Structural morphology of poly(styrene)-poly(butyl acrylate) polymer-polymer composites studied by dynamic mechanical measurements

The emulsion polymerization process allows production of polymer particles with different structural morphologies. Films obtained after coalescence keep some memory of this morphology, but large modifications can occur during coalescence. In the present case, one of the polymers, polystyrene (PS), exhibits a glass temperature (Tg) much higher than the filmification temperature (close to room temperature), while the other one, poly(butyl acrylate) (PBA), has a much lowerTg. Furthermore, it is well known that dynamic mechanical measurements can be very helpful in providing information on the morphology of polymer materials, i.e., on geometrical and topological arrangement of homopolymer domains. At first, this method was used for comparison of two types of films: i) the first one obtained from structured-core (PS)-shell (PBA) particles, ii) the second one obtained from a blend of homopolymer particles (PS and PBA). It appears that the expected core-shell particles lost their geometric structure in the second film. Second, comparison of the predicted dynamic modulus and experimental data shows that i) strong interactions exist between PS nodules unless their coalescence has occured, leading to an abnormally high modulus at room temperature, ii) after achieving their coalescence, PS forms a more or less continuous phase. Both phenomena strongly depend on the particle size and their respective volume fractions.     

Texture of zirconia obtained by forced hydrolysis of ZrOCl2 solutions

The structure and surface properties of ZrO₂ strongly depend on its preparation. In the present work the impact of prolonged aging at basic conditions (pH = 9, T = 100°C, t = 48 h), on the phase composition and textural properties, obtained by calcination of the precipitate, was investigated using several techniques conjointly (DTA/TG, DSC, XRD, porosimetry). The thermal effects accompanying the ZrO₂·xH₂O gel formation, the coalescence of the particles and crystallization were evaluated and discussed in terms of the structural differences between the aged and non-aged samples. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal transitions and fat droplet stability in ice-cream mixmodel systems

We studied thermal transitions and physical stability of oil-in-water emulsions containing different milk fat compositions, arising from anhydrous milk fat alone (AMF) or in mixture (2:1 mass ratio) with a high melting temperature (AMF–HMT) or a low melting temperature (AMF–LMT) fraction. Changes in thermal transitions in bulk fat and emulsion samples were monitored by differential scanning calorimetry (DSC) under controlled cooling and reheating cycles performed between 50 and –45°C (5°C min^–1). Comparison between bulk fat samples and emulsions indicated similar values of melting completion temperature, whereas initial temperature of fat crystallization (T_onset) seemed to be differently affected by storage temperature depending on triacylglycerols (TAG) composition. After storage at 4°C, T_onset values were very similar for emulsified and non-emulsified AMF–HMT blend, whereas they were lower (by approx. 6°C) for emulsions containing AMF or mixture of AMF–LMT fraction. After storage at –30°C, T_onset values of re-crystallization were higher in emulsion samples than in bulk fat blends, whatever the TAG fat composition. Light scattering measurements and fluorescence microscopic observations indicated differences in fat droplet aggregation-coalescence under freeze-thaw procedure, depending on emulsion fat composition. It appeared that under quiescent freezing, emulsion containing AMF–LMT fraction was much less resistant to fat droplet aggregation-coalescence than emulsions containing AMF or AMF–HMT fraction. Our results indicated the role of fat droplet liquid-solid content on emulsion stability.     

A NEW SYSTEM EXHIBITING A HIGH BARRIER TO ROTATION ABOUT THE P—N BOND. SYNTHESES AND SPECTRAL STUDIES OF 1,3,2-DIAZAPHOSPHETIDIN-4-ONE DERIVATIVES

Abstract

1,3,2-Diazaphosphetidin-4-one derivatives were synthesized. Their ¹H NMR signals at ambient temperature displaed a broad doublet which eventually coalesced before becoming sharp upon warming, and the ¹³C NMR spectra also showed that the α-and β-carbons of the dialkylamino group were non-equivalent. The phenomena were ascribed to restricted rotation about the exocyclic P—N bond.     

The boundary condition at the air–liquid interface and its effect on film drainage between colliding bubbles

The drainage of thin liquid films between colliding bubbles is strongly influenced by the boundary conditions at the air–liquid interface. Theoretically, the interface should not resist any tangential stress (fully mobile) in a clean water system, resulting in very fast film drainage and coalescence between bubbles within milliseconds. In reality, under most experimental and industrial conditions, the presence of impurities or surfactants can immobilize the interface and significantly hinder bubble coalescence by several orders of magnitude. In this opinion, we introduce the recent progress on understanding the boundary conditions at the air–water interface, and how they may affect the outcome of bubble collisions. The transition from mobile to immobile boundary conditions in the presence of contaminations is discussed. Despite the considerable recent progress, there are still experimental and theoretical challenges remaining on this topic, for example, finding the mechanism for hindered bubble coalescence by high salt concentrations.     

