1、聚合物納米復(fù)合材料,盧紅斌 博士、副教授 復(fù)旦大學(xué)高分子科學(xué)系 躍進(jìn)樓210室 電話(huà)：55664589（辦） Email:,2004年10月13日,Flexible chain,Stiff chain,Semi-Stiff chain,C T E,Low,High,Molecular Structure Adjustment,Topological Structure Adjustment,No polymer network No particle network,Polymer network + local particle network,Interpenetrating polyme

2、r and particle networks,Contribution to CTE and mechanical properties,Low,High,(1) Structural adjustment,(2) Low CTE Nanoparticles,Montmorillonite,Attapulgite,MWCNT,Polyoxometalate,研究思路,固體顆粒表面改性,(2) Attapulgite (ATT),(1) Montmorillonite (MMT),(3) Multiwall Carbon Nanotubes (MWCNT),(4) Polyoxometalat

3、e (POM),Na+,Na+,Na+,Na+,Na+,Na+,Ion Exchange,-OH,-OH,-OH,Activation, Covalently Bonding,Oxidation, Functionalization,Coordination/Anion Exchange,蒙脫土/環(huán)氧納米復(fù)合材料-受限松弛 （1）,相同條件下的純樹(shù)脂和復(fù)合材料的DSC 曲線：10 oC/min,相同過(guò)冷度下的不同材料的焓松弛比較：Tg-20 oC 退火372小時(shí),Anastasiadis, S.H., Phys. Rev. Lett. 2000, 84(5):915-918 (Greece);

4、,Hongbin Lu, Steven Nutt, Macromolecules, 2003, 36(11):4010-4016,蒙脫土/環(huán)氧納米復(fù)合材料-受限松弛 （2）,受限松弛的唯象解釋 (1),Dh*,x,b,Tf=Tg,Temperature, T,Heat capacity or enthalpy, Cp or Sc,Non-equilibrium glass,Equilibrium liquid,Non-Debye relaxation process,Sc, Tf,Segmental Relaxation,Nonlinearity:,Nonexponentiality:,（TN

5、M Model）,受限松弛的唯象解釋 (2),Using cooperatively rearranging concept to elucidate the change in configurational entropy during segmental motions.,High surface area + Good interface adhesion,Lower configurational entropy,Slower segmental motion,Good stability and mechanical properties,Results,Overview,Adam

6、-Gibbs model:,Hongbin Lu, Steven Nutt, Macromol. Chem. Phys. 2003, 204: 1832-1841,(C. A. Angell et al, Nature, 2001, 410, 663-667),玻璃化轉(zhuǎn)變的熱力學(xué)動(dòng)力學(xué)相關(guān)性,玻璃化轉(zhuǎn)變的構(gòu)象熵模擬,Configurational Entropy Model:,(Gomez Ribelles, J. L. et al. Macromolecules, 1995, 28, 5867; 1995, 28, 5878. ),構(gòu)象熵模擬結(jié)果,熱力學(xué)和動(dòng)力學(xué)脆性之間：反相關(guān),熱力學(xué)和動(dòng)力

7、學(xué)之間的聯(lián)系,我們的建議：,然而,m 16 ?,Hongbin Lu, Steven Nutt, Macromolecules, submitted,棒狀硅酸鹽/環(huán)氧納米復(fù)合材料,棒狀硅酸鹽/環(huán)氧納米復(fù)合材料-實(shí)驗(yàn)結(jié)果,Hongbin Lu, Steven Nutt et al., Adv. Mater., submitted,Discovered by Iijima in 1991 Outstanding properties: Tensile modulus SWNT: 1.25 TPa ; 56 times higher than steel wire 1.7 times higher

8、than silicon carbide nanonods Electrical conductivity 104 S/cm; higher than amorphous metal Calcium-Aluminum (103 S/cm) Thermal conductivity MWNT: 3000 W/m-K; higher than graphite (2000 W/m-K) Thermal expansion coefficient SWNT: -1.5 ppm K-1,多壁碳納米管/環(huán)氧納米復(fù)合材料,Two critical issues Uniform dispersion Goo

9、d interfacial adhesion Current strategy (Covalent bonding and Noncovalent bonding) Covalent Functionalization Sonication,Acylchloride:,Fluorination:,多壁碳納米管/環(huán)氧納米復(fù)合材料,Advantages: (1) rather mild reaction conditions (reflux at 80 oC) (2) shorter reaction time ( 1 h) (3) higher functionalization efficie

10、ncy ( 4 wt %),Simple Functionalization Method with Commercial Potential,多壁碳納米管/環(huán)氧納米復(fù)合材料,Only characteristic adsorptions of amine groups, no isocyanate groups 3.7 0.9 % weight loss of organic molecules,多壁碳納米管/環(huán)氧納米復(fù)合材料,MWNTs,MWNTs-epoxy Composites,多壁碳納米管/環(huán)氧納米復(fù)合材料,MWNT-Epon 862-DDM Nanocomposites (DMA)

11、,多壁碳納米管/環(huán)氧納米復(fù)合材料,Two important factors: Exclusive volume effect below Tg Confined segmental motions above Tg,多壁碳納米管/環(huán)氧納米復(fù)合材料,(Wei, Nano Letters, 2002, 2, 647),Dynamics simulation for SWNT-PS: CTE increases, whether in rubber state or in glass state,Neutron reflectivity experiments: CTE decreases in

12、the rubber state, due to the boundary confinement of polymer films,(Pochan, Macromolecules, 2001, 34, 3041),多壁碳納米管/環(huán)氧納米復(fù)合材料,即將開(kāi)展的工作,零膨脹有機(jī)高分子材料 有機(jī)熱電材料 受限鏈段動(dòng)力學(xué) 聚合物納米復(fù)合材料流變學(xué),DSPN Components: Low CTE Inorganic Nanoparticles,1. Mesoporous nanoparticles:,ZrW2O8 (CTE = -8.510-6 K-1) HfW2O8 (CTE = -5.310-6

13、K-1),2. Nanobuilding blocks:,(SiW10O36(RPO)2)4-) Zr10O6(OH)4(OPr)18(AAA)6,(Inorganic clusters with low CTE),Mesoporous particle,Polymer molecules,New Concepts and New Materials,零膨脹材料,應(yīng)用前景、研究現(xiàn)狀,加電制冷綠色冰箱，紅外傳感器制冷，電腦芯片制冷等; 溫差發(fā)電太陽(yáng)能熱電轉(zhuǎn)換電池，熱機(jī)式原子能電池，人 造衛(wèi)星電源等。,Brian C. Sales, Science, 2002, 295, 1248,有機(jī)熱電材料,

14、家用冰箱的能量轉(zhuǎn)換效率（卡諾系數(shù)）：30 大型中央空調(diào)設(shè)備的卡諾系數(shù)： 90 現(xiàn)有熱電材料(ZT 1.0)的卡諾系數(shù)： 10,基本原理、性能參數(shù),Seebeck 效應(yīng)：溫差產(chǎn)生電流 Peltier 效應(yīng)： 電場(chǎng)導(dǎo)致冷卻,熱電優(yōu)值 ZT = S2sT/k,熱電性能表征,S Seebeck 系數(shù)；s 電導(dǎo)率；k 熱導(dǎo)率。,有機(jī)熱電材料,最好的熱電材料PbSeTe/PbTe QDSL,ZT = 2.0 at 300 K, k = 3.3 W/m.K, DT = 42.7 K,T. C. Harman, P. J. Taylor, M. P. Walsh, B. E. LaForge Science, 2002,