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研究生： 陳永志
Yung-Chih Chen
論文名稱： PTFE-SiO2有機無機複合材料製備及性質之研究
Preparation and properties of PTFE-SiO2 organic-inorganic composite
指導教授： 李育德
Yu-Der Lee
口試委員:
學位類別： 博士
Doctor
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2004
畢業學年度： 92
語文別： 中文
論文頁數： 177
中文關鍵詞： 聚四氟乙烯 、二氧化矽 、複合材料 、填充材料含量 、填充材料尺寸大小 、混成材料
外文關鍵詞： polytetrafluoroethylene
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    • 摘　要
    有鑑於PTFE/SiO2複合材料為高頻或微波基板所使用之理想材料，其商業用途極為廣泛，而其性質又因組成及製作方法不同而有許多的變化，本研究目的即在於利用不同組成與製作方法製備出微米級(Micro)及奈米級(Nano)PTFE/SiO2複合材料，探討其介電性質、熱性質、機械性質及形態上的變化，以作為製作材料及調控基板性質的依據，希望能進一步了解填充材在複合材料中伴演的角色，並能有助於PTFE/SiO2複合材料未來之應用。
    本研究分為二系統進行，系統一以微米級SiO2填充材補強PTFE基材，系統二則利用溶膠-凝膠(Sol-gel)製程技術製作出PTFE/SiO2奈米級有機無機基板材料，除探討溶膠-凝膠組成中不同觸媒、溶劑含量與水量等成份對溶膠-凝膠材料性質之影響外，更針對表面改質處理與SiO2含量對PTFE/SiO2性質之影響性作探討。
    系統一以物理分散法製備PTFE/SiO2微米級複合材料並探討不同的Phenyltrimethoxysilane偶合劑含量(0-3wt%)對PTFE/SiO2材料的性質及形態上的影響，實驗數據分析後顯示：隨著偶合劑含量的增加，拉伸強度及熱膨脹係數皆增加，而吸水率減少；另外，在SiO2填充材料含量與尺寸大小對PTFE/SiO2 複合材料之性質影響研究方面，以兩種不同大小(5□m or 25□m SiO2)及0-60wt% SiO2添加含量，調配製作出各種PTFE/SiO2板材後進行各種物性測試，實驗數據分析後顯示：兩種不同大小的SiO2在含量對各種物性的影響皆有相同的趨勢，即隨著SiO2含量的增加，拉伸強度及熱膨脹係數皆減少，而拉伸剛性、吸水率及介電特性皆增加，且因為較小的SiO2填充材料具有較多之表面積，所以，添加較小的SiO2所得的PTFE/SiO2複合材料，有較高之吸水率及介電損失；再者，因PTFE基材化學反應性差，與SiO2填充物之間的作用力相當弱，是造成較低的拉伸強度及耐熱性無法提升的原因，而此現象可由SEM電子顯微鏡觀察拉伸破壞後的試片得以佐證；除此之外，本研究也將實驗數據與文獻推算兩相複合材料的理論計算值作相互比對，比對後發現介電常數與熱膨脹係數之實驗數據與理論計算值相當接近，而且Nicolais-Narkis修正計算式能有效的估算出PTFE/SiO2複合材料的拉伸強度。
    系統二以溶膠-凝膠法製備PTFE/SiO2奈米級複合材料並探討不同的siliylation agent對PTFE/SiO2複合材料的介電性質、熱性質、機械性質及形態上的影響。實驗上，以溶膠-凝膠法製備50wt% PTFE/SiO2混成材料及以雙滾輪碾壓機製作成板材，採用Trimethylchlorosilane (TMCS)及Hexamethydisilazane (HMDS)為本研究之改質劑(silylation agents),由實驗結果發現：經由改質後之PTFE/SiO2混成材料具有較低的吸水率及介電損失性質，可由IR及NMR分析發現SiO2表面之-OH基已被取代成-CH3，除此之外，已改質之PTFE/SiO2混成材料具有高的孔隙度(53.7%)、奈米級之孔洞(10-40nm)及奈米膠粒(粒徑20-50nm)等特點，使得PTFE/SiO2混成材料具有超低介電性質(Dk=1.9 & Df=0.0021)、小之熱膨脹係數(66.5 ppm/℃)、高的拉伸剛性(141 Mpa)、耐熱性(Td=612℃)及疏水性(接觸角(□)=114□)；在SiO2填充材料含量(0–60wt%)對PTFE/SiO2 複合材料之性質影響研究方面，由實驗數據分析後顯示：SiO2含量對物性的影響，與上述微米級SiO2對PTFE/SiO2基板材料的影響，有相同的趨勢，即隨著SiO2含量的增加，拉伸強度及熱膨脹係數皆減少，而拉伸剛性、吸水率及介電性質皆增加。

    目　　錄 摘要 I 謝誌 III 目錄 i 表目錄 iii 圖目錄 v 一、緒論 1 1-1 前言 1 1-2 印刷電路板的市場趨勢 1 1-3 高頻印刷電路板板材性質要求 3 1-4 印刷電路板板材常用之樹脂 9 1-5 有機-無機奈米複合材料 15 1-6 溶膠-凝膠法 17 二、理論與文獻回顧 21 2-1 PTFE材料及乳液特性 21 2-2 系統一微米級PTFE/SiO2複合材料(composite) 24 2-2-1 SiO2含量及粒徑大小之影響 25 2-2-2偶合劑種類之影響 27 2-2-3偶合劑含量之影響 28 2-3 系統二PTFE/SiO2奈米複合材料(nanocomposite) 28 2-3-1 溶膠-凝膠製備PTFE/SiO2材料 28 2-3-2 溶膠-凝膠法理論 30 2-3-3 SiO2表面的化學改質 46 2-3-4 以溶膠-凝膠法製備的有機無機混成材料 49 2-3-5 以溶膠-凝膠法製備的有機無機混成材料相關研究 52 三、研究動機及目的 57 四、研究方法與步驟 58 4-1 實驗架構 58 4-2 實驗用藥品 59 4-3 實驗流程 61 4-4 樣品製作 63 4-5 實驗儀器及測試方法 66 五、結果與討論 70 5-1 微米級PTFE/SiO2複合材料製備 70 5-2 偶合劑含量對微米級PTFE/SiO2複合材料之性質影響性研究 72 5-3 SiO2填充材料含量與尺寸大小對微米級PTFE/SiO2複合材料之性質影響性研究 83 5-4溶膠-凝膠法製備PTFE/SiO2混成材料 103 5-5 PTFE/SiO2混成材料化學表面改質研究 127 5-6 TEOS含量對PTFE/SiO2混成材料之性質影響性研究 144 六、結論 157 七、參考文獻 163 八、附錄 174 表目錄 表1-1. 基板板材的各種需求 8 表1-2. 各類高頻基板材料之介電性質與熱膨脹係數 9 表1-3. 有機高分子與無機陶瓷性質比較 16 表2-1. Characteristics of PTFE suspension 22 表2-2. Gelation time and pH for six catalysts 36 表2-3. 