A vapor collection and thermal desorption method to measure semiochemical release rates from controlled release formulations

Chemicals (bp 270–490 °C/1 atm) evaporated from a controlled-release formulation dispenser were carried by an airflow to a collector packed with a polymeric adsorbent. After a set time, the chemicals were recovered by thermally desorbing them onto a gas-liquid chromatograpic column. They were then separated and quantified. The apparatus is described, and the requirements for its successful use are discussed. The soundness of the thermal desorption technique was confirmed by comparison with another technique: solvent elution from the collector. The advantages of the former technique are discussed.Mention of a commercial or proprietary product in this paper does not constitute an endorsement of that product by the USDA.     

Apparatus and procedure for measuring release rates from formulations of lepidopteran semiochemicals

An apparatus was developed wherein a vacuum source was used to pull air across a controlled-release-formulation dispenser or a planchet containing a known quantity of a semiochemical and into a collector filled with a polymeric adsorbent. After a set time, the semiochemical was eluted with solvent and was quantified by gas-liquid chromatography (GLC). High percentages of known quantities of the lepidopteran semiochemicals (Z)-7-dodecen-l -ol acetate (Z7DDA), boiling point (bp) 275 ° C/1 atm, (Z)-9-tetradecen-1-ol formate (Z9TDF), bp 289 °C/1 atm, and (Z,Z)-3,13-octadecadien-1-ol acetate (ZZODDA), bp 490 °C/1 atm, were recovered. The semiochemicals did not oxidize and were recovered quantitatively from the adsorbent. The release rates of Z9TDF from a controlled-release dispenser were found to be directly proportional to the airflow rates. Release rate measurements on the Z9TDF dispensers were made for the purpose of estimating the method's precision. The method was shown to give internally consistent results by measurements on another Z9TDF formulation. The accuracy of the method is discussed.Mention of a commercial or proprietary product in this paper does not constitute an endorsement by the USDA.     

Pyrolysis–molecular weight chromatography–vapor-phase infrared spectrophotometry: An on-line system for analysis of polymers. IV. Influence of cis/trans ratio on the thermal degradation of 1,4-polybutadienes

The influence of the cis/trans ratio of 1,4-polybutadienes on the volatile products formed during temperature-programmed thermal degradation to 15% weight loss has been investigated using a mass chromatograph (a gas chromatograph which directly provides mass numbers of resolved components of a mixture) and an “on the fly” vapor-phase infrared spectrophotometer. In order of amounts, major volatile products were 4-vinyl-1-cyclohexene (dimer), 1,3-butadiene (monomer), cyclopentene, and 1,3-cyclohexadiene. With increasing trans content, the relative quantities of 4-vinyl-1-cyclohexene decreased strongly, cyclopentene increased strongly, 1,3-butadiene decreased moderately, and 1,3-cyclohexadiene increased moderately. For a high-trans polybutadiene, increasing the heating rate produced relatively more monomer and dimer but less cyclopentene. Mass chromatograms from 1,4-polybutadienes which had been heated to 15% weight loss in their prehistory were similar to those obtained from 1,2-polybutadiene, indicating that 1,4-polybutadiene undergoes isomerization prior to degradation. Mechanisms for the formation of the main volatile products of decomposition are discussed.     

Damage Mechanisms and the Mechanical Properties of a Laminated 0/90 Ceramic/Matrix Composite

The tensile properties of a 0/90 laminated CAS matrix composite reinforced with Nicalon fibers have been measured. Some effects of notches have also been explored. Changes in modulus and permanent strain caused by matrix cracking have been measured and compared with available models. For this comparison, independent measurements have been made of the constituent properties and the residual stress. The ultimate tensile strength has also been measured and compared with a global load-sharing model. It is concluded that lower-bound matrix cracking models provide good predictability of the stresses at which various matrix cracking mechanisms first operate. Also, the ultimate tensile strength is found to be consistent with a global load-sharing model, based on the in situ strength properties of the fibers. Conversely, the evolution of matrix cracks at stresses above the lower bound has yet to be adequately modeled. In addition, a need is identified for improved models relating elastic properties and permanent strains to matrix crack spacing.     

Solvation of ions—XX. The ferrocene—ferricinium couple and its role in the estimation of free energies of transfer of single ions

The ferrocene-ferricinium electrode (Pt/Foc, Fic⁺) was investigated in water, acetonitrile, ethanol, DMSO and DMF using single scan cyclic voltammetry and phase sensitive ac polarography. The oxidation-reduction is pseudo-reversible in all five solvents with an electrochemical rate constant of approximately 10⁻² cm/s. In all solvents a slow irreversible chemical step involving the ferricinium cation follows electron transfer, so that slow cyclic voltammetry or polarography rather than potentiometry is preferred if ferrocene is to be used as a reference electrode in non-aqueous solvents.

