Thermal analysis of styrene–alkyl methacrylate polymers. I. Glass transition temperatures

The glass transition temperatures (T_g's) of several polystyrenes and styrene–alkyl methacrylate copolymers and terpolymers were measured using thermomechanical analysis (TMA) and differential scanning calorimetry (DSC). The polymers studied had number-average molecular weights from 3000 to 250,000 g/mole. The results indicate that the composition dependence of the T_g's for the copolymers and terpolymers can be satisfactorily described by a general Fox equation. In general, the measured T_g's of the copolymer and terpolymer samples depend more on the steric effects of the constituent pendent groups than on their molecular weights. The chain flexibility rather than the size of the pendent group is the determining factor in the glass transition properties of the styrene polymers.     

Note: The Use of Triallyl Cyanurate in Bonding PVC Plastisols to Steel

The use of diallyl phthalate as the basis for a non-extractable plasticizer for poly(vinylchloride) (PVC) is well-known. Used in conjunction with a primary plasticizer and a polymerization initiator, a plastisol coating for steel can be formulated which is oil or grease tolerant and can also be used for bonding some structural steel parts if the area is relatively large compared with the load to be applied. Defrayne and Twiss¹ describe the bonding of automobile hood assemblies by vinyl plastisol adhesives and Schneberger² emphasizes their use in the automobile industry though neither article gives the formulations employed. Commercial formulations giving pull-off strengths of the order of 1 to 4 MN. m^-2 always incorporate a proportion of a phenolformaldehyde resin or even an epoxy, but sound-deadening and other coatings of steel do not necessarily need this reinforcement. Phillips and Longworth³ particularly studied the use of diallylphthalate (DAP) as a polymerizable plasticizer and the consequent improvement in adhesion to mild steel. Sherlock⁴ used a simple formulation without additives when investigating the effect of surface cleaning and conversion coatings (oxides and phosphates). It was suggested that, as outlined below, improved adhesion would be expected if a small proportion of triallyl cyanurate (TAC) were added to the polymerizable plasticizer. This paper shows this expectation to be achieved although the proportion of the more expensive TAC needed for substantial increase in bond strength is greater than was hoped.     

Development of optical anisotropy in vitrains during carbonization

The purpose of this work was to examine the possible significance in the formation of metallurgical coke of the anisotropic spherical mesophase exemplified by that found during the carbonization of pitch-like materials, and to ascertain if the various types of optical anisotropy found in coke could form a basis for the characterization of cokes produced from different coals. Vitrains from a wide range of coals were carbonized at temperatures from 370 to 1000 °C and the types and amounts of optical anisotropy in the resulting semi-cokes and cokes were determined from microscopic examination, the anisotropic components being classified according to grain size of the granular mosaics and appearance. The anisotropy developed directly from the isotropic phase, appearing initially as a fine-grained mosaic. With increasing carbonization temperature, this fine-grained mosaic was transformed into progressively coarser-grained anisotropy, the extent of this transformation depending on the rank of the vitrain. It is therefore concluded that the formation, growth and coalescence of anisotropic spherical bodies, such as occurs during the carbonization of pitch, is not a necessary precursor of the mosaic anisotropy in coke. The type and amount of anisotropy developed provide a quantitative means of characterising different cokes.     

Gas-Liquid chromatography of fatty derivatives. I. Separation of homologous series ofa-olefins,n-hydrocarbons,n-nitriles,and n-alcohols

Summary Gas-liquid chromatography has been shown to be applicable to the analysis of several fatty derivatives. The difficulties inherent in conventional separation schemes such as liquid-liquid chromatography, fractional distillation, and crystallization can be overcome through the use of gas-liquid chromatography. It becomes the preferred procedure for several reasons: a) fractions are more nearly pure, b) analysis time is a fraction of the time required for conventional separations, c) operational procedures are simple and highly reproducible, d) sample size requirements are low, e) the cost per unit analysis is low. These factors suggest that gas-liquid chromatography is highly useful as an analytical tool in fat research. In many cases the determination of chainlength distribution has already become a routine function. There remain areas in which gas-liquid chromatography has not been completely successful. Until very recently the separation of fatty methyl esters of similar chain length and varying degrees of unsaturation has been time-consuming and tedious. Several new partitioning agents hold out great promise in the separation of the isomeric C₁₈ fatty acids. More selective partitioning agents and refined techniques undoubtedly will equally improve the resolution of unsaturated alcohols and other unsaturated fatty derivatives. Presented at annual meeting, American Oil Chemists' Society, Memphis, Tenn., April 21–23, 1958. Technical Paper No. 160, Archer-Daniels-Midland Company.     

Corrosion-resistant ceramics and polymer composites based on the BaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

This paper reports on the results of investigations aimed at synthesizing ceramic materials with a high mechanical strength, as well as with high thermal and chemical resistances to corrosive media. The methods used for one-stage preparation of barite-based ceramic and polymer composites with these properties are considered.     

A new method for measuring the transfer of oxygen in liquids. MeasurementS of oxygen transfer from bubbles in water and in water + 1-butanol

At the base of a column of liquid 20 cm in diameter and well over 1 m in height, oxygen bubbles of constant volume were formed and released with a frequency of approximately one bubble per second. Measurements were carried out on bubbles with volumes ranging from 0·2 to 2 cm³. The mass transfer per bubble was determined by measuring the increase in oxygen concentration of the liquid phase with an oxygen electrode and counting the number of bubbles. The results were reproducible within 3 per cent, and it is probable that still better results are attainable with this method.The measurements were initially performed in distilled water to test the apparatus. Later, water—butanol mixtures were employed in order to determine the influence of butanol on the mass transfer. The results of the latter experiments have been checked with a theory published previously [23, 24]. Theory and results appear to be in satisfactory agreement.     

Effect of curing and heat treatment history on the dynamic mechanical response and the pore structure of hardened cement paste

Results for the dynamic mechanical response of hcp (hardened cement paste) specimens as a function of the curing-heat treatment history are reported. The temperature range investigated is from ?160°C to +100°C. In the temperature range from +25°C to +100°C, specimens cured at room temperature (R-cured) show a partially irreversible transition (reduction) in E. There are two low temperature transitions: the “adsorbate transition” between ?160°C and ?6-°C, and the “capillary transition” between ?50°C and 0°C. Both of these transitions are significantly affected by the curing-heat treatment history. Furthermore, both the E-modulus and the BET (water) surface area decrease as the severity of heat treatment increases.     

Retarding effects of DNA on the autoxidation of liposomal suspensions

Deoxyribonucleic acid (DNA) is associated with the cell membrane of prokaryotes and the inner nuclear membrane of eukaryotes. The unsaturated fatty acids of phospholipids, which constitute the bilaminar structure of membranes, undergo autoxidation in the presence of O₂. Calf thymus DNA was incubated with methyl archidonate-enriched phosphatidyl choline liposomes in order to study the effect of DNA upon the oxidation of phospholipids while present in their natural in vivo bilayer configuration. DNA retarded the rate of lipid oxidation and the TBA test, but it did not alter the induction period. These results suggest that DNA is scavenging free radicals produced within the phospholipid bilayer.