refer to the presence of other components between two components. "Electrical connection" as used herein may include physical connections (such as wired connections) and physical disconnections (such as wireless connections).
本文使用的「約」、「近似」或「實質上」包括所提到的值和在所屬技術領域中具有通常知識者能夠確定之特定值的可接受的偏差範圍內的平均值，考慮到所討論的測量和與測量相關的誤差的特定數量（即，測量系統的限制）。例如，「約」可以表示在所述值的一個或多個標準偏差內，或±30％、±20％、±10％、±5％內。再者，本文使用的「約」、「近似」或「實質上」可依光學性質、蝕刻性質或其它性質，來選擇較可接受的偏差範圍或標準偏差，而可不用一個標準偏差適用全部性質。As used herein, "about," "approximately" or "substantially" includes the recited value and the average within an acceptable range of deviations from the specific value that a person with ordinary skill in the art can determine, taking into account the Discuss the measurement and the specific amount of error associated with the measurement (i.e., the limitations of the measurement system). For example, "about" may mean within one or more standard deviations of the stated value, or within ±30%, ±20%, ±10%, ±5%. Furthermore, the terms "about", "approximately" or "substantially" used in this article can be used to select a more acceptable deviation range or standard deviation based on optical properties, etching properties or other properties, and one standard deviation does not apply to all properties. .
使用本文中所使用的用語僅為闡述例示性實施例，而非限制本揭露。在此種情形中，除非在上下文中另有解釋，否則單數形式包括多數形式。The terminology used herein is used only to describe illustrative embodiments and does not limit the disclosure. In such cases, the singular form includes the plural form unless the context dictates otherwise.
圖1為製備參考例1、製備實例1和製備實例2的掃描式電子顯微鏡（Scanning Electron Microscope，SEM）圖像。圖2為製備參考例1、製備實例1和製備實例2的振實密度比較圖像。圖3是製備參考例1和製備實例1的布厄特（BET）圖。圖4是製備參考例1和製備實例2的BET圖。Figure 1 is a scanning electron microscope (SEM) image of Preparation Reference Example 1, Preparation Example 1 and Preparation Example 2. Figure 2 is a comparison image of tap densities of Preparation Reference Example 1, Preparation Example 1 and Preparation Example 2. Figure 3 is a BET diagram of Preparation Reference Example 1 and Preparation Example 1. Figure 4 is a BET diagram of Preparation Reference Example 1 and Preparation Example 2.
用於電磁波屏蔽或電磁波吸收的複合材料可包括含有二維的石墨烯片材的電磁波吸收材料，如此可藉由二維的石墨烯片材具有在其內部可形成導電鏈或導電網絡的特性，使得進入至複合材料的電磁波能夠因極化而產生與電場方向相同的電流，而該電流於複合材料的內部形成封閉的電流迴路以產生渦電流（eddy current）。也就是說，進入至複合材料的電磁波能夠轉化成電能並再更進一步轉化成熱能而被消耗掉，使得複合材料能夠具有良好的電磁波屏蔽或電磁波吸收的效果。另一方面，石墨烯的高比表面積和結構特性可造成入射至複合材料的電磁波產生多次散射，藉此消耗電磁波的能量並達到吸收電磁波的目的。石墨烯片材可包括單層石墨烯、寡層石墨烯（few layer graphene）、多層石墨烯（multi layer graphene）或其組合。上述「寡層石墨烯」表示層數大於1層且小於10層的石墨烯。上述「多層石墨烯」表示層數大於等於10層的石墨烯。石墨烯片材的厚度可約介於2 nm至10 nm之間。Composite materials used for electromagnetic wave shielding or electromagnetic wave absorption may include electromagnetic wave absorbing materials containing two-dimensional graphene sheets. In this way, the two-dimensional graphene sheets have the property of forming conductive chains or conductive networks within them. The electromagnetic waves entering the composite material can generate current in the same direction as the electric field due to polarization, and this current forms a closed current loop inside the composite material to generate eddy current. That is to say, the electromagnetic waves entering the composite material can be converted into electrical energy and further converted into heat energy to be consumed, so that the composite material can have good electromagnetic wave shielding or electromagnetic wave absorption effects. On the other hand, the high specific surface area and structural characteristics of graphene can cause multiple scatterings of electromagnetic waves incident on composite materials, thereby consuming the energy of electromagnetic waves and achieving the purpose of absorbing electromagnetic waves. Graphene sheets may include single-layer graphene, few layer graphene, multi-layer graphene, or combinations thereof. The above-mentioned "oligolayer graphene" means graphene with a number of layers greater than 1 and less than 10. The above-mentioned "multilayer graphene" means graphene with 10 or more layers. The thickness of graphene sheets can range from approximately 2 nm to 10 nm.