不同r(H2O/TEOS莫耳比)所得到不同的膠體結構 43 表2-4. 利用溶膠-凝膠反應製備有機-無機混成複材的研究與產品分類表 ………………………………………………………… 55 表2-5. 利用溶膠-凝膠反應製備有機-無機混成複材的研究及發展機構 56 表5-1. Composition and content of SiO2 in PTFE composites 74 表5-2. The effect of silane on the properties of 60wt% SiO2-reinforced PTFE composites. 74 表5-3. Comparison between experimental results and theoretical values calculated by rule of mixture for 60wt% SiO2-reinforced PTFE composites. 82 表5-4. Weight fraction of SiO2 in composites and decomposition temperature of PTFE/SiO2 composites. 85 表5-5. Material Properties of PTFE and SiO2 85 表5-6. Summarized data obtained via the DSC measurements for pure PTFE and PTFE/SiO2 composites 89 表5-7. Models for predicting the tensile strength of filled polymer. 93 表5-8. Weight fraction of SiO2 in hybrids and decomposition temperature of PTFE/SiO2 hybrids via different HF content. 110 表5-9. Weight fraction of SiO2 in hybrids and decomposition temperature of PTFE/SiO2 hybrids via different ethanol content. 115 表 5-10. Weight fraction of SiO2 in hybrids and decomposition temperature of PTFE/SiO2 hybrids via different water content. 120 表5-11. Weight fraction of SiO2 in hybrids and decomposition temperature of PTFE/SiO2 hybrids via different TEOS content. 125 表5-12. The effect of different silylation agents and reaction times on the dielectric loss (Df) properties of PTFE/SiO2 hybrids. 129 表5-13. Weight fraction of SiO2 in hybrids and decomposition temperature of dried pure PTFE, SiO2 and PTFE/SiO2 hybrids. 131 表5-14. Provisional assignment of IR reflectance peaks 135 表5-15. Summarized vibrations mode of IR peaks in the unmodified and modified PTFE/SiO2 hybrids 135 表5-16. 29Si MAS NMR deconvolution results 137 表5-17. The measured density, surface area, average pore size, pore volume and porosity properties of pure PTFE and PTFE/SiO2 hybrids. 139 表5-18. Effect of HMDS/TMCS silylation agent on the various properties of PTFE/SiO2 hybrids. 143 表5-19. The measured density, surface area, average pore size, pore volume and porosity properties of different filler content of PTFE/SiO2 hybrids. 147 表 5-20. Summarized data obtained using the DSC measurements for pure PTFE and PTFE/SiO2 hybrids 152 表 5-21. The effect of filler contents and surface modification on the various properties of PTFE/SiO2 hybrids. 155 圖目錄 圖1-1.日本通訊發展傳送速度的評估 2 圖1-2.各類高頻基板材料之性能、加工溫度與成本挑戰關係圖 10 圖1-3.利用溶膠─凝膠反應製備奈米級(Nano)型態的複合材料 17 圖1-4.凝膠化過程 18 圖2-1.SEM of primary particles of PTFE (D60A) 22 圖2-2.Viscosity behavior of PTFE dispersion as a function of Temperature.. 24 圖2-3. Water equilibrium reaction at surface of fumed silica 26 圖2-4. Concept of a Polymer/Siloxane/Glass Interphase 27 圖2-5. PTFE/SiO2塊材的SEM (A) Acid-catalyzed; (B) Base-catalyzed 30 圖2-6.水解與聚合反應對膠體結構的影響 34 圖2-7. pH值與顆粒大小關係 34 圖2-8. pH值對silica-water系統所產生之膠體的凝膠時間影響 39 圖2-9.不同的酸性觸媒對凝膠時間的影響60 41 圖2-10. Density of silica aerogel vs. Ethanol/TEOS molar ratio58 42 圖2-11.