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研究生:李耀輝
研究生(外文):Yao-Hui Lee
論文名稱:應用於低溫共燒陶瓷之氧化鑭-氧化矽-氧化硼基玻璃陶瓷之製程及特性分析
論文名稱(外文):Processing and Characterization of La2O3-SiO2-B2O3 Based Glass-Ceramics for LTCC Application
指導教授:韋文誠韋文誠引用關係
指導教授(外文):Wen-Cheng J. Wei
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:材料科學與工程學研究所
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:英文
論文頁數:86
中文關鍵詞:氧化硼莫來石玻璃陶瓷燒結介電性質氧化鑭氧化矽
外文關鍵詞:La2O3SiO2dispersionB2O3mulliteglass-ceramicssinteringdielectric
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本研究以高溫熔融及刮刀成型的方法來製作含氧化鑭-氧化矽-氧化硼(LSB)基之玻璃陶瓷材料。鑭-矽-硼氧化物之混合物可在1300oC均勻熔融,部分玻璃系統呈現非晶形狀態,其中LSB3玻璃具有優良的燒結能力。以LSB3玻璃(莫爾百分比: La2O3 22%, SiO2 10%, B2O3 68%) 添加40%莫來石(Mullite) 所組成的玻璃陶瓷 (LSBM) 可在760oC的溫度燒結緻密,得到一燒結密度為3.39 g/cm3及孔隙率低於0.5%的玻璃陶瓷複合材料,符合低溫共燒陶瓷(LTCC)的需求。此外,本研究中嘗試以六種商用之分散劑及兩種溶劑做為分散LSBM玻璃陶瓷之研究,結果顯示甲苯及RE-610分散劑對於LSB玻璃具有最佳的分散效果。研究中並分析相變及微結構,結果顯示LSBM玻璃陶瓷在840oC持溫一小時產生兩種結晶相,一種為薄片狀的鑭-硼-矽結晶 (LaBO(SiO4)),另一結晶相為含鑭-硼的結晶 (LaB3O6)。同時進一步以TEM分析,驗證各個結晶相的成分以及結晶之型態。最後,LSBM玻璃陶瓷的介電常數(�捸^及介電損失(tan �唌^皆隨著LSB玻璃的含量增加而增加;在1 GHz的頻率下,介電常數及損失的值分別為4.85及 2.4×10-3。
Synthesis of La2O3-SiO2-B2O3 (LSB) based glass-ceramic composites using glass melting and tape-casting methods of glass powder/filler has been conducted in this study. The LSB mixture could be melted homogeneously at 1300oC. XRD result showed that some LSB glass systems were entirely amorphous. Among those glasses, LSB3 glass (molar ratio: La2O 3 22%, SiO2 10%, B2O3 68%) showed a superior sintering ability (∆T=115oC). The LSB/mullite (LSBM) glass-ceramics (with a mass ratio of 60/40) composite could be sintered at a low temperature of 760oC, giving an optimal sintered density of 3.39 g/cm3, and porosity less than 0.5 %, which matched the requirements for the low-temperature-cofired- ceramics (LTCC) application. Moreover, dispersive behavior of the L3 glass powder with six kinds of commercial dispersants in MEK and toluene solvents had been studied. Toluene and RE-610 (with an addition of 1.0 mass % to the glass) were found to be the optimal system to L3 glass powder. Furthermore, the investigation on crystal phase formation and microstructure analysis of the LSBM was conducted. LSBM system had two crystal phases, including flaky LaBO(SiO4) crystals and bulky crystalline LaB3O6 grains when sintered above 840oC for 1 h, while the LaBO3 crystal phase was a transient phase between 800oC and 840oC. The dielectric constant (��), and dielectric loss (tan ��) of the LSBM glass-ceramics increased as the content of L3 glass increased. The LSBM (60/40) glass-ceramic composites showed superior �� and tan �� properties of 4.85 and 2.4×10-3, respectively at 1 GHz.