二維的石墨烯片材可藉由液相剝離法中的空穴原理來對碳原料進行破碎，並經由烘箱乾燥或冷凍乾燥製成。舉例來說，二維的石墨烯片材可藉由以下步驟形成。Two-dimensional graphene sheets can be made by crushing carbon raw materials using the hole principle in the liquid phase exfoliation method and drying them in an oven or freeze-drying. For example, a two-dimensional graphene sheet can be formed by the following steps.
首先，藉由液相剝離法中的空穴原理來對碳原料進行破碎，以形成石墨烯懸浮液。舉例來說，可採用藉由連續式細胞破碎儀（continuous cell disrupter）對碳原料進行均質破碎。碳原料在高壓的環境下於連續式細胞破碎儀的出口端瞬間釋放，導致碳原料層間瞬間剝離，使得碳原料中層與層之間的碳可以脫層而形成石墨烯片材。液相剝離法所採用的壓力可為0 bar至3000 bar。液相剝離法的破碎次數可為1次至100次，其中每次破碎所採用的壓力可不同，例如可以不同的壓力破碎兩次。液相剝離法所採用的溫度可例如是大於4℃且小於50℃。液相剝離法中所使用的溶劑可為選自以下群組中的一者或多者：水、乙醇和N-甲基-2-吡咯烷酮（NMP）。碳原料於溶劑中的固含量可為1 wt%至10 wt%。First, the carbon raw material is broken up by the hole principle in the liquid phase exfoliation method to form a graphene suspension. For example, a continuous cell disrupter can be used to homogenize the carbon raw material. The carbon raw material is instantly released at the outlet of the continuous cell crusher in a high-pressure environment, causing the layers of carbon raw material to instantly peel off, allowing the carbon between the middle layers of the carbon raw material to delaminate to form graphene sheets. The pressure used in the liquid phase stripping method can range from 0 bar to 3000 bar. The number of crushing times in the liquid phase exfoliation method can be from 1 to 100 times, and the pressure used for each crushing can be different, for example, the crushing can be done twice with different pressures. The temperature used in the liquid phase exfoliation method may be, for example, greater than 4°C and less than 50°C. The solvent used in the liquid phase stripping method may be one or more selected from the following groups: water, ethanol, and N-methyl-2-pyrrolidone (NMP). The solid content of the carbon raw material in the solvent may be 1 wt% to 10 wt%.
接著，對石墨烯懸浮液進行烘箱乾燥或冷凍乾燥，以形成含有二維的石墨烯片材的電磁波吸收材料。烘箱乾燥所採用的溫度可為40℃至100℃。冷凍乾燥所採用的溫度可為-110℃至-30℃。Next, the graphene suspension is oven dried or freeze-dried to form an electromagnetic wave absorbing material containing two-dimensional graphene sheets. The temperature used for oven drying can be from 40°C to 100°C. The temperature used for freeze drying can be -110°C to -30°C.