CFD simulation of oil–water separation characteristics in a compact flotation unit by population balance modeling

Huge amounts of produced water are generated in offshore oil production. The Compact Flotation Unit (CFU) is an excellent pretreatment technology of produced water with high separation efficiency, low residence, and small split ratio. The Computational Fluid Dynamics-population balance model (CFD-PBM) method is used in the present work to study the oil–water separation characteristics in the self-developed Beijing Institute of Petrochemical Technology Compact Flotation Unit (BIPTCFU) at both micro-scale and macro-scale, which would help us gain more insights into the mechanism and the influence of flow field on the oil–water separation process such as the oil droplets’ diameter distribution and separation efficiency. The effects of the inlet diameter, the height of the preliminary separation zone, and the width of the annular space on the oil–water separation characteristics of CFU were discussed systematically. It is illustrated that the appropriate increase of inlet velocity, decrease of annular gap width, and increase of the height in the preliminary separation zone can effectively promote the collision and coalescence process of oil droplets. However, the overlarge height of the preliminary separation zone and the too narrow width of the annular space will both have a significant negative effect on the migration and separation of oil and water and lead to the decrease of separation efficiency.     

倾斜均质表面上等径水滴聚合过程的可视化实验

对倾斜均匀表面上等直径水滴的聚合过程及特性进行了可视化实验研究,获得了水滴直径和表面倾角等参数对液滴聚合过程中液滴液桥半径、接触角和接触线变化特性的影响,分析了水滴聚合对其运动的影响.实验结果表明:表面倾角越大,下滑的临界半径越小;液滴的直径越大,液滴聚合后越容易下滑;液滴聚合可以加快液滴的运动,使下滑临界半径减小.     

Rheology and microstructures formation of immiscible model polymer blends under steady state and transient flows

Viscoelastic properties of model immiscible blend were studied here under steady state condition at different initial conditions and transient flow conditions. The flow‐induced microstructure has been studied on these model blends. For this system, the elastic properties of the blend are mainly governed by the interface. Measurement of the dynamic modulus and of the first normal stress difference, both reflecting this enhanced elasticity, have been used to prove the blend morphology. The dynamic moduli after cessation of shear flow, the mean diameter of the disperse phase as generated by the shear flow, have been calculated using the model of Palierne. A procedure based on a direct fitting of the dynamic moduli with the model is compared with the one that uses a weight relaxation spectrum. On the other hand, the steady state normal stress data have been related to the morphology of the blend by means of Doi and Ohta model. The specific interfacial area is found to be inversely proportional to the ratio of interfacial tension over shear stress for the blend. The flow behavior during transient shear flow was also discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3519–3533, 2005     

Control of the dynamics of a boiling vapour bubble using pressure-modulated high intensity focused ultrasound without the shock scattering effect: A first proof-of-concept study

Boiling histotripsy is a promising High-Intensity Focused Ultrasound (HIFU) technique that can be used to induce mechanical tissue fractionation at the HIFU focus via cavitation. Two different types of cavitation produced during boiling histotripsy exposure can contribute towards mechanical tissue destruction: (1) a boiling vapour bubble at the HIFU focus and (2) cavitation clouds in between the boiling bubble and the HIFU source. Control of the extent and degree of mechanical damage produced by boiling histotripsy is necessary when treating a solid tumour adjacent to normal tissue or major blood vessels. This is, however, difficult to achieve with boiling histotripsy due to the stochastic formation of the shock scattering-induced inertial cavitation clouds. In the present study, a new histotripsy method termed pressure-modulated shockwave histotripsy is proposed as an alternative to or in addition to boiling histotripsy without inducing the shock scattering effect. The proposed concept is (a) to generate a boiling vapour bubble via localised shockwave heating and (b) subsequently control its extent and lifetime through manipulating peak pressure magnitudes and a HIFU pulse length. To demonstrate the feasibility of the proposed method, bubble dynamics induced at the HIFU focus in an optically transparent liver tissue phantom were investigated using a high speed camera and a passive cavitation detection systems under a single 10, 50 or 100 ms-long 2, 3.5 or 5 MHz pressure-modulated HIFU pulse with varying peak positive and negative pressure amplitudes from 5 to 89 MPa and −3.7 to −14.6 MPa at the focus. Furthermore, a numerical simulation of 2D nonlinear wave propagation with the presence of a boiling bubble at the focus of a HIFU field was conducted by numerically solving the generalised Westervelt equation. The high speed camera experimental results showed that, with the proposed pressure-modulated shockwave histotripsy, boiling bubbles generated by shockwave heating merged together, forming a larger bubble (of the order of a few hundred micron) at the HIFU focus. This coalesced boiling bubble then persisted and maintained within the HIFU focal zone until the end of the exposure (10, 50, or 100 ms). Furthermore, and most importantly, no violent cavitation clouds which typically appear in boiling histotripsy occurred during the proposed histotripsy excitation (i.e. no shock scattering effect). This was likely because that the peak negative pressure magnitude of the backscattered acoustic field by the boiling bubble was below the cavitation cloud intrinsic threshold. The size of the coalesced boiling bubble gradually increased with the peak pressure magnitudes. In addition, with the proposed method, an oval shaped lesion with a length of 0.6 mm and a width of 0.1 mm appeared at the HIFU focus in the tissue phantom, whereas a larger lesion in the form of a tadpole (length: 2.7 mm, width: 0.3 mm) was produced by boiling histotripsy. Taken together, these results suggest that the proposed pressure-modulated shockwave histotripsy could potentially be used to induce a more spatially localised tissue destruction with a desired degree of mechanical damage through controlling the size and lifetime of a boiling bubble without the shock scattering effect.