Quenching poly

Tsuji, H., Kamo, S. Horii, F. (2010). Solid-state i C NMR analyses of the structures of crystallized and quenched poly(lactide)s Effects of crystallinity, water absorption, hydrolytic degradation, and tacticity. Polymer, Vol. 51, No. 10, pp. 2215-2220... 

The glass transition can be observed in other amorphous polymers, such as poly(vinyl chloride), poly (vinyl acetate), poly(methyl acrylates), quenched poly(ethylene terephthalate) or quenched polycarbonates. A trace amount of organic solvent remaining in the sample following solvent casting shifts Tg to lower temperatures. Samples containing low molecular mass compounds measured in open-... 

DSC heating curves of quenched poly(thio-l,4-phenylene-phenylphosphonyl-1, 4-phenylenethio-4,... 

The DSC curves of a quenched poly(thio-l,4-phenylenephenylphosphonyl-l,4-phenylenethio-4,4 -biphenylene) sample are presented in Figure 5.9. The quenched sample whose is 493 K was... 

Zhang, T., Hu,)., Duan, Y., Pi, E, and Zhang, J, (2011) Physical aging enhanced mesomorphic structure in melt-quenched poly(L-lactic acid). ]. Phys. Chem. B, 115, 13835-1384. 

Hendra et ai. have quenched poly(oxymethylene) and polyethylene at various cooling rates quenched in liq. Nj, and from 40 to 320 K min and different melt temperatures, 650 to 430 K, and observed that the lamellae thickness varied markedly with both parameters. Since the random coil dimensions are temperature dependent, they suggest that the crystallized material retains a memory of the melt random coil dimensions. Similarly, hydrostatic pressure applied to the melt also reduced the lamellae thickness. The authors have dismissed the effect of heat losses on crystallization as irrelevant. 

Figure 2.89. The total heat flow, reversing heat flow, and the nonreversing heat flow from an MTDSC heating of quenched poly(ethylene terephthalate) (courtesy of TA Instruments).

Figure 7.10. Micro-TMA (sensor deflection) and micro-DTA (derivative power) curves for quenched poly (ethylene terephthalate).

Nojima S, Akutsu Y, Washino A, Tanimoto S. Morphology of melt-quenched poly(c-caprolactone)-Wock-polyethylene copolymers. Polymer 2004 45 7317-7324. 

Figure 11.7. DSC thermograms of a quenched poly(ethylene terephthalate) (PET) sample ...

Quenching poly(l-vinylnaphthalene) and 1-ethyl-naphthalene phosphorescence at 77 K as a function of piperylene molarity. From Cozzens and Fox (1). 

Quenched sheet is pulled horizontally from the stack and is then either wound on roUs or sheared into sheets of the required dimension. Among the polymers made into sheet this way are the polyolefins, poly(vinyl chloride), amorphous polyester, polycarbonate, and polyarjiate. 

HoUow-fiber fabrication methods can be divided into two classes (61). The most common is solution spinning, in which a 20—30% polymer solution is extmded and precipitated into a bath of a nonsolvent, generally water. Solution spinning allows fibers with the asymmetric Loeb-Soufirajan stmcture to be made. An alternative technique is melt spinning, in which a hot polymer melt is extmded from an appropriate die and is then cooled and sohdified in air or a quench tank. Melt-spun fibers are usually relatively dense and have lower fluxes than solution-spun fibers, but because the fiber can be stretched after it leaves the die, very fine fibers can be made. Melt spinning can also be used with polymers such as poly(trimethylpentene), which are not soluble in convenient solvents and are difficult to form by wet spinning. 

The maximum rates of crystallisation of the more common crystalline copolymers occur at 80—120°C. In many cases, these copolymers have broad composition distributions containing both fractions of high VDC content that crystallise rapidly and other fractions that do not crystallise at all. Poly(vinyhdene chloride) probably crystallises at a maximum rate at 140—150°C, but the process is difficult to foUow because of severe polymer degradation. The copolymers may remain amorphous for a considerable period of time if quenched to room temperature. The induction time before the onset of crystallisation depends on both the type and amount of comonomer PVDC crystallises within minutes at 25°C. 

Poly(ethylene terephthalate) film is produced by quenching extruded film to the amorphous state and then reheating and stretching the sheet approximately three-fold in each direction at 80-100°C. In a two-stage process machine direction stretching induces 10-14% crystallinity and this is raised to 20-25% by... 