採用冷凍乾燥來乾燥石墨烯懸浮液可維持石墨烯與石墨烯之間的空隙，以減少乾燥過程中的團聚現象，使得以冷凍乾燥所形成之石墨烯具有良好的電磁波屏蔽或電磁波吸收的效果。如圖1所示，以冷凍乾燥所形成之石墨烯（如製備實例2）的振實密度（約0.0909 g/ml）小於以烘箱乾燥所形成之石墨烯（如製備實例1）的振實密度（約0.1961 g/ml），且從圖2可看出，以烘箱乾燥所形成之石墨烯有明顯的層跟層之間的堆疊紋路，且表面形貌較為規則，而以冷凍乾燥所形成之石墨烯並未有明顯的層跟層之間的堆疊紋路，且石墨烯的表面形貌較為不規則且長寬比較大。以烘箱乾燥或冷凍乾燥所形成之石墨烯的振實密度皆小於石墨片材（如製備參考例1）的振實密度（約0.2778 g/ml）。Using freeze-drying to dry the graphene suspension can maintain the gap between graphene and graphene to reduce agglomeration during the drying process, so that the graphene formed by freeze-drying has a good electromagnetic wave shielding or electromagnetic wave absorption effect. As shown in Figure 1, the tap density (approximately 0.0909 g/ml) of graphene formed by freeze-drying (such as Preparation Example 2) is smaller than the tap density of graphene formed by oven drying (such as Preparation Example 1) (approximately 0.1961 g/ml), and as can be seen from Figure 2, the graphene formed by oven drying has obvious stacking patterns between layers, and the surface morphology is relatively regular, while the graphene formed by freeze-drying Graphene does not have obvious stacking patterns between layers, and the surface morphology of graphene is relatively irregular and has a large aspect ratio. The tap density of graphene formed by oven drying or freeze drying is smaller than the tap density of graphite sheets (such as Preparation Reference Example 1) (about 0.2778 g/ml).
請參照圖3和圖4，以BET的分析結果來看，以烘箱乾燥所形成之石墨烯的比表面積（如圖3所示之製備實例1的比表面積為37.488 m 2/g）或以冷凍乾燥所形成之石墨烯的比表面（如圖4所示之製備實例2的比表面積為35.2 m 2/g）皆優於石墨片材的比表面積（如圖3和圖4所示之製備參考例1的比表面積分別為29.431 m 2/g和29.4 m 2/g）。 Please refer to Figures 3 and 4. Judging from the BET analysis results, the specific surface area of graphene formed by oven drying (the specific surface area of Preparation Example 1 shown in Figure 3 is 37.488 m 2 /g) or frozen The specific surface area of the graphene formed by drying (the specific surface area of the preparation example 2 shown in Figure 4 is 35.2 m 2 /g) is better than the specific surface area of the graphite sheet (the specific surface area of the preparation example 2 shown in Figure 3 and Figure 4 The specific surface areas of Example 1 are 29.431 m 2 /g and 29.4 m 2 /g respectively).
在一些實施例中，複合材料還可包括含有一維的碳材的導電材料，如此可藉由一維的碳材來填補二維的石墨烯片材之間的縫隙，以形成更緻密的導電網絡，使得複合材料的電磁波屏蔽或電磁波吸收的效果能夠進一步地提升。基於100重量份的所述電磁波吸收材料，導電材料的含量可為1重量份至10重量份。一維的碳材可為奈米碳管，但本發明不以此為限。在本實施例中，用於電磁波屏蔽或電磁波吸收的複合材料的製造方法包括以下步驟：混合電磁波吸收材料與導電材料。可藉由將含有一維的碳材的導電材料混合至電磁波吸收材料中以形成包括電磁波吸收材料和導電材料的複合材料。In some embodiments, the composite material may also include a conductive material containing one-dimensional carbon material, so that the one-dimensional carbon material can be used to fill the gaps between the two-dimensional graphene sheets to form a denser conductive layer. The network enables the electromagnetic wave shielding or electromagnetic wave absorption effect of composite materials to be further improved. The content of the conductive material may be 1 to 10 parts by weight based on 100 parts by weight of the electromagnetic wave absorbing material. The one-dimensional carbon material can be carbon nanotubes, but the invention is not limited thereto. In this embodiment, a method of manufacturing a composite material for electromagnetic wave shielding or electromagnetic wave absorption includes the following steps: mixing an electromagnetic wave absorbing material and a conductive material. A composite material including an electromagnetic wave absorbing material and a conductive material can be formed by mixing a conductive material containing a one-dimensional carbon material into an electromagnetic wave absorbing material.
