臺灣博碩士論文加值系統

近年來通訊技術發展迅速，電磁波干擾問題日趨嚴重，而在國防工業上，電磁脈衝防護的能力以及雷達波吸收的匿蹤隱形技術更是日形重要，研究及開發高性能吸波材料已成為各國國防上互相競爭的一大課題。雷達匿蹤及電磁脈衝屏蔽材料主要的訴求就是重量輕、厚度薄、作用頻率寬、吸收能力強，而近年來的研究發現，在奈米碳材料中，因石墨烯質量輕且厚度薄，更具有高比表面積的特性，極為適合作為吸收劑使用，本論文作者團隊以往在以石墨烯作為微波吸收劑之研究亦發現團隊自製之多孔石墨烯在添加量1 wt.%時具有良好的吸波能力，但由於材料本身高比表面積特性，頻寬控制不易。而且石墨烯之價格昂貴，應用於大面積之吸收漆料成本極高，因此本論文嘗試使用價格低廉、層數較厚的奈米石墨薄片(xGnP)來代替石墨烯，希望能降低吸波材之成本，並達到良好之吸波效果。
本研究主要分為兩個部分。第一部分為藉由後製程對奈米石墨薄片進行表面型態的變化，希望藉由改變xGnP的幾何形狀，而產生額外的電磁波吸收機制，同時增加比表面積來提升其介面極化效應。研究中分別利用高溫KOH腐蝕、高溫KNO3腐蝕以及在xGnP上成長奈米碳管(CNT)等方式製作三種異型結構奈米石墨薄片(KOHxGnP、KNO3xGnP、CNTxGnP)，並探討形貌變化對材料特性及吸波性能的影響。研究結果顯示，在10 wt.%添加量與1 mm膠片厚度之測試條件下，KOHxGnP之表面型態呈現略微被侵蝕狀，其測得之反射損失在14.99 GHz可達到-27.04 dB之最大值。而KNO3xGnP之表面被腐蝕出不規則孔洞，其測得之反射損失在17.09 GHz可達到-19.23 dB之最大值。CNTxGnP之表面形貌為類似毛氈狀形貌，其測得之反射損失在14.24 GHz可達到-21.85 dB之最大值。由實驗結果可見，改變原xGnP之形貌會使其最大反射損失往高頻位移，而由上述各材料之吸波特性分析比較，推論片徑尺寸為改變吸波頻帶之主要因素。
第二部分則是藉由比較片徑極小之市售石墨烯(UC)與利用超音震盪方式改變xGnP片徑大小，並測試與比較其吸波特性來驗證前節之推論。在10 wt.%添加量與1 mm膠片厚度之測試條件下，UC於1 mm膠片厚度實測時幾無吸波效果，而震盪時間0.5 hr之xGnP，其測得之反射損失在14.84 GHz可達到-21.23 dB之最大值；震盪時間1 hr之xGnP，其測得之反射損失在15.89 GHz可達到-38.76 dB之最大值；震盪時間3 hr之xGnP，其測得之反射損失在17.99 GHz時可達到-21.94 dB之最大值，此結果證實xGnP可透過改變其片徑尺寸來控制其所作用之頻帶範圍。