The Strehlow assumption, ΔG_tr(Foc) = ΔG_tr(Fic⁺ gives very different free energies of transfer of single ions from non-aqueous solvents to water when compared with the TATB assumption that ΔG_tr(Ph₄As⁺) = ΔG_tr(Ph₄B⁻). This discrepancy is likely to be because ferricinium is only a moderately large cation, so that ΔG_tr(Fic⁺) is less positive than ΔG_tr(Foc) for transfer to water. The discrepancy is not because of abnormal electrochemical behavior of the Pt/Foc, Fic⁺ electrode in water or other solvents. Values of E° vs nhe, H₂O in a variety of solvents based on the TATB assumption are presented.     

Spin coating behavior of polyimide precursor solutions

Experimental data confirm the utility of the following simple equation in predicting the spin coating behavior of polyimide precursor solutions: in which .     

Mechanical properties and transition temperatures of copolymers of N-n-alkylacrylamides and vinylidene chloride

Mechanical and solution properties, melting transitions, torsional stiffness temperatures, T_f, and selected modulus-temperature curves are presented for copolymers of the N-n-alkylacrylamides with vinylidene chloride. Copolymers were prepared at 60°C across the range of compositions, using as comonomers N-n-butyl-, octyl-, dodecyl- and oleyl-acrylamide, which have amorphous side-chains, and N-n-octadecyl acrylamide and n-octadecyl acrylate whose side-chains are crystalline. The mechanical properties reflected the effect of the decline in backbone crystallinity and the simultaneous development of strong intermolecular interactions in the amorphous stage. Copolymers were stiff or showed brittle failure across the compositional range except when intermolecular forces were reduced (with n-octadrcyl acrylate) and side-chain crystallization eliminated (with N-oleylacrylamide). These systems and the n-dodecylacrylamide copolymers had yield strengths less than brittle strengths and substantial elongations. Backbone crystallinity was eliminated at about 15 mole % amide and side-chain crystallinity vanished at less than 10 mole % of the amide in the N-n-octadecylacrylamide series. No depression in side-chain melting point occurred with dilution by segments of vinylidene chloride. Over-all decline in the flex-temperature was the normal monotonic function of composition except that values increased in magnitude at high vinylidene chloride contents, the effect presumably being caused by the presence of crystallinity. An empirical equation was developed which permitted the calculation of T_f for any N-n-alkylacrylamide composition with any number of carbon atoms in the side-chain, above 3.     

Aqueous gel permeation chromatography: The effect of solvent ionic strength

Porous glass packing materials have been used for gel permeation chromatography using an aqueous phosphate buffer. Elution volumes were determined for polystyrene sulfonates, dextrans, and small neutral and charged molecules at three different ionic strengths, viz., 0.01M, 0.1M, and 1.0M phosphate, pH 7.0. The pore diameters of the glasses studied were 75, 240, 700, and 2000 Å. Elution volumes of nonionic species were unaffected by changing the solvent ionic strength. Elution volumes of charged species were markedly affected by the ionic strength of the solvent. This was attributed to a combination of decreased polymer dimensions and decreased ionic exclusion with increasing buffer concentration. The use of low ionic strength solvents may be exploited to tailor the separating range for polyelectrolytes with porous glass packings. This is particularly useful in the low molecular weight range where the lowest pore size available is 75 Å.     

Nonaqueous poly(methyl methacrylate) dispersions: radical dispersion polymerization in the presence of AB block copolymers of polystyrene and poly(dimethyl siloxane)

Well defined AB block copolymers of polystyrene (PS) and poly(dimethyl siloxane) (PDMS) have been prepared with PS molecular weights in the range 8 800 to 43 600 and PDMS molecular weights in the range 2 400 to 48 000. Provided the PS and PDMS molecular weights have a ratio within the range 0.5 to 4.0, these block copolymers stabilize particles of poly(methyl methacrylate) in n-alkanes. The particle size over the range 0.1 to 0.5 μm may be varied by performing dispersion polymerizations of methyl methacrylate as a function of monomer content of the seed stage and as a function of the concentration, molecular weight and composition of the block copolymer. From silicon analyses of the poly(methyl methacrylate) particles, values of the surface area stabilized per PDMS chain were established. The results indicate complete surface coverage of the particles.