在本實施例中，藉由液相剝離法中的空穴原理來對碳原料進行破碎而製備出的石墨烯片材的厚度為奈米級，但其片徑只會略小於碳原料的片徑。舉例來說，片徑（d 50）約為11.15 μm的石墨片材可經由上述的液相剝離法而製備出片徑（d 50）約為8-9 μm且厚度約為2 nm至10 nm的石墨烯片材，其中以烘箱乾燥所形成之石墨烯的片徑較大（例如約8.59 μm），而以冷凍乾燥所形成之石墨烯的片徑較小（例如約8.11 μm）。 In this embodiment, the graphene sheet prepared by crushing the carbon raw material using the hole principle in the liquid phase exfoliation method has a thickness of nanometer level, but its sheet diameter is only slightly smaller than that of the carbon raw material. diameter. For example, graphite sheets with a sheet diameter (d 50 ) of approximately 11.15 μm can be prepared by the above-mentioned liquid phase exfoliation method with a sheet diameter (d 50 ) of approximately 8-9 μm and a thickness of approximately 2 nm to 10 nm. Graphene sheets, wherein the graphene formed by oven drying has a larger sheet diameter (for example, about 8.59 μm), while the graphene formed by freeze-drying has a smaller sheet diameter (for example, about 8.11 μm).
在一些實施例中，複合材料可依據需求而進一步包括其他添加物。舉例來說，複合材料可包括碳黑、氧化鐵或其組合。In some embodiments, the composite material may further include other additives as needed. For example, the composite material may include carbon black, iron oxide, or combinations thereof.
在一些實施例中，複合材料可進一步包括包覆材或支撐材，例如石蠟、矽橡膠或環氧樹脂，以作成用於電磁波屏蔽或電磁波吸收的複合塊材。在本實施例中，磁波吸收材料和導電材料可基於包覆材或支撐材的重量，以1 wt%至80 wt%的比例添加於包覆材或支撐材中。In some embodiments, the composite material may further include a coating material or a supporting material, such as paraffin, silicone rubber or epoxy resin, to form a composite block for electromagnetic wave shielding or electromagnetic wave absorption. In this embodiment, the magnetic wave absorbing material and the conductive material may be added to the cladding material or the supporting material in a proportion of 1 wt% to 80 wt% based on the weight of the cladding material or the supporting material.
下文將參照參考例1和參考例2以及實施例1至實施例9來更具體地描述本發明的特徵。雖然描述了以下實施例，但是在不逾越本發明範疇之情況下，可適當地改變所用材料、其量及比率、處理細節以及處理流程等等。因此，不應由下文所述之實施例對本發明作出限制性地解釋。Features of the present invention will be described in more detail below with reference to Reference Examples 1 and 2 and Examples 1 to 9. Although the following embodiments are described, the materials used, their amounts and ratios, processing details, processing procedures, and the like may be appropriately changed without exceeding the scope of the present invention. Therefore, the present invention should not be interpreted restrictively by the examples described below.
參考例Reference example 11
首先，秤取7.5 g的石蠟，並以70℃加熱至完全融化。接著，將1.875 g的石墨片材加到石蠟中，並以均質機攪拌2小時（轉速為3000 rpm）直到分散均勻於液態的石蠟溶液中。然後，將該溶液倒入至3 cm×3 cm的正方形模具中，待其凝固後以17000 lbf的壓力加壓成型。First, weigh 7.5 g of paraffin and heat it at 70°C until it is completely melted. Next, 1.875 g of graphite sheets were added to the paraffin and stirred with a homogenizer for 2 hours (rotation speed: 3000 rpm) until evenly dispersed in the liquid paraffin solution. Then, the solution was poured into a 3 cm × 3 cm square mold, and after solidification, it was pressed and formed with a pressure of 17,000 lbf.
