臺灣博碩士論文加值系統

本研究探討碳黑加量、電漿處理、60Coγ-ray輻射劑量對高密度聚乙烯/碳黑複合材料之正溫度係數（Positive Temperature Coefficient, PTC）與負溫度係數（Negative Temperature Coefficient, NTC）效應的影響。另一方面也研究了高密度聚乙烯/碳黑材料的表面型態、斷面型態以及動態機械性質。研究中發現，電漿處理能輕微的消除複合材料NTC效應，而添加DCP與使用60Co γ-ray輻射交聯都是提升PTC效應的有效方法，且利用動態機械分析觀察也得到相同的結果。當複合材料組成為PHDPE(40W,30min)/CB(40wt%)DCP(2phr)/5M-rad時， PTC強度可達到7個Order，並且經過了10次的熱循環測試，此組成材料具有相當好的回覆性。而PHDPE(40W,30min)/CB(40wt%)/ DCP(2phr)/10M-rad的組成PTC強度可達到8個Order。在經濟上的考量下，這二組材料都可被用來當作PTC元件。

In this investigation, the effect of carbon black content, plasma treatment, 60Co γ-ray irradiate dose and additives on the positive temperature coefficient(PTC) behavior and negative temperature coefficient(NTC) behavior of high density polyethylene/carbon black(HDPE/CB) composites were studied. On the other hand, the surface morphology observations, the fracture surface morphology observations and the dynamic mechanical properties of HDPE/CB composite were also studied. It was found that the plasma pretreated was slightly decreased the NTC effect. On the other hand, adding dicumyl peroxide(DCP) and irradiation by 60Coγ-ray irradiation were good methods for increasing the PTC intensity. Used the dynamic mechanical analysis were processed the same result. In this investigation, the composites of PHDPE(40W.30min)/CB(40wt%)/DCP(2phr)/5M-rad possessed 7 order of PTC intensity. After 10 times thermal cycle measurement the reproducibility of PHDPE(40W.30min)/CB(40wt%)/
DCP(2phr)/5M-rad was very good. PHDPE(40W.30min)/CB(40wt%)/
DCP(2phr)/10M-rad possessed 8 order of PTC intensity. These two composites could be used PTC element under economical consideration.

List of Figures…………………………………………………………….I
List of Schemes and Tables…………………………………………….VII
Abstract (Chinese)…………………………………………………….VIII
Abstract (English)…………………………………………………..…. IX

Chapter 1: Introduction………………………………….………………..1
Chapter 2: Theories and Literatures Review……………………………..5
2.1: Compatibilization of Polymer blends…………………………..5
2.2: Conductive Filler……………………………………………….6
2.3: Carbon Black…………………………………………………...7
2.3.1 Manufacture and Characteristics………………………...7
2.3.2 Classification and Grade…………………………………8
2.4: Conductive polymeric composites….………………...….....9
2.5:Cross-linked polyethylene and Cross-linked by Organic
Peroxide………………………………………………………..10
2.6: Plasma………………………………………………………....11
2.7: Dynamic Mechanical Analysis………………………………..12
2.8: PTC effect…………………………………………………......15
2.9: Polymer PTC composites…………………………………......17
2.10: Conductive mechanism………………….………..…………19
Chapter 3: Experiment…………………………………………………..31
3.1: Experimental Flowchart………………………………………31
3.2: Materials………………………………………………………32
3.2.1: Matrix………………………………………..………...32
3.2.2: Conductive filler……………………………………….32
3.2.3: Processing additives…………………………………...32
3.2.5: Copper foil…………………………………………......33
3.3: Method……………………………………………………….34
3.3.1: Argon plasma treatment…..............................................34
3.3.2: Compounding process………………............................34
3.3.3: Compression molding………………………………….34
3.3.4: Irradiate by 60Coγ-ray…………..………………….....35
3.3.5: Electric resistance measurement…………………….....35
3.3.5: Scanning electron microscopy…………………………35
3.3.7:Dynamic mechanical measurements…………………...36
3.3.8 Gel extraction…………………………………………..36
3.3.9 Thermal cycles………………………………………….37
Chapter 4: Results and Discussion……………………………………...46
4.1. Effect of plasma treatment on PTC effectiveness…………….46
4.2: Effect of different cross-linking agent content on PTC and NTC effectiveness……………………………………………….…48
4.3. Influence of radiation cross-linking on the PTC effect and NTC effect………………………………………………………….50
4.4. Surface morphology observation by scanning electron microscopy................................................................................54
4.5 Dynamic mechanical properties of HDPE/CB composites.…...57
4.6 Relation between Degree of cross-linking and radiation dose…60
4.7 Reproducibility of electrical resistance was passing through thermal cycle…………………………………………………...61

