Softening and melting mechanisms of polyamides interfering with sliding stability under adhesive conditions

The thermal stability of polymers is a main issue when used as friction elements under dry sliding. Cast polyamide grades processed with either natrium or magnesium catalysors are slid on a small-scale and a large-scale test configuration to reveal the effect of softening or degradation on the sliding stability and to investigate possibilities for extrapolation of friction and wear rates between both testing scales. The combination of softening and afterwards transition into the glassy state is detrimental for the sliding stability of natrium catalysed polyamides, characterised by heavy noise during sliding. A transfer film formed under continuous softening also provides high friction. Melting during initial sliding is necessary for stabilisation in both friction and wear, and eventual softening of a molten film near the end of the test then not deteriorates the sliding stability. Softening of magnesium catalysed polyamides is favourable for the formation of a coherent transfer film resulting in more stable sliding than natrium catalysed polyamides. The differences in softening mechanisms of both polyamide grades is correlated to structural changes investigated by thermal analysis and Raman spectroscopy: the γ crystalline structure prevails in magnesium catalysed samples and the α crystalline structure is predominant in natrium catalysed samples. For internal oil lubricated polyamides, a time dependent degradation of the polyamide bulk deteriorates the supply of internal oil lubricant to the sliding interface, resulting in high friction and wear under overload conditions. As the degradation mechanisms during sliding are strongly correlated to the test set-up, extrapolation is only possible for friction in a limited application range, while wear rates cannot be extrapolated.     

The effect of feedstock and process conditions on the synthesis of high purity CNTs from aromatic hydrocarbons

High purity multi-walled carbon nanotubes were synthesized from aromatic hydrocarbons (benzene, toluene, xylene and trimethyl benzene) using ferrocene as the source of Fe catalyst. Screening studies of aromatic feeds at 675 °C, residence time of 14 s and Fe/C atom ratio of 1.07%, resulted in feedstock carbon conversion of 20-31%, CNT yield of 19.8-30.5%, and catalyst yield of 5.3-8.3 (g CNT/g catalyst). While the quality of the CNTs as determined by TGA, SEM, TEM and Raman spectroscopy, were high and comparable for different feedstocks; their carbon conversion, CNT yield and catalyst yield differed noticeably. A process optimization study for toluene feed showed that carbon conversion of more than 39%, CNT yield of 38.7% and catalyst yield of 18.3 can be achieved at temperature of 800 °C, Fe/C atom ratio of 0.47%, and residence time of 10-20 s.     

Raman spectra of virgin and damaged graphite edge planes

First-order Raman spectra of virgin and ion irradiated highly oriented pyrolytic graphite were performed along the basal and edge planes. Ion irradiation was performed in the low fluence regime (≈ 10¹²–10¹³ ions cm⁻²) using a 400 keV Ar⁺ beam in order to a introduce controlled amount of defects in the structure. Virgin edge Raman spectra reveal the presence of a 1351 cm⁻¹ structure (D^*) shifted 10 cm⁻¹ away from the disorder induced D-line found upon irradiating or grinding the graphite surface.The 1351 cm⁻¹ D^* structure is then considered as the feature coming from the rupture of the D_6h⁴ space group symmetry. A comparison between D^* and the classical 1360 cm⁻¹ D-line is discussed in terms of induced disorder.     

Investigation of the effect of surface phosphate ester dispersant on viscosity by coarse-grain modeling of BaTiO slurry

To understand the role of phosphate ester dispersant, we investigated the rheology of a BaTiO slurry. For the model case, a coarse-grain molecular dynamics (CGMD) simulation was performed with the butyral polymer didodecyl hydrogen phosphate (DHP) in the toluene/ethanol solvent. By systematically analyzing the effect of DHP from an atomic-scale first principle and from all-atom MD to microscale CGMD simulation, we investigated how the adsorption of a DHP dispersant on a BaTiO surface affects the microstructure rheology of a BaTiO slurry. The first-principle and all-atom MD simulation suggests that DHP molecules prefer to locate near the BaTiO surface. CGMD simulation shows a reduction in viscosity with an increase in dispersants, suggesting that the dispersant population near the BaTiO surface plays a key role in controlling the rheology of the BaTiO slurry. In this study, we propose an approach for understanding the BaTiO slurry with molecular-level simulations, which would be a useful tool for efficient optimization of slurry preparation.     