實施例Example 11
首先，秤取7.5 g的石蠟，並以70℃加熱至完全融化。接著，將1.875 g的經烘箱乾燥的石墨烯片材加到石蠟中，並以均質機攪拌2小時（轉速為3000 rpm）直到石墨烯片材分散於液態的石蠟溶液中。然後，將該溶液倒入至3 cm×3 cm的正方形模具中，待其凝固後以17000 lbf的壓力加壓成型。First, weigh 7.5 g of paraffin and heat it at 70°C until it is completely melted. Next, 1.875 g of oven-dried graphene sheets were added to the paraffin and stirred with a homogenizer for 2 hours (3000 rpm) until the graphene sheets were dispersed in the liquid paraffin solution. Then, the solution was poured into a 3 cm × 3 cm square mold, and after solidification, it was pressed and formed with a pressure of 17,000 lbf.
實施例Example 22
首先，秤取7.5 g的石蠟，並以70℃加熱至完全融化。接著，將1.85625 g的經烘箱乾燥的石墨烯片材和0.01875 g的奈米碳管加到石蠟中，並以均質機攪拌2小時（轉速為4000 rpm）直到石墨烯片材和奈米碳管均勻分散於液態的石蠟溶液中。然後，將該溶液倒入至3 cm×3 cm的正方形模具中，待其凝固後以17000 lbf的壓力加壓成型。First, weigh 7.5 g of paraffin and heat it at 70°C until it is completely melted. Next, 1.85625 g of oven-dried graphene sheets and 0.01875 g of carbon nanotubes were added to the paraffin, and stirred with a homogenizer for 2 hours (4000 rpm) until the graphene sheets and carbon nanotubes were Evenly dispersed in liquid paraffin solution. Then, the solution was poured into a 3 cm × 3 cm square mold, and after solidification, it was pressed and formed with a pressure of 17,000 lbf.
實施例Example 33
首先，秤取7.5 g的石蠟，並以70℃加熱至完全融化。接著，將1.81875 g的經烘箱乾燥的石墨烯片材和0.05625 g的奈米碳管加到石蠟中，並以均質機攪拌2小時（轉速為4000 rpm）直到石墨烯片材和奈米碳管均勻分散於液態的石蠟溶液中。然後，將該溶液倒入至3 cm×3 cm的正方形模具中，待其凝固後以17000 lbf的壓力加壓成型。First, weigh 7.5 g of paraffin and heat it at 70°C until it is completely melted. Next, 1.81875 g of oven-dried graphene sheets and 0.05625 g of carbon nanotubes were added to the paraffin, and stirred with a homogenizer for 2 hours (4000 rpm) until the graphene sheets and carbon nanotubes were Evenly dispersed in liquid paraffin solution. Then, the solution was poured into a 3 cm × 3 cm square mold, and after solidification, it was pressed and formed with a pressure of 17,000 lbf.
實施例Example 44
首先，秤取7.5 g的石蠟，並以70℃加熱至完全融化。接著，將1.78125 g的經烘箱乾燥的石墨烯片材和0.09375 g的奈米碳管加到石蠟中，並以均質機攪拌2小時（轉速為4000 rpm）直到石墨烯片材和奈米碳管均勻分散於液態的石蠟溶液中。然後，將該溶液倒入至3 cm×3 cm的正方形模具中，待其凝固後以17000 lbf的壓力加壓成型。First, weigh 7.5 g of paraffin and heat it at 70°C until it is completely melted. Next, 1.78125 g of oven-dried graphene sheets and 0.09375 g of carbon nanotubes were added to the paraffin, and stirred with a homogenizer for 2 hours (4000 rpm) until the graphene sheets and carbon nanotubes were Evenly dispersed in liquid paraffin solution. Then, the solution was poured into a 3 cm × 3 cm square mold, and after solidification, it was pressed and formed with a pressure of 17,000 lbf.
實施例Example 55
首先，秤取7.5 g的石蠟，並以70℃加熱至完全融化。接著，將1.74375 g的經烘箱乾燥的石墨烯片材和0.13125 g的奈米碳管加到石蠟中，並以均質機攪拌2小時（轉速為4000 rpm）直到石墨烯片材和奈米碳管均勻分散於液態的石蠟溶液中。然後，將該溶液倒入至3 cm×3 cm的正方形模具中，待其凝固後以17000 lbf的壓力加壓成型。First, weigh 7.5 g of paraffin and heat it at 70°C until it is completely melted. Next, 1.74375 g of oven-dried graphene sheets and 0.13125 g of carbon nanotubes were added to the paraffin, and stirred with a homogenizer for 2 hours (4000 rpm) until the graphene sheets and carbon nanotubes were Evenly dispersed in liquid paraffin solution. Then, the solution was poured into a 3 cm × 3 cm square mold, and after solidification, it was pressed and formed with a pressure of 17,000 lbf.