Chapter 5: Conclusion..…….……………………………………….…105
Reference……..……………………………………………………..…107

List of Figures

Figure 2.1 Summary of the factors contributing to end-use properties in
melt compounded blends, highlight the role of compatibilisers
………………………………………………………………21
Figure 2.2 The conductive mechanism of conductive filler…………….24
Figure 2.3 Typical coupling systems for plasma generation…………....28
Figure 2.4 Scheme of direct irradiation method………………………...29
Figure 2.5 Dynamic Mechanical properties of composites…………......29
Figure 2.6 The characteristic of PTC effect……………………………..30
Figure 2.7 The PTC effect work principle………………………………30
Figure 3.1 The schematic diagram of the self-designed rotary plasma equipment………………………………………………….40
Figure 3.2 The photograph of Ultra-Centrifugal Mill (Retsch ZM-1000)
………………………………………………….…………..41
Figure 3.3 The photograph of Brabender Plasti-Corder Torque Reometer (PLE-330) instrument………………………..……………..41
Figure 3.4 The photograph of Compression Molding Machine (Hyengy Hydraulic Industry Co.,Ltd.)………………………………42
Figure 3.5 The photograph of resistance measurement instrument, comprising a computer, a multi-meter (KELTHLEY 7002 switch system and 2400 source meter), and a programmable oven (DELTA 9039)………………………………………43
Figure 3.6 The test specimen of volume resistance measured………….44
Figure 3.7 The photograph of SEM(JEQL JSM-6300) instrument……..44
Figure 3.8 The photograph of DMA (2980) instrument………………...45
Figure 3.9 The test specimen of thermal cycles………………………...45
Figure 4.1 Resistance as a function of temperature for HDPE/CB composites with various CB contents………………………60
Figure 4.2 Resistance as a function of temperature for PHDPE/CB composites with various CB contents…………………..……61
Figure 4.3 Resistance of PHDPE/CB composites with adding 0.5phr DCP
with various CB content at different temperature…………..62
Figure 4.4 Resistance of PHDPE/CB composites adding 1.0phr DCP with various CB content at different temperature………………63
Figure 4.5 Resistance of PHDPE/CB composites adding 2.0phr DCP with various CB content at different temperature………………64
Figure 4.6 Resistance of PHDPE/CB composites adding 4.0phr DCP with various CB content at different temperature………………65
Figure 4.7 Resistance of PHDPE/CB composites adding 1.0phr DCP and 1.0phr MA with various CB content at different temperature
………………………………………………………………66
Figure 4.8 Resistance of PHDPE/CB composites adding 2.0phr DCP and 2.0phr MA with various CB content at different temperature
……………………………………………………………..67
Figure 4.9 Resistance of PHDPE/CB composites adding 0.5phr DCP, 60Coγ- ray irradiation dose was 5M-rad with various CB content at different temperature……………………………68
Figure 4.10 Resistance of PHDPE/CB composites adding 0.5phr DCP, 60Coγ- ray irradiation dose was 10M-rad with various CB content at different temperature……………………………69
Figure 4.11 Resistance of PHDPE/CB composites adding 0.5phr DCP, 60Coγ- ray irradiation dose was 20M-rad with various CB content at different temperature……………………………70
Figure 4.12 Resistance of PHDPE/CB composites adding 1phr DCP, 60Coγ- ray irradiation dose was 5M-rad with various CB content at different temperature……………………………………71
Figure 4.13 Resistance of PHDPE/CB composites adding 1phr DCP, 60Coγ- ray irradiation dose was 10M-rad with various CB content at different temperature…………………………...72
Figure 4.14 Resistance of PHDPE/CB composites adding 1phr DCP, 60Coγ- ray irradiation dose was 20M-rad with various CB content at different temperature……………………………73
Figure 4.15 Resistance of PHDPE/CB composites adding 2phr DCP, 60Coγ- ray irradiation dose was 5M-rad with various CB content at different temperature…………………………..74
Figure 4.16 Resistance of PHDPE/CB composites adding 2phr DCP, 60Coγ- ray irradiation dose was 10M-rad with various CB content at different temperature……………………………75
Figure 4.17 Resistance of PHDPE/CB composites adding 2phr DCP, 60Coγ- ray irradiation dose was 20M-rad with various CB content at different temperature……………………………76
Figure 4.18 Resistance of PHDPE/CB composites adding 4phr DCP, 60Coγ- ray irradiation dose was 5M-rad with various CB content at different temperature……………………………………77
Figure 4.19 Resistance of PHDPE/CB composites adding 4phr DCP, 60Coγ- ray irradiation dose was 10M-rad with various CB content at different temperature……………………………78
