Studies on the lamellar thickening of a 4-arm poly(ethylene oxide) with Mn=5000 for each arm are reported. The samples were prepared by quenching from 70 ℃ to 10 ℃. Small-angle X-ray scattering (SAXS) was used to track the variation of lamellar structure during heating process. Then the SAXS data were further analyzed using one-dimensional correlation function. The following parameters
such as long period
linear crystallinity
crystalline layer thickness and amorphous layer thickness
were determined. Their changes with increasing temperature suggest three temperature regions. Region Ⅰ is in 26~45 ℃. There are three broad scattering peaks with low scattering intensity. They correspond to lamellae with different thicknesses. The crystalline layer thickness of the dominated lamella is about 9.3 nm. Importantly
the parameters mentioned above remain unchanged in Region Ⅰ. Region Ⅱ within 45~52 ℃ is a transition one. The main peak of the SAXS curves turns into two. The long period
linear crystallinity
crystalline layer thickness and amorphous layer thickness began to increase. Region Ⅲ (52~60 ℃) is a thickening region within which the crystalline layer thickness clearly increased with increasing temperature. At 60 ℃ its value is 15.8 nm. These observed results found in the three regions were further explained based on the role of metastable states of polymer lamellae. Within region Ⅰ macromolecules were in a frozen state
thus it was impossible to detect any change related to the lamellar structure. Within region Ⅱ
the temperature is higher enough to let some thin crystalline layers melt and then the melted macromolecules would recrystallize around the thicker ones. In region Ⅲ the continuous melting-recrystallization process proceeds until the melting point of the sample. The observed melting-recrystallization process reflects the metastability of polymer lamellae: Thinner lamellae are in a metastable state with a lower stability
thus will melt to recrystallize to form thicker lamellae with a higher stability. Acctually
the continuous melting-recrystallization process is a typical Ostwald ripening of polymer lamellae.
CONFINED CRYSTALLIZATION AND MELTING BEHAVIOR OF POLY(ETHYLENE OXIDE) CAPPED WITH n-OCTADECYL GROUPSTHE EFFECT OF TETHERING DENSITY
EVOLUTION OF CRYSTAL PATTERNS OF SINGLE-LAYER LAMELLAE OF STAR-SHAPED PEO SAMPLES
THICKENING PROCESS OF LAMELLAR CRYSTALS OF A LOW MOLECULAR WEIGHT POLY(ETHYLENE OXIDE)
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Key Laboratory of Advanced Materials MOE, Department of Chemical Engineering, Tsinghua University
Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Nankai University
School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066004