實施例Example 66
首先，秤取7.5 g的石蠟，並以70℃加熱至完全融化。接著，將1.875 g的經冷凍乾燥的石墨烯片材加到石蠟中，並以均質機攪拌2小時（轉速為3000 rpm）直到石墨烯片材和奈米碳管均勻分散於液態的石蠟溶液中。然後，將該溶液倒入至3 cm×3 cm的正方形模具中，待其凝固後以17000 lbf的壓力加壓成型。First, weigh 7.5 g of paraffin and heat it at 70°C until it is completely melted. Next, 1.875 g of freeze-dried graphene sheets were added to the paraffin, and stirred with a homogenizer for 2 hours (rotation speed: 3000 rpm) until the graphene sheets and carbon nanotubes were evenly dispersed in the liquid paraffin solution. . Then, the solution was poured into a 3 cm × 3 cm square mold, and after solidification, it was pressed and formed with a pressure of 17,000 lbf.
實施例Example 77
首先，秤取7.5 g的石蠟，並以70℃加熱至完全融化。接著，將1.78125 g的經冷凍乾燥的石墨烯片材和0.09375 g的奈米碳管加到石蠟中，並以均質機攪拌2小時（轉速為4000 rpm）直到石墨烯片材和奈米碳管均勻分散於液態的石蠟溶液中。然後，將該溶液倒入至3 cm×3 cm的正方形模具中，待其凝固後以17000 lbf的壓力加壓成型。First, weigh 7.5 g of paraffin and heat it at 70°C until it is completely melted. Next, 1.78125 g of freeze-dried graphene sheets and 0.09375 g of carbon nanotubes were added to the paraffin, and stirred with a homogenizer for 2 hours (4000 rpm) until the graphene sheets and carbon nanotubes were Evenly dispersed in liquid paraffin solution. Then, the solution was poured into a 3 cm × 3 cm square mold, and after solidification, it was pressed and formed with a pressure of 17,000 lbf.
參考例Reference example 22
首先，秤取25 g的矽橡膠，並將2.5 g的石墨片材加到矽橡膠中，以行星式攪拌裝置分散15分鐘後再以三滾筒分散。接著加入2.5 g的交聯劑，再以行星式攪拌裝置分散15分鐘。然後，倒入至15 cm×15 cm的正方形模具中，熱壓成型。First, weigh 25 g of silicone rubber, add 2.5 g of graphite sheets to the silicone rubber, disperse it with a planetary stirring device for 15 minutes, and then use three rollers to disperse it. Then add 2.5 g of cross-linking agent and disperse for 15 minutes using a planetary stirring device. Then, pour it into a 15 cm × 15 cm square mold and heat press it.
實施例Example 88
首先，秤取25 g的矽橡膠，並將2.5 g的經烘箱乾燥的石墨烯片材加到矽橡膠中，以行星式攪拌裝置分散15分鐘後再以三滾筒分散。接著加入2.5 g的交聯劑，再以行星式攪拌裝置分散15分鐘。然後，倒入至15 cm×15 cm的正方形模具中，熱壓成型。First, weigh 25 g of silicone rubber, add 2.5 g of oven-dried graphene sheets to the silicone rubber, disperse it with a planetary stirring device for 15 minutes, and then use three rollers to disperse it. Then add 2.5 g of cross-linking agent and disperse for 15 minutes using a planetary stirring device. Then, pour it into a 15 cm × 15 cm square mold and heat press it.
