Characterization of Glassy State Relaxations in Styrene and Methacrylate Based Nonlinear Optical Materials

1992 ◽  
Vol 247 ◽  
Author(s):  
Michael A. Schen ◽  
Fred I. Mopsik

ABSTRACTSub-Ts relaxations in polymethylmethacrylate (PMMA) and in narrow molecular weight polystyrene (PS) thin films with and without second order nonlinear optical dyes have been examined using time domain dielectric spectrometry. Dyes used include 4-[N, N-dimethylamino]-4’-nitrostilbene (DANS) and 4-[N-ethyl, N-hydroxyethylaminoJ-4’-nitroazobenzene (DR1) at a level of 0.19 mole percent. In dye/PS blends, dye relaxations are seen to occur at frequencies similar to the frequencies of the β-relaxation of pure PS below the glass transition temperature. Analysis of the glassy phase dispersion leads us to conclude that, at near room temperature, appreciable dye reorientation occurs on a time scale of a few seconds. This dye reorientation is coupled to the dynamic motions of the localized polystyrene subunits. Experiments using dye in PMMA did not conclusively reveal dye motions because of the intrinsically large dispersion of PMMA itself. The β-relaxation frequency range is higher in the PMMA dye/polymer blend than in dye-containing PS implying dye reorientation would likewise occur more rapidly than in PS. Our results indicate that the randomization of dye orientation observed in a dye/polymer system depends on the rapid, local chain motions which continue at temperatures well below the glass transition temperature, as well as on the long range, slow relaxations associated with the glass-to-rubber transition.

Polymers ◽  
2021 ◽  
Vol 13 (6) ◽  
pp. 954
Author(s):  
Xavier Monnier ◽  
Sara Marina ◽  
Xabier Lopez de Pariza ◽  
Haritz Sardón ◽  
Jaime Martin ◽  
...  

The present work aims to provide insights on recent findings indicating the presence of multiple equilibration mechanisms in physical aging of glasses. To this aim, we have investigated a glass forming polyether, poly(1-4 cyclohexane di-methanol) (PCDM), by following the evolution of the enthalpic state during physical aging by fast scanning calorimetry (FSC). The main results of our study indicate that physical aging persists at temperatures way below the glass transition temperature and, in a narrow temperature range, is characterized by a two steps evolution of the enthalpic state. Altogether, our results indicate that the simple old-standing view of physical aging as triggered by the α relaxation does not hold true when aging is carried out deep in the glassy state.


2018 ◽  
Vol 16 (36) ◽  
pp. 153-171
Author(s):  
Nahida J. H.

The present work studies the mechanical properties of SiO2 μPs, and NPs in St/PVA blends. The samples were prepared by casting method as PVA, St/PVA blends at different concentrations (30, 40, 50, and 60 %). DSC and TGA tests were carried out to the samples evolved. The result showed a single glass transition temperature (Tg) for all St /PVA blends that was attributed to the good miscibility of the blends involved. It was found that (Tg) decrease with starch ratio increase. It was seen that (PVA) of (Tg=105 oC); The glass transition temperature which was decrease with starch ratio that was attributed to glass transition relaxation process due to micro-Brownian motion of the main chain back bond. The endothermic peak at 200 oC was attributed to melting point of (PVA). Thermal properties of PVA; and St /PVA blends at different concentration (30, 40, 50, and 60 %) were evaluated by thermo gravimetric analysis (TGA). The analyses were carried out from 20 to 600 oC at 10 oC)/min heating rate in air oxygen atmosphere. The weight loss stages depended on polymer system. The starch addition causing shifting in the second degradation temperature to the higher temperature; which result in overlapping between the two main degradation steps, these result was attributed to the St/ PVA blend compatibility. The mechanical properties results showed a decrease in ultimate strength with starch ratio increase. The ultimate strength of (PVA) was (47 MPa), whereas the ultimate strength of 60 %St/PVA was (11 MPa) and for 30 %St/PVA was the highest ultimate strength of blends involved (26 MPa). SiO2μPs (753.7 nm), and NPs (263.1 nm) were added at different concentrations (1.5, 2, and 2.5 %). 1.5% SiO2μPs, and NPs of the best ultimate strength (69 MPa), (86 MPa) respectively then it was decreased by SiO2μPs, and NPs increase. Optical microscope of the samples involved was investigated. It was concluded the prepared samples were suggested to be used as packaging materials for agriculture application and its ultimate strength could be controlled by SiO2μPs, and NPs addition.


2015 ◽  
Vol 1105 ◽  
pp. 259-263
Author(s):  
Shih Yu Hung ◽  
Yu Ting Hung ◽  
Ming Ho Shen

Double-layer heterogeneous photoresist method will be used firstly to obtain the round photoresist column with two layers of different photoresists. Since both photoresists are the positive-type, the exposure is only required once. During the thermal reflow processing, the upper photoresist layer (AZ-4620 and nanomagnetic powder mixture) reaches the glass transition temperature, which is transformed from a glassy state into a rubbery state. Since the glass transition temperature of the lower photoresist layer (AZ-5214E) is higher than the temperature of thermal reflow, the lower photoresist layer is still able to maintain its solid state. The lower layer creates a round base during the thermal reflow process, and then subjected to an appropriate magnetic field. The base can not only restrict the bottom shape of the liquid photoresist to a round shape but also prevent the sliding of liquid photoresist during the thermal reflow process, so the tilted microlens array can be obtained. We can vary the strength of magnetic field to control the oblique angle of the tilted microlens.


2020 ◽  
Vol 62 (10) ◽  
pp. 1706
Author(s):  
Д.С. Сандитов ◽  
В.В. Мантатов ◽  
С.Ш. Сангадиев

Using the model of delocalized atoms, a substantiation and generalization of the Schmelzer glass transition criterion is proposed. In contrast to the Bartenev and Volkenstein - Ptitsyn approaches, in the generalized kinetic glass transition criterion, along with the relaxation time and the cooling rate of the melt, the glass transition temperature and an almost universal dimensionless constant appear, which is determined by the fraction of the fluctuation volume frozen at the glass transition temperature. The idea is developed that the liquid goes into a glassy state when its cooling rate q reaches a certain fraction of C_g of the characteristic cooling rate q_g=(T_g/taug), which is closely related to the relaxation time of the structure tau_g at the glass transition temperature T_g.


2011 ◽  
Vol 6 (2) ◽  
pp. 91-95
Author(s):  
Ion Dranca ◽  
Igor Povar ◽  
Tudor Lupascu

This research has been carried out in order to demonstrate the use of differential scanning calorimetry (DSC) in detecting and measuring α- and β-relaxation processes in amorphous pharmaceutical systems. DSC has been employed to study amorphous samples of poly (vinylpyrrolidone) (PVP), indomethacin (InM), and ursodeoxycholic acid (UDA) that are annealed at temperature (Ta) around 0.8 of their glass transition temperature (Tg). Dynamic mechanical analysis (DMA) is used to measure β- relaxation in PVP. Yet, the DSC has been used to study the glassy indomethacin aged at 0 and -10 oC for periods of time up to 109 and 210 days respectively. The results demonstrate the emergence of a small melting peak of the α-polymorph after aging for 69 days at 0°C and for 147 days at -10°C (i.e., ~55°C below the glass transition temperature) that provides evidence of nucleation occurring in the temperature region of the β-relaxation.


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