Polymer Analyses
GPC, TEM, SEM
Speaker : 王睿詡
Date : 2009/11/23
Outline
• GPC (Gel Permeation Chromatography)
• TEM (Transmission Electron Microscopy)
• SEM (Scattering Electron Microscopy)
GPC
(Gel Permeation Chromatography,
Size Exclusion Chromatography)
A Kind of LC Mechanisms
LC Separation Mechanisms
 Gel-Permeation Chromatography is a
mechanical sorting of molecules based
on the size of the molecules in solution.
 Small molecules are able to permeate
more pores and are, therefore, retained
longer than large molecules.
Ref. : Rubinson and Rubinson, Contemporary Instrumental Analysis, Prentice Hall Publishing.
Structural Picture
Filter (ca 0.5 um)
GPC Columns
Pump
Injector Loop
To Waste
Concentration Detector
To Waste
Waste
Optional Detector #2
e.g Light Scattering
Optional Detector #1
e.g. Viscosity
Flow
Voids: Uniform Diameter D
helps minimize voids
Pore: Size is given by the
correlation length x
x
D = 1 - 50 mm
Column of GPC
Hydrodynamic radius (Stoke’s radius)
K = cS /cM = (Ve - Vo)/Vi, since Vt = Vi + Vo + VG
(Vi is the volume of solvent held in its pores)
(Vg is the volume occupied by the solid matrix of the gel)
(Vo is the free volume outside the gel particles.)
K is distribution coefficient, we assume that
VG ≈ 0
•
•
•
•
•
Both are normally values between 0 and 1
Molecules that are too big to penetrate any of the pores
elute in Vo and give K = 0
Molecules that are small enough to penetrate all of the
pores elute in Vi + Vo and give K = 1
Between 0 and 1, larger molecules give smaller K values.
If a molecule gives a K larger than 1, it is likely interacting
with the gel beads themselves (adsorption).
Retention Time vs. Molecular Weight
Calibration Curve of GPC
Common Detectors
 UV – one of most common
 Fluorescence – much greater sensitivity than UV
 Refractive Index – widely used general detector
 Electrochemical – based on amperometry, polarography, coulometry,
or conductometry. High sensitivity, wide applicability range
 Mass Spectrometry – becoming increasingly used since interfacing
problems figured out. Expensive.
GPC Analysis
Cheng-Jyun Huang and Feng-Chih Chang* Macromolecules 2008, 41, 7041-7052
GPC Analysis
Chih-Feng Huanga, Hsin-Fang Leea, Shiao-Wei Kuoa, Hongyao Xua,b, Feng-Chih
Changa,* Polymer 45 (2004) 2261–2269
GPC Analysis
Chih-Feng Huang, Shiao-Wei Kuo, Hsin-Fang Lee, Feng-Chih Chang* Polymer 46 (2005) 1561–1565
TEM (Transmission Electron Microscopy)
SEM (Scanning Electron Microscopy)
Size !!
 肉眼可見物體的範圍：~10-3m
 光學顯微鏡(OM)可見的範
圍：~10-6m
 掃描式電子顯微鏡(SEM)可
見的範圍： ~10-8 m (~10
nm)
 穿透式電子顯微鏡(TEM)可
見的範圍： ~10-10 m (~0.1
nm)
光學顯微鏡
掃瞄式電鏡
穿透式電鏡
光源
可見光
電子槍
電子槍
透鏡
玻璃透鏡
電磁透鏡
電磁透鏡
放大倍率
1000~2000倍
10萬倍
100萬倍
解析度
0.2μm
1~10nm
0.1nm~
真空環境
不需要
需要
需要
景深
0.1~5 μm
0.1mm
500 μm
影像色彩
真實色彩
黑白
黑白
成分分析
無
可
可
樣品
大
大
薄,小
金屬鍍膜
不需
需
不需
影像
表面或穿透影像
表面影像
穿透影像
TEM (Transmission Electron Microscopy)
From 交通大學貴儀中心
TEM (Transmission Electron Microscopy)
When E0-ΔE values become
smaller, the Images become
darker; When E0-ΔE values
become bigger, the Images
become lighter.
http://www.jeol.com/tem/jem2100f.html
Scanning Electron Microscope
(SEM)
From 交通大學貴儀中心
Structural Image of SEM
http://cem.ess.nthu.edu.tw/K12/Article.asp?ColId=7806A63102F19
Principle of Imaging
0~50 ev
EDX(S) and WDX(S)
http://en.wikipedia.org/wiki/Wavelength_dispersive_X-ray_spectroscopy
Images are Different
Between in TEM and SEM
SEM Image
OM Image
TEM Image
Material Science
Angew. Chem. Int. Ed. 2002, 41, 688
Self-organization Morphology
Solution state
Bulk state
N : polymerization index
χ: Flory-Huggins interaction parameter
ƒ A : volume fraction of block A in the block copolymer
Angew. Chem. Int. Ed. 2002, 41, 688
TEM (Transmission Electron Microscopy)
Ref : Wan-Chun Chen,† Shiao-Wei Kuo,*,‡ U-Ser Jeng,§ and Feng-Chih Chang*,† Macromolecules 2008, 41, 1401-1410
TEM (Transmission Electron Microscopy)
Ref : Shiao-Wei Kuo a,*, Pao-Hsaing Tung b, Feng-Chih Chang b European Polymer Journal 45 (2009)
TEM (Transmission Electron Microscopy)
Ref : Chu-Hua Lu,† Chih-Feng Huang,† Shiao-Wei Kuo,‡ and Feng-Chih Chang*,† Macromolecules 2009, 42, 1067-1078
TEM (Transmission Electron Microscopy)
Ref : Yuung-Ching Sheen a, Chu-Hua Lu a, Chih-Feng Huang a, Shiao-Wei Kuo b, Feng-Chih Chang a,* Polymer 49 (2008) 4017–4024
Scanning Electron Microscope (SEM)
Y.-C. Yen et al. Polymer 49 (2008) 3625–3628
SHIH-CHI CHAN,1 SHIAO-WEI KUO,1 HWOSHUENN SHE,2 HO-MAY LIN,1 HSIN-FANG LEE,1
FENG-CHIH CHANG1 Journal of Polymer
Science: Part A: Polymer Chemistry, Vol. 45,
125–135 (2007)
Scanning Electron Microscope (SEM)
Pao-Hsaing Tung, Shiao-Wei Kuo,*Shih-Chien Chan, Chih-Hao Hsu,
Chih-Feng Wang, Feng-Chih Chang* Macromol. Chem. Phys. 2007, 208, 1823–1831
Scanning Electron Microscope (SEM)
Chih-Feng Wang,1 Shih-Feng Chiou,2 Fu-Hsiang Ko,3 Cheng-Tung Chou,2 Han-Ching Lin,1 Chih-Feng Huang,1 Feng-Chih Chang*1; Macromol. Rapid Commun. 2006, 27, 333–337
Conclusion
• Micro-Structural Analysis – TEM, SEM
• Molecular Weight Determination - GPC
Thank You for Your Attention