Content
摘 要 I
Abstract II
Content III
List of Figure V
List of Table IX
Chapter 1 Introduction and Objectives 1
Chapter 2 Literature Review 3
2.1 Trend of Multi-layer Ceramics and LTCC Technology 3
2.2 Glass-Ceramic Systems 4
2.3 La2O3-B2O3-SiO2 Phase Diagrams 8
Chapter 3 Experimental Procedure 17
3.1 Materials 17
3.1.1 Glass Powders (La2O3, SiO2, and B2O3) 17
3.1.2 Filler Material 18
3.1.3 Dispersant and Solvent 18
3.2 Synthesis of LSB Glass Powder 18
3.2.1 Glass Melting 18
3.2.2 Grinding and Sieving 19
3.3 Colloidal Processing and Sintering 20
3.3.1 Tape-Casting process 20
3.3.2 Binder Burn-Out (BBO) and Sintering Process 21
3.4 Thermal Analyses of LSBM glass-ceramics 21
3.5 Property Analysis 22
3.5.1 Sedimentation Tests 22
3.5.2 Green Density Measurement 23
3.5.3 Bulk Density Measurement 23
3.5.4 X- ray Diffractometric (XRD) Analysis 23
3.5.5 Microstructural Observation by SEM 24
3.5.6 Microstructural Observation by TEM 24
3.5.7 Boron Dissolution Test 25
3.6 Measurement of Dielectric Property 25
Chapter 4 Results and Discussion 42
4.1 Ternary Phase Diagram and XRD Results of LSB Glass-Ceramics 42
4.2 Thermal Analysis 42
4.2.1 DTA (differential thermal analysis) Results 42
4.2.2 Sintering Behaviors of Glass and Glass-Ceramics 44
4.2.3 TGA (Thermogravimetric Analysis) 45
4.3 Dispersion of Glass and Mullite Powders in Solvent 57
4.3.1 Sedimentation of L3 glass 57
4.3.2 Rheological behaviors of LSBM slurry 57
4.4 Properties of LSBM Glass-Ceramics 61
4.4.1 Green State 61
4.4.2 Sintered State 61
4.4.3 Transformation of Crystalline Phases 62
4.4.4 SEM Micrographs of LSBM Glass-Ceramics 63
4.4.5 TEM Micrographs of LSBM Glass-Ceramics 64
4.5 Dielectric Properties of LSBM and LSBQ 73
4.6 Dissolving Results 79
Chapter 5 Conclusions 82
Reference 83
List of Figure
Figure 2-1 Trend of the wireless communication and the potentials of LTCC technologies with high integration, high frequency, miniaturization, and low loss. 11
Figure 2-2 Loss tangent (tan ��) vs. frequency of dielectric materials. [5] 12
Figure 2-3 Schematic of fabrication processes of multilayer co-fired substrate. [11] 13
Figure 2-4 Binary phase diagram of La2O3 and B2O3. [30] 14
Figure 2-5 Binary phase diagram of La2O3 and SiO2. [30] 15
Figure 2-6 Binary phase diagram of SiO2 and B2O3. [30] 16
Figure 3.1 Experimental flow chart. 28
Figure 3-2 (a) SEM micrograph, and (b) EDS result of the La2O3 powder. 29
Figure 3-3 XRD spectrum of the La2O3 powder (JCPD file, # 05-0602). [31] 30
Figure 3-4 (a) SEM micrograph, and (b) EDS result of the SiO2 powder. 31
Figure 3-5 XRD spectrum of the SiO2 powder. 32
Figure 3-6 (a) SEM micrograph, and (b) EDS result of the B2O3 powder. 33
Figure 3-7 XRD spectrum of the B2O3 powder. 34
Figure 3-8 (a) SEM micrograph and, (b) EDS result of the mullite powder. 35
Figure 3-9 XRD spectrum of mullite powder (JCPD #79-1456). [32] 36
Figure 3-10 Particle size distribution of the LSB3 glass powder by wet-grinding process (a) without adding dispersing agent; (b) with dispersing agent. The final average size (d50) of the glass powder by 72 h is 1.07 �慆. 37
Figure 3-11 Relationship between grinding time and d50 by wet-grinding process with (dotted line) and without (solid line) dispersant (Darven C, 2 wt %). 38
Figure 3-12(a) SEM micrograph and (b) EDS result of the L3 glass powder. 39
Figure 3-13 Flow chart of the slurry preparation and tape-casting process used in this study. 40
Figure 3-14 BBO and sintering processes of (a) LSBM tape and (b) Dupont 951 tape. 41
Figure 4-1 Ternary diagram of LSB glass-ceramics system and the phases synthesized at 1300oC for 1 h in air. The glass region is marked near the B2O3 corner. 48
Figure 4-2 XRD spectra of LSB glass-ceramics synthesized at 1300oC for 1 h in air. 49
Figure 4-3 DTA curves of LSB3 and LSB4 glasses sintered from room temperature to 900oC in air. The curves (a) and (b) represent the LSB3 glass sintered at a heating rate of 2oC/min and 10oC/min, respectively. The curve (c) represents the LSB4 glass sintered at a heating rate of 10oC/min. 50