Figure 4.20 Resistance of PHDPE/CB composites adding 4phr DCP, 60Coγ- ray irradiation dose was 20M-rad with various CB content at different temperature……………………………79
Figure 4.21 Resistance of PHDPE/CB composites adding 1phr DCP, 1phr MA, 60Coγ- ray irradiation dose was 5M-rad with various CB content at different temperature……………………….80
Figure 4.22 Resistance of PHDPE/CB composites adding 1phr DCP, 1phr MA, 60Coγ- ray irradiation dose was 10M-rad with various CB content at different temperature……………………….81
Figure 4.23 Resistance of PHDPE/CB composites adding 1phr DCP, 1phr MA, 60Coγ- ray irradiation dose was 20M-rad with various CB content at different temperature……………………….82
Figure 4.24 Resistance of PHDPE/CB composites adding 2phr DCP, 2phr MA, 60Coγ- ray irradiation dose was 5M-rad with various CB content at different temperature……………………….83
Figure 4.25 Resistance of PHDPE/CB composites adding 2phr DCP, 2phr MA, 60Coγ- ray irradiation dose was 10M-rad with various CB content at different temperature……………………….84
Figure 4.26 Resistance of PHDPE/CB composites adding 2phr DCP, 2phr MA, 60Coγ- ray irradiation dose was 20M-rad with various CB content at different temperature……………………….85
Figure 4.27 Resistance of HDPE/CB composites adding 2.0phr DCP with various CB content at different temperature………………86
Figure 4.28 Resistance of HDPE/CB composites adding 2phr DCP, 60Coγ- ray irradiation dose was 5M-rad with various CB content at different temperature……………………………………87
Figure 4.29 Resistance of HDPE/CB composites adding 2phr DCP, 60Coγ- ray irradiation dose was 10M-rad with various CB content at different temperature……………………………88
Figure 4.30 Resistance of PHDPE/CB composites adding 2phr DCP, 60Coγ- ray irradiation dose was 20M-rad with various CB content at different temperature……………………………89
Figure 4.31 shows the morphology of various samples(HDPE/CB40) that was fractured in liquid N2………………………………….90
Figure 4.32 shows the morphology of various samples that was fractured in liquid N2 which different additive with irradiated dose (5M-rad) and plasma pretreated…………………………...91
Figure 4.33 The matte side of copper foil which tears off specimen which irradiated dose was 5-Mrad and with or without plasma pretreated…………………………………………………..92
Figure 4.34 The matte side of copper foil which tears off specimen (PHDPE/CB40) which irradiated dose was 10M-rad and 20M-ray with plasma pretreated…………………………...93
Figure 4.35 The matte side of copper foil which tears off specimen in different agent which irradiated dose was 5-Mrad and with plasma pretreated…………………………………………..94
Figure 4.36 Reproducibility of electrical resistivity was passing through thermal cycle 10 times……………………………………..95
Figure 4.37 The relation between gel(wt%) and radiation dose M-rad…96
Figure 4.38 The temperature dependence of the storage modulus of composites with difference amount of additives…………..97
Figure 4.39 The temperature dependence of the loss modulus of composites with difference amount of additives…………..98
Figure 4.40 The temperature dependence of the storage modulus of CB40D2 with various doses of 60Coγ-ray irradiation……99
Figure 4.41 The temperature dependence of the loss modulus of CB40D2
with various doses of 60Coγ-ray irradiation…………….100
Figure 4.42 The temperature dependence of the storage modulus of PCB40D2 with various doses of 60Coγ-ray irradiation…101
Figure 4.43 The temperature dependence of the loss modulus of PCB40D2 with various doses of 60Coγ-ray irradiation…102









List of Schemes and Tables

Table 2.1 Classification of conductive filler……………………..……...22
Table 2.2 Electrical conductive of metals, conductive plastics and various insulation materials at 25°C……………………..……………23
Table 2.3 Manufacturing Methods and Characteristics of Rubber-Grade Carbon Blacks………………………………………………..25
Table 2.4 Classification of Carbon Blacks……………………………...26
Table 2.5 Application for conductive polymeric composites…………...27
Table 3.1 The physical properties of HDPE (LH606)…………………..38
Table 3.2 The typical properties of CB (N-660)………………………...38
Table 3.3 The physical properties of add agents………...........................38
Table 3.4 The typical properties of copper foil………………………….39
Table 3.5 Abbreviations of specimens…………………………………..39

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