實施例Example 99
首先，秤取25 g的矽橡膠，並將2.5 g的經冷凍乾燥的石墨烯片材加到矽橡膠中，以行星式攪拌裝置分散15分鐘後再以三滾筒分散。接著加入2.5 g的交聯劑，再以行星式攪拌裝置分散15分鐘。然後，倒入至15 cm×15 cm的正方形模具中，熱壓成型。First, weigh 25 g of silicone rubber, add 2.5 g of freeze-dried graphene sheets to the silicone rubber, disperse it with a planetary stirring device for 15 minutes, and then disperse it with three rollers. Then add 2.5 g of cross-linking agent and disperse for 15 minutes using a planetary stirring device. Then, pour it into a 15 cm × 15 cm square mold and heat press it.
將上述參考例1和參考例2以及實施例1至實施例9整理於下表1中。The above-mentioned Reference Examples 1 and 2 and Examples 1 to 9 are summarized in Table 1 below.
表1
實驗
對參考例1和實施例1-7進行X波段下的電磁波屏蔽效率的測試。參考例1和實施例1-7的實驗數據示於圖5A、5B、6A和6B和下表2。參考例1和實施例1-5於X波段下的總屏蔽效率（SE
T）可見於圖5A，而參考例1、實施例1、6、7於X波段下的總屏蔽效率（SE
T）可見於圖6A。參考例1和實施例1、6、7於X波段下的反射貢獻（SE
R）和吸收貢獻（SE
A）的屏蔽效率的比較可見於圖5B，而參考例1、實施例1、6、7的反射貢獻（SE
R）和吸收貢獻（SE
A）的屏蔽效率的比較可見於圖6B。
The electromagnetic wave shielding efficiency in the X-band was tested for Reference Example 1 and Examples 1-7. Experimental data for Reference Example 1 and Examples 1-7 are shown in Figures 5A, 5B, 6A and 6B and Table 2 below. The total shielding efficiency (SE T ) of Reference Example 1 and Embodiments 1-5 under the X-band can be seen in Figure 5A, and the total shielding efficiency (SE T ) of Reference Example 1,
[表2]
由表1所示出的結果可知，實施例1-7的電磁波屏蔽效率優於參考例1的電磁波屏蔽效率。另外，從實施例1和實施例6以及實施例4和實施例7的屏蔽效率測試結果可知，以冷凍乾燥製程的二維的石墨烯片材因可避免石墨烯層與層之間於乾燥製程中相互堆疊，故具有更佳的屏蔽效率。此外，從實施例2-4的屏蔽效率測試結果可知，隨著導電材料於複合材料中的比例越來越高，則屏蔽效率越好。然而，請參考實施例5所示出的結果，當導電材料於複合材料中的比例過高時，屏蔽效率反而會因團聚現象的產生而下降。From the results shown in Table 1, it can be seen that the electromagnetic wave shielding efficiency of Examples 1-7 is better than that of Reference Example 1. In addition, from the shielding efficiency test results of Examples 1 and 6 as well as Examples 4 and 7, it can be seen that the two-dimensional graphene sheet produced by the freeze-drying process can avoid the drying process between the graphene layers. They are stacked on each other, so they have better shielding efficiency. In addition, it can be seen from the shielding efficiency test results of Examples 2-4 that as the proportion of conductive material in the composite material becomes higher and higher, the shielding efficiency becomes better. However, please refer to the results shown in Example 5. When the proportion of conductive material in the composite material is too high, the shielding efficiency will decrease due to the occurrence of agglomeration.
實驗
對參考例2和實施例8、9進行反射損失測試，實驗結果分別顯示於圖7A至圖7C。圖7A至圖7C分別為參考例2、實施例8和實施例9於不同厚度下的頻率與反射損失（RL）關係圖。反射損失越高且涵蓋頻率越寬則代表電磁波屏蔽效率越佳，從圖7A至圖7C所示出的結果可知，實施例8和實施例9具有優於參考例2的反射損失，且實施例9具有優於實施例8的反射損失。The reflection loss test was performed on Reference Example 2 and Examples 8 and 9, and the experimental results are shown in Figures 7A to 7C respectively. 7A to 7C are respectively graphs showing the relationship between frequency and reflection loss (RL) of Reference Example 2, Example 8 and Example 9 at different thicknesses. The higher the reflection loss and the wider the frequency coverage, the better the electromagnetic wave shielding efficiency. From the results shown in Figures 7A to 7C, it can be seen that Example 8 and Example 9 have better reflection losses than Reference Example 2, and Example 9 has better reflection loss than Example 8.