二氧化矽表面的矽氫氧基型態73 47 圖2-12.二氧化矽之表面去水及去氧基反應機構73 47 圖2-13. Si-OH表面改質反應機構 49 圖2-14.線性有機高分子崁入無機高分子的示意圖84 50 圖4-1.系統一微米級PTFE/SiO2基板的製作流程圖 62 圖4-2.系統二奈米級PTFE/SiO2基板的製作流程圖 63 圖4-3. Sintering thermal profile of the PTFE/SiO2 hybrids. 66 圖5-1. DSC curve of the 60wt% SiO2-reinforced PTFE composites. 76 圖5-2. Thermogravimetric profile of the 60wt% SiO2-reinforced PTFE composites 76 圖5-3.Tensile strength versus sintering time for the 60wt% SiO2-reinforced PTFE composites. 78 圖5-4. Tensile strength versus concentration of phenyltrimethroxy silane for the 60wt% SiO2-reinforced PTFE composites. 78 圖5-5. Cross-section SEM microghraphs of the PTFE/silica composites and pure PTFE. (a) PTFE containing 60wt% untreated SiO2, (b) PTFE containing 60wt% SiO2 treated with 3% coupling agent (c) PTFE containing 60wt% untreated SiO2, and (d) pure PTFE 80 圖5-6. Water absorption versus concentration of phenyltrimethroxy-silane for the 60wt% SiO2-reinforced PTFE composites. 83 圖5-7. Heating and cooling DSC curves of the 60wt% SiO2 (25 □m)-reinforced PTFE composite. 87 圖5-8. Tensile modulus vs. various SiO2 filler content for 25□m SiO2 (▲), 5□m SiO2 (●). 90 圖5-9. Tensile strength vs. various SiO2 filler content for 25□m SiO2 (▲), 5□m SiO2 (●). 91 圖5-10. Typical tensile strength-concentration curves for filled polymers showing upper and lower bound responses 102. 92 圖5-11. Comparison between calculated and experimental results of tensile strength. 94 圖5-12. Cross-section SEM microghraphs of the pure PTFE and PTFE/silica composites with different filler size. (A) Blank pure PTFE (Mag.=x500), (B) PTFE containing 60wt% 25□m SiO2 treated with 3% coupling agent (Mag.=x1500); and (C) PTFE containing 60wt% 5□m SiO2 treated with 3% coupling agent (Mag.=x1500). 96 圖5-13. SEM microghraphs of tensile fractured cross-section for the PTFE/SiO2 composites. (A) PTFE containing 60wt% 25□m SiO2 untreated (Mag.=x200); (B) PTFE containing 60wt% 25□m SiO2 treated with 3% coupling agent (Mag.=x200); (C) PTFE containing 60wt% 25 □m SiO2 treated with 3% coupling agent (Mag.=x1500); (D) PTFE containing 60wt% 5□m SiO2 treated with 3wt% coupling agent (Mag.=x1500); (E) PTFE containing 60wt% 5□m SiO2 treated with 3wt% coupling agent (Mag. = x1500). 96 圖5-14. Water absorption vs. various SiO2 filler content for 25□m SiO2 (▲), 5□m SiO2 (●). 98 圖5-15. Dielectric constant (Dk) vs. various SiO2 filler content for 25□m SiO2 (▲), 5□m SiO2 (●). 100 圖5-16. Dielectric loss (Df) vs. various SiO2 filler content for 25□m SiO2 (▲), 5□m SiO2 (●). 100 圖5-17. Comparison between calculated and experimental results of Dk. The curve shown is calculated by eq 5-1. 101 圖5-18. Comparison between calculated and experimental results of Df. The curve shown is calculated by eq 5-2. 101 圖5-19. CTEz vs. various SiO2 filler content for 25□m SiO2 (▲), 5□m SiO2 (●). 103 圖5-20. Comparison between calculated and experimental results of CTEz. The curve shown is calculated by eq 5-10. 103 圖5-21. PTFE Coagulation time與TEOS Gelation time 比較圖 106 圖5-22.