Structures and morphologies of cast and plastically strained polyamide 6 films as evidenced by confocal Raman microspectroscopy and atomic force microscopy

Both confocal Raman microspectroscopy and atomic force microscopy (AFM) have been undertaken to study the crystalline and the morphological aspects of cast PA 6 films at a sub-microscopic scale. The percentages of the different crystalline structures present within PA 6 cast films, i.e. the monoclinic α, the pseudo-hexagonal β, and the monoclinic γ, have been measured by confocal Raman microspectroscopy. In cast films, the prevailing structure is the β one. AFM has been used to characterize the morphology of the PA 6 films. Simultaneously, the deformed state has been considered as well. Our main interest has been to follow the evolution of the percentage of each crystalline structure as a function of the plastic deformation mechanisms which are responsible of the yielding of PA 6 films: shear banding for temperatures T lower than 160 °C and formation of fibrils for      

Raman spectroscopic study of conformational changes in the amorphous phase of poly(lactic acid) during deformation

The conformational distribution change of amorphous poly(lactic acid) (PLA) induced by deformation has been studied using Raman spectroscopy. Spectroscopic features associated with the rotational isomeric states (ttt, ttg′, tg′t, tg′g′) have been established experimentally and supported by normal coordinate analysis. Deformation induced a significant increase in the most favorable tg′t conformation. Based on the relative intensities of Raman-active skeletal modes, a quantitative method has been developed that can be used to elucidate structural changes in a variety of deformed polymer samples. For biaxially oriented PLA films, the overall tg′t conformation increased from the 76% in undeformed sample to a value as high as 92%. The change in conformational distribution in the amorphous phase follows a different trend (76-88%) as compared to the increase in sample crystallinity (0-43%). A large change in amorphous chain conformation occurred at relatively low draw ratios. In contrast, the large change in the degree of crystallinity occurred at higher draw ratios.     

Effect of hydrocarbons precursors on the formation of carbon nanotubes in chemical vapor deposition

High-temperature decomposition of hydrocarbons may lead to the formation of carbon deposits. However in our present studies, we found that the morphology of carbon deposits over MgO supported Fe catalyst during chemical vapor deposition (CVD) process was closely related to the thermodynamic properties and chemical structures of hydrocarbon precursors. Six kinds of hydrocarbons (methane, hexane, cyclohexane, benzene, naphthalene and anthracene) were used as carbon precursors in this study. Methane which has a pretty simple composition and is more chemically stable was favorable for the formation of high-purity single walled carbon nanotubes (SWNTs). For high-molecular weight hydrocarbons, it was found that the chemical structures rather than thermodynamic properties of carbon precursors would play an important role in nanotube formation. Specifically, the CVD processes of aromatic molecules such as benzene, naphthalene and anthracene inclined to the growth of SWNTs. While the cases of aliphatic and cyclic hydrocarbon molecules seemed a little more complicated. Based on different pyrolytic behaviors of carbon precursors and formation mechanism of SWNTs and multi-walled carbon nanotubes (MWNTs), a possible explanation of the difference in CVD products was also proposed.     

Isomerization of n-hexane over mono- and bimetallic Pd–Pt catalysts supported on ZrO2–Al2O3–WOx prepared by sol–gel

The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO₂ (70, 85 wt.%)–Al₂O₃ (15, 0 wt.%)–WO_x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N₂ physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO_x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO₃ bulk phase. The catalysts increased their S_BET for about 15% promoted by Al₂O₃ addition. Various oxidation states of WO_x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO_x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W⁶⁺ and reduced-state WO_x species (either W⁴⁺ or W⁰). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.     

Carbon-encapsulated Fe nanoparticles from detonation-induced pyrolysis of ferrocene

Carbon-encapsulated Fe nanoparticles with size between 5 and 20 nm were synthesized via a picric acid-detonation-induced pyrolysis of ferrocene, which is characterized by a self-heating and extremely fast process. The nanoparticles exhibit well-constructed core-shell structures, with bcc-Fe cores and graphitic shells. The graphitic shells can protect effectively the cores against the attack of HNO₃ solution. The formation of the core-shell nanoparticles can be selectively controlled by adjusting the composition of the picric acid-ferrocene mixture, which determines C/Fe atomic ratio of the reaction system. The core-shell nanoparticles are preferably formed at low C/Fe atomic ratios, while tubular structures are formed at high C/Fe ratio. The possible pathway for the carbon-encapsulated Fe nanoparticles formation is discussed briefly.