綜上所述，在依本發明的一實施例的複合材料及其製造方法中，由於包括二維的石墨烯片材的電磁波吸收材料可在材料內部形成導電鏈或導電網絡，使得進入至複合材料的電磁波能夠因極化而產生與電場方向相同的電流，而該電流於複合材料的內部形成封閉的電流迴路以產生渦電流，如此電能夠進一步轉化成熱能而被消耗掉，使得複合材料能夠具有良好的電磁波屏蔽或電磁波吸收的效果。另一方面，在複合材料還包括含有一維的碳材的導電材料的情況下，可藉由一維的碳材來填補二維的石墨烯片材之間的縫隙，以形成更緻密的導電網絡，使得複合材料的電磁波屏蔽或電磁波吸收的效果能夠進一步地提升。To sum up, in the composite material and its manufacturing method according to an embodiment of the present invention, since the electromagnetic wave absorbing material including two-dimensional graphene sheets can form conductive chains or conductive networks inside the material, it can enter the composite material. The electromagnetic wave of the material can generate a current in the same direction as the electric field due to polarization, and this current forms a closed current loop inside the composite material to generate eddy current, so that the electricity can be further converted into heat energy and consumed, making the composite material It has good electromagnetic wave shielding or electromagnetic wave absorption effect. On the other hand, when the composite material also includes a conductive material containing one-dimensional carbon material, the one-dimensional carbon material can be used to fill the gaps between the two-dimensional graphene sheets to form a denser conductive layer. The network enables the electromagnetic wave shielding or electromagnetic wave absorption effect of composite materials to be further improved.
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed above through embodiments, they are not intended to limit the present invention. Anyone with ordinary knowledge in the technical field may make some modifications and modifications without departing from the spirit and scope of the present invention. Therefore, The protection scope of the present invention shall be determined by the appended patent application scope.
無without
圖1為製備參考例1、製備實例1和製備實例2的掃描式電子顯微鏡（Scanning Electron Microscope，SEM）圖像。
圖2為製備參考例1、製備實例1和製備實例2的振實密度比較圖像。
圖3是製備參考例1和製備實例1的布厄特（BET）圖。
圖4是製備參考例1和製備實例2的BET圖。
圖5A為參考例1和實施例1至實施例5於X波段下的頻率與總屏蔽效率（SE
T）的關係圖。
圖5B為參考例1和實施例1至實施例5的反射貢獻（SE
R）和吸收貢獻（SE
A）的屏蔽效率比較圖。
圖6A為參考例1和實施例1、實施例6和實施例7於X波段下的頻率與總屏蔽效率（SE
T）的關係圖。
圖6B為參考例1、實施例1、實施例6和實施例7的反射貢獻（SE
R）和吸收貢獻（SE
A）的屏蔽效率比較圖。
圖7A至圖7C分別為參考例2、實施例8和實施例9於不同厚度下的頻率與反射損失（RL）關係圖。
Figure 1 is a scanning electron microscope (SEM) image of Preparation Reference Example 1, Preparation Example 1 and Preparation Example 2. Figure 2 is a comparison image of tap densities of Preparation Reference Example 1, Preparation Example 1 and Preparation Example 2. Figure 3 is a BET diagram of Preparation Reference Example 1 and Preparation Example 1. Figure 4 is a BET diagram of Preparation Reference Example 1 and Preparation Example 2. FIG. 5A is a graph showing the relationship between frequency and total shielding efficiency (SE T ) in the X-band of Reference Example 1 and Examples 1 to 5. 5B is a comparison diagram of the shielding efficiency of the reflection contribution (SE R ) and the absorption contribution (SE A ) of Reference Example 1 and Examples 1 to 5. 6A is a graph showing the relationship between frequency and total shielding efficiency (SE T ) of Reference Example 1 and
Claims (9)
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| TW109136085A TWI834001B (en) | 2020-10-19 | Composite material and method for manufacturing the same | |
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| TWI834001B true TWI834001B (en) | 2024-03-01 |
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