Figure 4-4 DTA curves of LSB3 glass and L40M sample sintered from room temperature to 900oC in air at a heating rate of 10oC/min. 51
Figure 4-5 Dilatometric behavior of die-pressed L3 glass sample at a heating rate of 10oC/min in air. 52
Figure 4-6 Dilatometric curve of the die-pressed LSBQ sample with 30 mass % of quartz and 70 mass % of L3 glass tested at a heating rate of 10oC/min in air. 53
Figure 4-7 Dilatometric curves of the die-pressed LSBM samples with various contents (mass %) of L3 glass and mullite powder tested at a heating rate of 10oC/min in air. 54
Figure 4-8 TGA and DTG curves of a PMMA binder tested at heating rate of 2oC/min or 10oC/min in air. 55
Figure 4-9 TGA and DTG curves of the LSBM green tape at a heating rate of 2oC/min in air. 56
Figure 4-10 Sedimentation results of the L3 slurries using six dispersants in MEK and RE-610 in toluene (as indicated in the inserted box). 59
Figure 4-11 Rheological behaviors of LSBM slurry. The curve (a) represents the relationship of shear stress and shear rate, the curve (b) represent the relationship between Casson viscosity and shear rate. 60
Figure 4-12 SEM, secondary electron imaging (SEI) micrographs of as-casted LSBM green tape, (a) top surface, and (b) bottom surface next to Mylar carrier. 65
Figure 4-13 Sintered properties of the LSBM glass-ceramics sintered at 760oC at heating rates of 5 or 10oC/min in air. The sintered density and porosity of one LSBM sample sintered at 865oC/ 0.5 h at a heating rate of 10oC/min in air were shown as and in the diagram. 66
Figure 4-14 XRD spectra of the LSBM glass-ceramics sintered at different temperatures and holding times. 67
Figure 4-15 SEM (SEI) micrograph of a polished LSBM glass-ceramics sintered at 865oC for 0.5 h at a heating rate of 10oC/min in air. 68
Figure 4-16 SEM (SEI) micrographs of the LSBM glass-ceramics sintered at 760oC for (a) 2 h and (b) 3 h at a heating rate of 5oC/min in air. 69
Figure 4-17 SEM, back-scattered imaging (BSI) micrographs of the polished cross-section of the LSBM tapes sintered at 760oC for (a) 1 h and (b) 2 h at a heating rate of 10oC/min in air. 70
Figure 4-18 (a) SEM, back-scattered imaging (BSI) micrograph of the polished cross-section of one LSBM sample sintered at 760oC for 2 h, then 840oC for 0.5 h at a heating rate of 5oC/min in air. (b) Magnification image of the center region of (a). 71
Figure 4-19 TEM images of LSBM sample which has been sintered at 760oC/ 2 h, then heat-treated at 840oC/ 2 h. (a) Bright field (BF) image, (b) center dark field (CDF) image with inserted diffraction patterns, (c), (d), and (e). 72
Figure 4-20 (a) Relationship between dielectric constant and frequency of various LSBM samples. (b) Sintered density vs. contents of mullite in sintered LSBM glass-ceramics, which had been sintered at 760oC for 2 h, then heat-treated at 840oC for 30 min in air. 77
Figure 4-21 (a) Relationship between dielectric constant and frequency of various LSBQ samples. (b) Sintered density vs. contents of mullite in sintered LSBQ glass-ceramics, which had been sintered at 760oC for 2 h, then heat-treated at 840oC for 30 min in air. 78
Figure 4-22 Relationship between (a) mass of the testing samples and testing time; (b) pH value of the aqueous solutions against the testing time. 80
Figure 4-23 Relationship between (a) mass of the testing samples and testing time; (b) pH value of the acidic solutions against the testing time. 81


List of Table
Table 2-1 Characteristics and physical properties of ceramic tape technologies [7] 9
Table 2-2 LTCC package systems reported by different manufactures 10
Table 3-1 Compositions (in molar fraction, %) of LSB glass-ceramics in this study 26
Table 3-2 Physical properties and chemical composition of the quartz 27
Table 4-1 Maximum linear shrinkage and sintered density of the LSBM samples appeared in Fig. 4-7 47
Table 4-2 Sintered and dielectric properties of various LSBM samples tested at various frequency ranges 75
Table 4-3 Sintered and dielectric properties of various LSBQ samples tested at various frequency ranges 76
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