不同HF/TEOS molar ratio之反應時間與樣品溫度關係圖 107 圖5-24. PTFE與PTFE/SiO2 在氮氣環境下之TGA比較圖 109 圖5-25.利用高斯方程式Fitting 29Si NMR圖譜126 112 圖5-26.不同HF/TEOS molar ratio之29Si NMR圖譜 113 圖5-27.不同HF/TEOS molar ratio對交聯密度的影響 113 圖5-28.不同m(Ethanol/TEOS molar ratio)對Gelation time的影響 115 圖5-29不同m(Ethanol/TEOS molar ratio)之29Si NMR圖譜 118 圖5-30不同m(Ethanol/TEOS molar ratio)對交聯密度的影響 118 圖5-31不同r(Water/TEOS molar ratio)對Gelation time的影響 119 圖5-32不同r(Water/TEOS molar ratio)之29Si NMR圖譜 122 圖5-33不同r(Water/TEOS molar ratio)對交聯密度的影響 123 圖5-34.不同k(TEOS/PTFE Weight ratio)對Gelation time的影響 123 圖5-35.不同k(TEOS/PTFE Weight ratio)在氮氣環境下之TGA 比較圖 125 圖5-36.不同k(TEOS/PTFE Weight ratio)對交聯密度的影響 127 圖5-37.不同k(TEOS/PTFE Weight ratio)之29Si NMR圖譜 127 圖5-38.Dielectric loss (Df) versus sintering time for unmodified 50wt% SiO2-reinforced PTFE hybrid. 128 圖5-39. Thermogravimetric curve for (a) pure TEOS derived silica; (b) unmodified PTFE/SiO2 containing 50wt% SiO2; (c) modified PTFE/SiO2 containing 50wt% SiO2; (d) pure PTFE. 129 圖5-40. DSC curve of sintered PTFE/SiO2 hybrid (a) modified; (b) unmodified. 133 圖5-41. IR spectra of sintered PTFE/SiO2 hybrid (a) modified; (b) unmodified. 134 圖5-42. 29Si MAS NMR spectra of PTFE/SiO2 hybrids, (A) modified; (B) unmodified. 137 圖5-43. Pore size distribution in modified and unmodified PTFE/SiO2 hybrids. Lines are drawn as guides for the eye. 139 圖5-44. Cross-sectional SEM images of pure PTFE, SiO2 and PTFE/SiO2 hybrids. (A) Blank pure PTFE (Mag.=x500), (B) pure SiO2 by sol-gel synthesis (Mag.=x30,000) and (C) PTFE containing 50wt% equivalently SiO2 modified with HMDS/TMCS (Mag.=x60,000). Small black arrows in (B) and (C) indicate the nano-size SiO2 filler. (D) PTFE containing 50wt% equivalently SiO2 powder overly heat-treated at 900℃ for 4 h (Mag.= x10,000). 141 圖5-45. TEM images (A) and EDX spectrum (B) of the modified PTFE/SiO2 hybrids. Dark regions represent SiO2 particles. 142 圖5-46. Effect of SiO2 filler content on pore size distribution of PTFE/silica hybrids. Lines are draw as guides for the eye. 146 圖5-47. Cross-sectional SEM images of pure SiO2 and PTFE/SiO2 hybrids. (A) Blank pure SiO2 by sol-gel synthesis (Mag.=×30,000), (B) PTFE containing 30wt% equivalently SiO2 modified with HMDS/TMCS (Mag.=×60,000), and (C) PTFE containing 50wt% equivalently SiO2 modified with HMDS/TMCS (Mag.=×60,000)…. 148 圖5-48. Typical heating and cooling DSC curve of SiO2-reinforced PTFE/SiO2 hybrids. 149 圖5-49. Heating DSC curves of pure PTFE and PTFE/SiO2 hybrids. 151 圖5-50. Cooling DSC curves of pure PTFE and PTFE/SiO2 hybrids. 151 圖5-51. Tensile modulus vs. various SiO2 filler contents for PTFE/SiO2 hybrids. 153 圖5-52. Tensile strength vs. various SiO2 filler contents for PTFE/SiO2 hybrids. 154 圖 5-53. Dielectric loss (Df) vs. various SiO2 filler contents for PTFE/SiO2 hybrids. 156 圖 5-54. X-axis CTE vs. various SiO2 filler contents for PTFE/SiO2 hybrids. 157

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