Analysis of semibatch emulsion polymerization: role of ultrasound and initiator

In this work semibatch miniemulsion was carried out wherein the effect of free radicals produced by ultrasound and an external addition of initiator was examined. Influence of different variables on polymerization rate and polymer particle size has also been investigated. Over a range of 0-4% (by wt) initiator, the polymerization rate was found to increase over a range of 0.56-1.33 g L⁻¹ min⁻¹. Similarly monomer concentration range (7.2-15 wt.%) changed the polymerization rate from 1.33 to 2.61 g L⁻¹ min⁻¹. Under optimum parametric conditions polymer particle size 50 nm were obtained with a narrow size distribution. Syndiotactic phase of PMMA was observed by controlling the formulation recipe. Although, number of reports could be found in the literature [9], [13], [17], [18], [20] and [22] related to batch emulsion polymerization, this experimental data could be useful for the production of large scale monodispersed PMMA latex as all of the scale-up and design parameters have been qualitatively addressed.     

Nano-sized polystyrene prepared using bifunctional vinyl urethane macromonomer in emulsion polymerization

The linear-type bifunctional vinyl urethane macromonomer (L-VUM: Mw; 40,453) was synthesized and applied to emulsion polymerization of styrene in DDI water. The structure of L-VUM was confirmed using ¹H NMR and FT-IR. The macromonomer served as a good nonionic surfactant resulted in stable polystyrene nanospheres. Polystyrene particles were prepared with various concentrations of macromonomoer (1–30 wt% refer to monomer), initiator (0.5–2 wt%) and different temperatures (60–80 °C). Monodisperse PS nanospheres with 30 wt% L-VUM have a number-average diameter (D_n) of 200 nm with good uniformity (1.011) and molecular weight (M_w) 231,180 g/mol. The particle morphology, molecular weight and distribution, uniformity and the stability of the nanospheres upon the reaction temperature and concentration of L-VUM will be thoroughly discussed.     

Synthesis of sub-micronic and nanometric PMMA particles via emulsion polymerization assisted by ultrasound: Process flow sheet and characterization

PMMA particle synthesis was performed from MMA (methyl methacrylate) and water mixtures, exposed to different ultrasonic systems and frequencies. The sonication sequence was 20 kHz → 580 kHz → 858 kHz → 1138 kHz, and the solution was sampled after each irradiation step for polymerization. Effects of sonication parameters (time, power), polymerization method (thermo-initiated or photo-initiated), use of small amounts of surfactant (Triton X-100™ or Tween® 20) and initial MMA quantity were investigated on particle size and synthesis yields. Particle size and size distribution were measured by DLS (Dynamic Light Scattering), and confirmed via SEM (Scanning Electron Microscopy) images. Synthesis yield was calculated using the dry weight method. Particle composition was estimated using FTIR (Fourier Transform Infra-Red) spectroscopy. PMMA (polymethylmethacrylate) monodispersed particles were successfully synthesized, with a possibility of control in the 78–310 nm size range. These sized-controlled particles were synthesized with a 7.5–85% synthesis yield (corresponding to 7.5–40 g/L particle solid content), depending on operational parameters. Furthermore, a trade-off between particle size and synthesis yield can be proposed: 20 kHz → 10 min waiting time → 580 kHz → 858 kHz leading to 90 nm particles diameter with 72% yield in less than 40 min for the whole sequence. Thus, the synthesis under ultrasound can be found easy to implement and time efficient, ensuring the success of the scale-up approach and opening up industrial applications for this type of polymeric particles.     

