Inhibition of acrylic acid polymerization by phenothiazine and p-methoxyphenol

The major features of polymerization induction periods for acrylic acid inhibited with phenothiazine and p-methoxyphenol have been characterized at 100°C, including duration of the induction periods, and rates of inhibitor disappearance, molecular oxygen absorption, and peroxide formation. Surprisingly, thermally produced radicals react more rapidly with phenothiazine than with oxygen since there is no detectable oxygen absorption or peroxide for mation during phenothiazine-induced induction periods. Thus, phenothiazine has been used to estimate the thermal rate of radical formation. Phenothiazine's effectiveness as an inhibitor is not directly affected by oxygen, although it does undergo oxygen-promoted, noninhibition-related side reactions. p-Methoxyphenol, on the other hand, depends entirely on the presence of oxygen to function as an inhibitor. Compared with equivalent concentrations of p-methoxyphenol, induction periods obtained with phenothiazine are very long, and the rate of inhibitor disappearance is slower by at least an order of magnitude. The characteristics of p-methoxyphenol inhibition reflect a greater radical flux deriving from the significant rates of oligomeric peroxide formation and decomposition which we measured during p-methoxyphenol-induced induction periods at 100°C. MEHQ is an effective inhibitor at ambient temperatures in part because of the greater stability of the peroxides at these lower temperatures.     

The mechanical degradation of polystyrene

The catastrophic failure of a polymeric material is preceded by a number of complex, partially understood events occurring on the molecular level. These events range from the flow of ordered regions to the cleavage of primary bonds in the chain. In recent years, stress-induced bond cleavage in polymers has received increased attention, many authors nothing the presence of free radicals and/or volatile products released upon fracture; a free-radical decomposition mechanism involving up to 10³ molecules per chain rupture also has been postulated. A special tensile stress–strain and shear apparatus was developed and located inside the ion-source housing of a time-of-flight mass spectrometer to characterize the volatile products released during mechanical degradation of polystyrene. Volatile compounds evolved during stress and fracture of polystyrene were monitored either continuously or by z-axis modulated oscilloscopic display. The polystyrene was purified by two methods: vacuum outgassing and fractional reprecipitation. Large amounts of styrene evolved from both the as-received and outgassed samples; however, essentially none was observed from the reprecipitated samples. Previous reports on monomer evolution during mechanical stress of polystyrene may be the result of residual monomer and not mechanical degradation products. The product of the surface density of primary radicals and the chain length for unzipping is less than 3 × 10¹⁰ radicals/mm² indicating a maximum radical concentration of approximately 10¹⁰ radicals/mm².     

Ultrasonic study of dysprosium in a magnetic field

The ultrasonic attenuation of longitudinal waves propagating along the c axis of single crystal dyprosium is reported, as a function of the applied basal plane field in the paramagnetic region, and as a function of the temperature, at constant applied basal plane field, in the spin-spiral region. In the paramagnetic region, anomalous attenuation behavior is explained on the basis of competing spin-polarization and spin-fluctuation effects. Two anomalous maxima in the temperature dependence of the attenuation were observed: one near T_N is attributed to spin fluctuations associated with short range ferromagnetic ordering; another one at 130 K is attributed to a magnetic phase transition from a fanstructure phase, intermediate between the spin-spiral and ferromagnetically ordered phase     

Determination des angles d'obliquite d'un cristal liquide en phase nematique au voisinage d'une surface

Using several laser sources the dispersion of the quadrupole nonlinear tensor d⁽²⁾(CaCO₃) has been determined in the ultraviolet and visible range 265 – 592 nm. The measured dependence is in a good agreement with the predicted dispersion d⁽²⁾(CaCO₃) ~ λ^-1.     

Purification of molybdenum : volatilisation processes using MoO3

Various volatilisation processes for the purification of MoO₃ were investigated. Of these, fusion Of MoO₃ with NACl at 600°C gave the best results. Thermal analysis of the MoO₃/NaCl and WO₃/NaCl systems illustrates details of the processes involved.     

Biaxial magnetic structures in rare-earth compounds: GdMg and HoP

The flopside spin structure, where the magnetic moments form two sublattices which at low temperatures are mutually perpendicular was first found in HoP and then in other rare-earth pnictides. There are large orbital contributions to the magnetic moments of these compounds and it had been thought that they play an important role in stabilizing the flopside spin structure. However, recently this spin structure has been found in GdMg. As Gd³⁺ is an S-state ion, there are negligible orbital effects. We have developed a model Hamiltonian which is able to explain both the occurence of initially a ferromagnetic phase and then at low temperature the flopside spin structure in two very dissimilar compounds GdMg and HoP. For GdMg we find that the competition between the near neighbor ferromagnetic and antiferromagnetic bilinear exchange interactions is such that while they produce a transition to a ferromagnetic phase at 110 K, an unusually small amount of biquadratic (quadrupolar) coupling is able to stabilize a flopside phase at low temperature which is able to resist collapse in a field as large as 150 kOe. For HoP we find that although anisotropic bilinear pair interactions - as for example pseudo-dipole - exist, they cannot be the primary origin of the flopside phase; quadrupole pair interactions are essential to explain the appearance of first the ferromagnetic and then the flopside phases found in HoP. On the basis of our model calculations we are able to explain the data extant on these compounds and we make some predictions which are open to experimental verification.