Citation: Yi-xin Liu, Er-qiang Chen. Thickening Kinetics of Monolayer Crystals of Low Molecular Weight Poly(ethylene oxide) Fractions on Mica Surfaces[J]. Acta Polymerica Sinica, ;2018, 0(9): 1212-1220. doi: 10.11777/j.issn1000-3304.2017.17333 shu

Thickening Kinetics of Monolayer Crystals of Low Molecular Weight Poly(ethylene oxide) Fractions on Mica Surfaces

Yi-xin Liu ^1,, ,
Er-qiang Chen ²

1.
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438
2.
Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871

Corresponding author: Yi-xin Liu, 2754093878@qq.com
Received Date: 18 December 2017
Revised Date: 16 January 2018
Available Online: 1 March 2018

The thickening of monolayer crystals of low molecular weight poly(ethylene oxide) (PEO) fractions on mica surface are in situ monitored by an atomic force microscopy (AFM) coupled with a hot stage. Two PEO fractions, with different molecular weights (HPEO2K, M_n = 2000; HPEO3K, M_n = 3000), have been examined. It is found that thickening domains continuously emerge when smooth once-folded-chain crystals are annealed isothermally below their melting temperature. A single thickening domain can grow in thickness and lateral size simutaneously. The growth of the thickness of the thickening domain follows a sigmoidal curve and depends significantly on the annealing temperature. It is found that the thickness of the thickening domain grows linearly with the logarithm of time. Such linear relation implies that its underlying mechanism should be nucleation and growth, as confirmed by a theoretical derivation of the thickness of the thickening domain as a function of time based on this mechanism. For each annealing temperature, a linear regression between the thickness of the thickening domain and the logarithm of time is performed and the obtained reciprocal of the slope linearly depends on the reciprocal of the annealing temperature. Then the surface free energy of the lateral surface of the folded-chain crystals can be inferred from the relation between the reciprocal of the slope and the annealing temperature. In this study, the value of the lateral surface free energy is found to be 1.25 and 1.22 kJ/mol for HPEO2K and HPEO3K, respectively. These values agree well with each other and also with reported values, which further validates our proposed mechanism. The lateral size of the thickening domain grows linearly with time as long as its thickeness approaches the extended-chain crystal. Such type of growth resembles the direct growth of the polymer crystals from the melt. However, its reltation between the growth rate and the annealing temperature is quite different from that of the growth of polymer crystals: the growth rate increases with the annealing temperature in the thickening case while it decreases with the crystallization temperature in the crystallization case. It indicates that there is an activation process rather than a nucleation process during thickening, which has been attributed to the chain sliding diffusion within the folded-chain crystals.
- Thin film crystallization,
- Folded-chain crystal,
- Thickening,
- Growth kinetics
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