Synergic effects of ultrasound and ionic liquids on fluconazole emulsion

The aim of this work was to evaluate the influence of US on the properties of the fluconazole emulsions prepared using imidazolium-based ILs ([C_n C₁im]Br). The effects of the preparation method (mechanical stirring or US), US amplitude, alkyl chain length (of [C₁₂C₁im]Br or [C₁₆C₁im]Br), and IL concentration on the physicochemical properties were evaluated. Properties such as droplet size, span index, morphology, viscosity encapsulation efficiency, and drug release profile were determined. The results showed that US-prepared emulsions had a smaller droplet size and smaller polydispersity (Span) than those prepared by mechanical stirring. Additionally, the results showed that emulsions prepared with [C₁₆C₁im]Br and US had spherical shapes and increased stability compared to emulsions prepared by MS, and also depended on the IL concentration. The emulsion prepared by US at 40% amplitude had increased encapsulation efficiency. US provided a decrease in the viscosity of emulsions containing [C₁₂C₁im]Br; however, in general, all emulsions had viscosity close to that of water. Emulsions containing [C₁₆C₁im]Br had the lowest viscosities of all the emulsions. The emulsions containing the IL [C₁₆C₁im]Br had more controlled release and a lower cumulative percentage of drug release. The IL concentration required to prepare these emulsions was lower than the amount of conventional surfactant required, which highlights the potential synergic effects of ILs and US in preparing emulsions of hydrophobic drugs.     

High-intensity ultrasound modified the functional properties of Neosalanx taihuensis myofibrillar protein and improved its emulsion stability

This study aimed to investigate the effects of high-intensity ultrasound treatment on the functional properties and emulsion stability of Neosalanx taihuensis myofibrillar protein (MP). The results showed that the carbonyl groups, emulsification properties, intrinsic fluorescence intensity, and surface hydrophobicity of the ultrasound treated MP solution were increased compared to the MP without ultrasound treatment. The results of secondary structure showed that the ultrasound treatment could cause a huge increase of β-sheet and a decline of α-helix of MP, indicating that ultrasound induced molecular unfolding and stretching. Moreover, ultrasound reduced the content of total sulfhydryl and led to a certain degree of MP cross-linking. The microscopic morphology of MP emulsion indicated that the emulsion droplet decreased with the increase of ultrasound power. In addition, ultrasound could also increase the storage modulus of the MP emulsion. The results for the lipid oxidation products indicated that ultrasound significantly improved the oxidative stability of N. taihuensis MP emulsions. This study offers an important reference theoretically for the ultrasound modification of aquatic proteins and the future development of N. taihuensis deep-processed products represented by surimi.     

Alternate pulses of ultrasound and electricity enhanced electrochemical process for p-nitrophenol degradation

A novel alternated ultrasonic and electric pulse enhanced electrochemical process was developed and used for investigating its effectiveness on the degradation of p-nitrophenol (PNP) in an aqueous solution. The impacts of pulse mode, pH, cell voltage, supporting electrolyte concentration, ultrasonic power and the initial concentration of PNP on the performance of PNP degradation were evaluated. Possible pathway of PNP degradation in this system was proposed based on the intermediates identified by GC–MS. Experimental results showed that 94.1% of PNP could be removed at 2 h in the dual-pulse ultrasound enhanced electrochemical (dual-pulse US-EC) process at mild operating conditions (i.e., pulse mode of electrochemical pulse time (T_EC) = 50 ms and ultrasonic pulse time (T_US) = 100 ms, initial pH of 3.0, cell voltage of 10 V, Na₂SO₄ concentration of 0.05 M, ultrasonic powder of 48.8 W and initial concentration of PNP of 100 mg/L), compared with 89.0%, 58.9%, 2.4% in simultaneous ultrasound enhanced electrochemical (US-EC) process, pulsed electrochemical (EC) process and pulsed ultrasound (US), respectively. Moreover, energy used in the dual-pulse US-EC process was reduced by 50.4% as compared to the US-EC process. The degradation of PNP in the pulsed EC process, US-EC process and dual-pulse process followed pseudo-first-order kinetics. Therefore, the dual-pulse US-EC process was found to be a more effective technique for the degradation of PNP and would have a promising application in wastewater treatment.     

