NMR and sedimentation studies of a polymeric steric stabilizer for alumina

The sedimentation behavior of alumina powder has been studied in the presence of poly-vinylpyrrolidone (PVP) and poly(vinylpyrrolidone-co-vinyl acetate) (PVP/VA) in both thermodynamically “good” and “poor” solvents for the PVP homopolymer. PVP/VA provides higher sediment densities than does its PVP homopolymer counterpart. Solutionstate ¹³C-T₁ spin-lattice relaxation measurements were made on analogous mixtures both with and without alumina powder. The NMR results suggest that the PVP/VA copolymer is anchored to the alumina powder surface by means of VA moieties, whereas the PVP moieties extend into the continuous phase of the slurry medium. Thus, the higher settling densities that are observed in the presence of PVP/VA can be attributed to a steric stabilization mechanism. © 1993 John Wiley & Sons, Inc.     

Characterisation of the adsorption sites of hydrogen on Pt/C fuel cell catalysts

A key component of a hydrogen fuel cell is a catalyst to dissociate dihydrogen to hydrogen atoms. In the present study, the adsorption of hydrogen on Pt/C fuel cell catalysts has been investigated by inelastic neutron scattering spectroscopy.

Monitoring a clean Pt(50%)/C catalyst with low energy neutron spectroscopy, after exposure to dihydrogen at 20 K, as it was heated to room temperature, showed three distinct temperature regimes: (i) a decrease in intensity from 10 to 60 K, (ii) a rise to a maximum between 60 and 120 K and then (iii) a slow fall-off towards room temperature. We assign the three regions as: (i) desorption of physisorbed dihydrogen, (ii) dissociation of dihydrogen to give an adsorbed layer and (iii) damping of the response by an increasing Debye–Waller factor.

The vibrational INS spectra of a series of Pt/C catalysts prepared under varying conditions were similar indicating that the same types of site are common to all the catalysts, although the relative proportions of each site are sample dependent. Features at 520, 950 and part of the intensity at 1300 cm⁻¹ are assigned to hydrogen on (1 1 1) faces, in good agreement with single crystal data. The mode at 640 cm⁻¹ is assigned as the doubly degenerate asymmetric stretch of Pt(1 0 0) faces with the symmetric stretch near 550 cm⁻¹.

We assign the bending mode of the on-top site to the feature at 470 cm⁻¹. The Pt–H stretch mode was observed at 2079 cm⁻¹. This is a significant result: this is the first time that hydrogen on the on-top sites has been observed on nanosized platinum particles supported on high surface area carbon black. The width of the INS peak is surprisingly large and may give additional information on the type and relative proportions of the crystallographic faces present on the catalyst particles.     

Flow patterns in granulating systems

Particle flow patterns were investigated for wet granulation and dry powder mixing in ploughshare mixers using Positron Emission Particle Tracking (PEPT). In a 4-l mixer, calcium carbonate with mean size 45 μm was granulated using a 50 wt.% solution of glycerol and water as binding fluid, and particle movement was followed using a 600-μm calcium hydroxy-phosphate tracer particle. In a 20-l mixer, dry powder flow was studied using a 600-μm resin bead tracer particle to simulate the bulk polypropylene powder with mean size 600 μm. Important differences were seen between particle flow patterns for wet and dry systems. Particle speed relative to blade speed was lower in the wet system than in the dry system, with the ratios of average particle speed to blade tip speed for all experiments in the range 0.01–0.25. In the axial plane, the same particle motion was observed around each blade; this provides a significant advance for modelling flow in ploughshare mixers. For the future, a detailed understanding of the local velocity, acceleration and density variations around a plough blade will reveal the effects of flow patterns in granulating systems on the resultant distribution of granular product attributes such as size, density and strength.     

Al2TiO5-ZrTiO4-ZrO2 Composites: A New Family of Low-Thermal-Expansion Ceramics

The characterization and properties of ceramic composites containing the phases Al₂TiO₅, ZrTiO₄, and ZrO₂ are described. The range of compositions investigated gives very low average thermal expansions (α_24–1000°C as low as −2.0 × 10⁻⁶°C⁻¹) and excellent high-temperature stability. The low thermal expansions are apparently due to a combination of microcracking by the titanate phases and a contractive phase transformation by the ZrO₂. The crystal chemistry and microstructure of the product are processing dependent. Although the composites represent a complex microcracking system, the low thermal expansions and high-temperature stability make them potential candidates for commercial applications requiring thermal shock resistance.     

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.     

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.     

Viscosity index. I. Evaluation of selected copolymers incorporating n-octadecyl acrylate as viscosity index improvers

Compositionally and structurally varied copolymers all containing n-octadecyl acrylate were prepared and evaluated as viscosity index improvers in a common base oil under conditions of low shear. Systems evaluated over a range of copolymer and blend composition were: copolymers of n-octadecyl acrylate with, respectively, methyl methacrylate, 2-ethylhexyl acrylate, and n-dodecyl acrylate; and homopolymers of poly(n-octadecyl acrylate), prepared with a wide range of molecular weights. Properties were compared with those of blends of commercial methacrylate copolymers (acryloids) which had been freed of their entraining liquid. Mixtures of base oil with copolymers of n-octadecyl acrylate and methyl methacrylate, compared at fixed SAE viscosities, were the most efficient of all blends studied. They had the smallest rate of change of viscosity with temperature (as measured by their ASTM slopes), particularly in the composition region of incipient polymer precipitation at room temperature. Efficiency of certain of these composition was somewhat greater than that of the acryloids. A parameter that related concentration and weight-average molecular weight was used to correlate all of the data for ASTM slope and viscosity. Empirical relations developed by using this parameter enabled rheological data to be estimated that agree within 6% of experimental values for the case of thermodynamically good base oil solvents. These data demonstrated the relatively small contributions of copolymer structure to viscosity index improvement.