In recent years, communication technology has developed rapidly, and electromagnetic interference has become more and more serious. Meanwhile, in the defense industry, the ability of electromagnetic pulse protection and the stealth technology of radar wave absorption are also more and more important. Research and development of high-performance wave absorbing materials have become a major issue in competition for national defense between countries. The main requirements of radar stealth and electromagnetic pulse shielding materials are light weight, thin thickness, wide band of frequency and good absorption capacity. Recent studies have found that, in nano carbon materials, graphene is light in weight and thin in thickness. It also has high specific surface area and is very suitable for use as an absorbent for microwaves. The author's team used to use graphene as a microwave absorber and found that the team-made holy graphene has good wave -absorbing capability even when the added amount is as low as 1 wt%. However, due to the high specific surface area of the holy graphene itself, the bandwidth of absorber is not easy to be controlled. Moreover, the price of graphene is expensive, and the cost of such absorbing paint applied to a large area is extremely high. Therefore, this thesis attempts to replace graphene with low-cost, thick-layer nano graphite sheets (xGnP), hoping to reduce the cost of absorbing materials and achieve good absorbing effect.
This thesis is mainly divided into two parts. The first part is to change the surface morphology of xGnPs by post-process. It is hoped that by changing the geometry of xGnPs, an additional electromagnetic wave absorption mechanism is generated, and the specific surface area is increased to enhance the interface polarization effect. In the thesis, three kinds of morphology-altered graphite nano platelets (KOHxGnP, KNO3xGnP, CNTxGnP) were fabricated by high temperature KOH corrosion, high temperature KNO3 corrosion and the growth of carbon nanotubes (CNT) on xGnPs. The effect of morphology changes on their wave absorbing properties was investigated. The results show that, under the test conditions of 10 wt% adding amount and 1 mm film thickness, the surface morphology of KOHxGnP was slightly eroded, and the measured reflection loss reached a maximum of -27.04 dB at 14.99 GHz. The surface of KNO3xGnP is corroded to form irregular holes, and the measured reflection loss reached a maximum value of -19.23 dB at 17.09 GHz. The morphology of CNTxGnP was similar to a felt-like structure, and the measured reflection loss reached a maximum of -21.85 dB at 14.24 GHz. It can be seen from the experimental results that changing the morphology of the original xGnP will cause its maximum reflection loss to shift to the high frequency. From the analysis of the absorbing characteristics of the above materials, it is inferred that the flake size of xGnP is the main factor for changing the absorbing band.
The second part of this thesis is to verify the inference of the previous section by comparing the absorbing properties of a commercially available graphene (UC) with a very small diameter and xGnPs with different flake size changed by means of different supersonic oscillation period. Under the test conditions of 10 wt% adding amount and 1 mm film thickness, UC has no absorbing effect in the range of 2 to 18 GHz. For the xGnPs with an oscillating time of 0.5 hr., the measured reflection loss can reach a maximum of -21.23 dB at 14.84 GHz. The reflected loss of xGnP with an oscillating time of 1 hr. can reach a maximum of -38.76 dB at 15.89 GHz. And for the xGnPs with an oscillating time of 3 hr., the measured reflection loss can reach a maximum value of -21.94 dB at 17.99 GHz. This result confirms that we can control the acting frequency band of the xGnP absorber by changing its flake size.

誌謝 ii
摘要 iii
Abstract v
目錄 vii
表目錄 ix
圖目錄 x
1. 緒論 1
1.1. 前言 1
1.2. 研究動機及目的 2
2. 文獻回顧與理論基礎 4
2.1. 電磁波吸波原理 4
2.1.1. 電磁波吸波材料損耗機制 8
2.1.2. 電滋波吸收模擬公式推算 9
2.2. 不同碳材對於吸波效能之比較文獻回顧 12
2.2.1. 奈米剝落石墨薄片之文獻回顧 15
2.2.2. 石墨烯簡介 16
2.2.3. 異型石墨烯應用於吸波之文獻回顧 19
3. 實驗方法 24
3.1. 實驗步驟 24
3.1.1. 實驗架構 24
3.1.2. 奈米石墨薄片製備方法 25
3.1.3. 異型結構奈米石墨薄片製備方法 26
3.1.4. 膠片製作流程 27
3.2. 實驗檢測方法 32
3.2.1. 反射損失及電磁參數量測方法 32
3.3. 實驗藥品、設備及儀器 34
3.3.1. 實驗藥品 34
3.3.2. 實驗設備及儀器 34
4. 結果與討論 36
4.1. 異型結構奈米石墨薄片對吸波效能之影響 36
4.1.1. 奈米石墨薄片之材料特性與吸波性能 36
4.1.2. KOH侵蝕奈米石墨薄片之材料特性與吸波性能 43
4.1.3. KNO3侵蝕奈米石墨薄片之材料特性與吸波性能 50
4.1.4. 奈米石墨薄片複合奈米碳管之材料特性與吸波性能 57
4.1.5. 小結 64
4.2. 片徑大小對奈米石墨薄片吸波效能之影響 65
4.2.1. 市售石墨烯粉體之材料特性與吸波性能 65
4.2.2. 不同片徑大小奈米石墨薄片之材料特性與吸波性能 71
5. 結論 82
未來展望 84
參考文獻 85

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