Low oil emulsion gel stabilized by defatted Antarctic krill (Euphausia superba) protein using high-intensity ultrasound

Emulsion gels with low oil contents have been continuously developed in recent decades. In this study, the use of high-intensity ultrasound for the preparation of low oil emulsion gel (oil fraction of 0.25) was investigated. Specifically, defatted Antarctic krill protein (dAKP) was used to stabilize the interface of soybean oil and water. Then, the microstructure and the stabilization mechanism of the formed emulsion gel were evaluated by cryo-SEM, CLSM, zeta potential, rheological measurements, and FTIR. Besides, the particle diameter was measured to be around 5 μm. The results of CLSM indicated that the emulsion gel was the oil-in-water type. The emulsion gel exhibited gel-like viscoelastic behavior even at a low concentration of dAKP due to the formation of a rigid particle network while the rheological behavior of the emulsion gel was significantly affected by the concentration of dAKP. The stabilization of the emulsion gel can be maintained by space steric hindrance and hydrophobic interactions between particles in the emulsion gel system.     

Degradation of nitrobenzene in aqueous solution by dual-pulse ultrasound enhanced electrochemical process

The present work reports a novel dual-pulse ultrasound enhanced electrochemical degradation (US-ECD) process that synchronizes alternatively ultrasound pulses and potential pulses to degrade nitrobenzene in aqueous solution with a high percentage degradation and low energy consumption. In comparison to the test results generated from the conventional US-ECD and original electrochemical degradation (ECD) process, the dual-pulse US-ECD process increased degradation percentages to nitrobenzene by 2% and 17%, respectively, while energy used in the pulse process was only about 46.5% of that was used in the conventional US-ECD process. Test results demonstrated a superior performance of the dual-pulse US-ECD process over those of other conventional ones. Impacts of pulse mode, initial pH value, cell voltage, supporting electrolyte concentration and ultrasonic power on the process performances were investigated. With operation conditions optimized in the study at pH = 3.0, cell voltage = 10 V, ultrasonic power = 48.84 W, electrolyte concentration = 0.1 M and an experiment running time of 30 min, the percentage degradation of nitrobenzene could reach 80% (US pulse time = 50 ms and ECD pulse time = 50 ms). This process provided a reliable and effective technical approach to degrade nitrobenzene in aqueous solution and significantly reduced energy consumption in comparison to the conventional US-ECD or original ECD treatment.     

Enhancement of thermal and mechanical properties of poly(MMA-co-BA)/Cloisite 30B nanocomposites by ultrasound-assisted in-situ emulsion polymerization

This study reports synthesis and characterization of poly(MMA-co-BA)/Cloisite 30B (organo-modified montmorillonite clay) nanocomposites by ultrasound-assisted in-situ emulsion polymerization. Copolymers have been synthesized with MMA:BA monomer ratio of 4:1, and varying clay loading (1–5 wt% monomer). The poly(MMA-co-BA)/Cloisite 30B nanocomposites have been characterized for their thermal and mechanical properties. Ultrasonically synthesized nanocomposites have been revealed to possess higher thermal degradation resistance and mechanical strength than the nanocomposites synthesized using conventional techniques. These properties, however, show an optimum (or maxima) with clay loading. The maximum values of thermal and mechanical properties of the nanocomposites with optimum clay loading are as follows. Thermal degradation temperatures: T_10% = 320 °C (4 wt%), T₅₀ = 373 °C (4 wt%), maximum degradation temperature = 384 °C (4 wt%); glass transition temperature = 64.8 °C (4 wt%); tensile strength = 20 MPa (2 wt%), Young’s modulus = 1.31 GPa (2 wt%), Percentage elongation = 17.5% (1 wt%). Enhanced properties of poly(MMA-co-BA)/Cloisite 30B nanocomposites are attributed to effective exfoliation and dispersion of clay nanoparticles in copolymer matrix due to intense micro-convection induced by ultrasound and cavitation. Clay platelets help in effective heat absorption with maximum surface interaction/adhesion that results in increased thermal resistivity of nanocomposites. Hindered motion of the copolymer chains due to clay platelets results in enhancement of tensile strength and Young’s modulus of nanocomposite. Rheological (liquid) study of the nanocomposites reveals that nanocomposites have higher yield stress and infinite shear viscosity than neat copolymer. Nonetheless, nanocomposites still display shear thinning behavior – which is typical of the neat copolymer.     