In systems of LP the dynamic response to a temperature quench is characterized by a different mechanism, namely monomer-mediated equilibrium polymerization (MMEP) in which only single monomers may participate in the mass exchange. For this no analytic solution, even in terms of MFA, seems to exist yet [70]. Monomer-mediated equilibrium polymerization (MMEP) is typical of systems like poly(a-methylstyrene) [5-7] in which a reaction proceeds by the addition or removal of a single monomer at the active end of a polymer chain after a radical initiator has been added to the system so as to start the polymerization. The attachment/detachment of single monomers at chain ends is believed to be the mechanism of equilibrium polymerization also for certain liquid sulphur systems [8] as well as for self-assembled aggregates of certain dyes [9] where chain ends are thermally activated radicals with no initiators needed. 

Figure 2 Light permeability of polyolefins after quenching (1-4) and of nonquenched samples (l -4 ) l,l -poly-propylene (PP) 2,2 -high-pressure polyethylene (HPPE) 3,3 -low-pressure polyethylene (LPPE) 4,4 -medium-pres-sure polyethylene (MPPE). Film thickness-150 fic moulding time-10 minutes, moulding pressure HPPE-160°C LPPE, MPPE, PP-190-200X.

Webber et al. [60, 78] also studied the fluorescence quenching of diphenylan-thracene (DPA) covalently bound to poly(methacrylic acid), PMAvDPA (23) [60], and to sodium poly(styrenesulfonate), PSSvDPA (24 )[78]. The fluorescence quenching of the excited DPA moiety by MV2+ and Cu2+ was also highly efficient. For example, with PMAvDPA of 0.073 mol% DPA content, the kq values at pH... 

Despite the fact that the Phen moieties are tightly incorporated in the compartment of the hydrophobic microdomain, the fluorescence from the Phen residues in poly(A/St/Phen) is very efficiently quenched by MV2+ in aqueous solution. The quenching efficiency is much higher than the APh-2 (8 with x = 2)... 

As discussed in the previous chapter, the Phen residue in APh-x forms the CT complex with MV2 + in aqueous solution [76]. Interestingly, the CT formation is suppressed in the poly(A/St/Phen)-MV2+ system in spite of the Phen fluorescence being quenched by MV2 + very effectively. This fact indicates that it becomes very less likely for the Phen moiety to come into a face-to-face contact with MV2+, while the fluorescence from the compartmentalized Phen residue can be quenched effectively via a collision-less ET to MV2 +. ... 

Also the polymorphic behavior of s-PS can be altered by blending, in particular with poly-2,6-dimethyl-l,4-phenylene oxide (PPO), both for the case of crystallization from the melt [104] and for the case of crystallization from the quenched amorphous phase [105]. 

The introduction of bulky side chains that contain adamantyl groups to poly(p-phenylenevinylene) (PPV), a semiconducting conjugated polymer, decreases the number of interchain interactions. This action will reduce the aggregation quenching and polymer photoluminescence properties would be improved [93]. 

It has been demonstrated that dendrimers can be used also as fluorescent sensors for metal ions. Poly(propylene amine) dendrimers functionalized with dansyl units at the periphery like 34 can coordinate metal ions by the aliphatic amine units contained in the interior of the dendrimer [80]. The advantage of a dendrimer for this kind of application is related to the fact that a single analyte can interact with a great number of fluorescent units, which results in signal amplification. For example, when a Co ion enters dendrimer 34, the fluorescence of all the 32 dansyl units is quenched with a 32-fold increase in sensitivity with respect to a normal dansyl sensor. This concept is illustrated in Fig. 3. 

Zinc sulfide, with its wide band gap of 3.66 eV, has been considered as an excellent electroluminescent (EL) material. The electroluminescence of ZnS has been used as a probe for unraveling the energetics at the ZnS/electrolyte interface and for possible application to display devices. Fan and Bard [127] examined the effect of temperature on EL of Al-doped self-activated ZnS single crystals in a persulfate-butyronitrile solution, as well as the time-resolved photoluminescence (PL) of the compound. Further [128], they investigated the PL and EL from single-crystal Mn-doped ZnS (ZnS Mn) centered at 580 nm. The PL was quenched by surface modification with U-treated poly(vinylferrocene). The effect of pH and temperature on the EL of ZnS Mn in aqueous and butyronitrile solutions upon reduction of per-oxydisulfate ion was also studied. EL of polycrystalline chemical vapor deposited (CVD) ZnS doped with Al, Cu-Al, and Mn was also observed with peaks at 430, 475, and 565 nm, respectively. High EL efficiency, comparable to that of singlecrystal ZnS, was found for the doped CVD polycrystalline ZnS. In all cases, the EL efficiency was about 0.2-0.3%. 

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