Effect of ultrasonic power on the emulsion stability of rice bran protein-chlorogenic acid emulsion

In this study, rice bran protein–chlorogenic acid (RBP–CA) emulsion was subjected to an ultrasonic-assisted treatment technique. The encapsulation efficiency and loading capacity of chlorogenic acid (CA), and the morphology, particle size, zeta (ζ)-potential, atomic force microscopy image, viscosity, turbidity, and interfacial protein content of the emulsion under different ultrasonic power were investigated. The results revealed that the emulsion exhibited an encapsulation efficiency and loading capacity of 86.26 ± 0.11% and 17.25 ± 0.06 g/100 g, respectively, at an ultrasonic power of 400 W. In addition, the size of the emulsion droplets decreased and became more evenly distributed. Furthermore, the viscosity of the emulsion decreased significantly, and it exhibited a turbidity and interfacial protein content of 24,758 and9.34 mg/m², respectively. Next, the storage, oxidation, thermal, and salt ion stabilities of the emulsion were evaluated. The results revealed that the ultrasonic-assisted treatment considerably improved the stability of the emulsion.     

Alkaline and ultrasound assisted alkaline pretreatment for intensification of delignification process from sustainable raw-material

Alkaline and ultrasound-assisted alkaline pretreatment under mild operating conditions have been investigated for intensification of delignification. The effect of NaOH concentration, biomass loading, temperature, ultrasonic power and duty cycle on the delignification has been studied. Most favorable conditions for only alkaline pretreatment were alkali concentration of 1.75 N, solid loading of 0.8% (w/v), temperature of 353 K and pretreatment time of 6 h and under these conditions, 40.2% delignification was obtained. In case of ultrasound-assisted alkaline approach, most favorable conditions obtained were alkali concentration of 1 N, paper loading of 0.5% (w/v), sonication power of 100 W, duty cycle of 80% and pretreatment time of 70 min and the delignification obtained in ultrasound-assisted alkaline approach under these conditions was 80%. The material samples were characterized by FTIR, SEM, XRD and TGA technique. The lignin was recovered from solution by precipitation method and was characterized by FTIR, GPC and TGA technique.     

Enzymolysis kinetics and structural characteristics of rice protein with energy-gathered ultrasound and ultrasound assisted alkali pretreatments

This research investigated the structural characteristics and enzymolysis kinetics of rice protein which was pretreated by energy-gathered ultrasound and ultrasound assisted alkali. The structural characteristics of rice protein before and after the pretreatment were performed with surface hydrophobicity and Fourier transform infrared (FTIR). There was an increase in the intensity of fluorescence spectrum and changes in functional groups after the pretreatment on rice protein compared with the control (without ultrasound and ultrasound assisted alkali processed), thus significantly enhancing efficiency of the enzymatic hydrolysis. A simplified kinetic equation for the enzymolysis model with the impeded reaction of enzyme was deduced to successfully describe the enzymatic hydrolysis of rice protein by different pretreatments. The initial observed rate constants (K_in,0) as well as ineffective coefficients (k_imp) were proposed and obtained based on the experimental observation. The results showed that the parameter of k_in,0 increased after ultrasound and ultrasound assisted alkali pretreatments, which proved the effects of the pretreatments on the substrate enhancing the enzymolysis process and had relation to the structure changes of the pretreatments on the substrate. Furthermore, the applicability of the simplified model was demonstrated by the enzymatic hydrolysis process for other materials.     

Numerical assessment of ultrasound supported coalescence of water droplets in crude oil

In this study, a numerical assessment of the coalescence of binary water droplets in water-in-oil emulsion was conducted. The investigation addressed the effect of various parameters on the acoustic pressure and coalescence time of water droplets in oil phase. These include transducer material, initial droplet diameter (0.05–0.2 in), interfacial tension (0.012–0.082 N/m), dynamic viscosity (10.6–530 mPas), temperature (20–100 °C), US (ultra sound) frequency (26.04–43.53 kHz) and transducer power (2.5–40 W). The materials assessed are lead zirconate titanate (PZT), lithium niobate (LiNbO₃), zinc oxide (ZnO), aluminum nitride (AlN), polyvinylidene fluoride (PVDF), and barium titanate (BaTiO₃). The numerical simulation of the binary droplet coalescence showed good agreement with experimental data in the literature. The US implementation at a fixed frequency produced enhanced coalescence (t = 5.9–8.5 ms) as compared to gravitational settling (t = 9.8 ms). At different ultrasound (US) frequencies and transducer materials, variation in the acoustic pressure distribution was observed. Possible attenuation of the US waves, and the subsequent inhibitive coalescence effect under various US frequencies and viscosities, were discussed. Moreover, the results showed that the coalescence time reduced across the range of interfacial tensions which was considered. This reduction can be attributed to the fact that lower interfacial tension produces emulsions which are relatively more stable. Hence, at lower interface tension between the water and crude oil, there was more resistance to the coalescence of the water droplets due to their improved emulsion stability. The increment of the Weber number at higher droplet sizes leads to a delay in the recovery of the droplet to spherical forms after their starting deformation. These findings provide significant insights that could aid further developments in demulsification of crude oil emulsions under varying US and emulsion properties.     

A novel process for asparagus polyphenols utilization by ultrasound assisted adsorption and desorption using resins

The ultrasound assisted purification of asparagus polyphenols by adsorption and desorption on the macroporous resins was investigated. The ultrasound within the selected intensities (12–120 W) and temperatures (25–35 °C) increased the adsorption and desorption capacities of asparagus polyphenols on D101 resins. Higher ultrasound intensity (120 W) and lower temperature (25 °C) benefited the adsorption process and the adsorption capacity of total polyphenols after ultrasound was 3.95 mg/g, which was 2 times than that obtained after shaking at 120 rpm. Meanwhile, ultrasound can significantly shorten the equilibrium time and the adsorption process of asparagus polyphenols could be well described by Pseudo-second order model and Freundlich model. Stereoscopic microscope was first used to investigate the microstructure characterization of resins, indicating that ultrasound mainly enhanced the surface roughness of resins. Interestingly, rutin possessed the highest adsorption capacities and ferulic acid had the highest the desorption capacities among the studied individual polyphenols. The obtained results evidenced on a progressive insight of application of ultrasound assisted resins for purification of asparagus polyphenols.     

Ultrasonically assisted evaluation of the impact of atherosclerotic plaque on the pulse pressure wave propagation: a clinical feasibility study

The purpose of this work was to evaluate ultrasound modality as a non-invasive tool for determination of impact of the degree of the atherosclerotic plaque located in human internal carotid arteries on the values of the parameters of the pulse wave. Specifically, the applicability of the method to such arteries as brachial, common, and internal carotid was examined. The method developed is based on analysis of two characteristic parameters: the value of the mean reflection coefficient modulus |Γ|_a of the blood pressure wave and time delay Δt between the forward (travelling) and backward (reflected) blood pressure waves. The blood pressure wave was determined from ultrasound measurements of the artery’s inner (internal) diameter, using the custom made wall tracking system (WTS) operating at 6.75 MHz. Clinical data were obtained from the carotid arteries measurements of 70 human subjects. These included the control group of 30 healthy individuals along with the patients diagnosed with the stenosis of the internal carotid artery (ICA) ranging from 20% to 99% or with the ICA occlusion. The results indicate that with increasing level of stenosis of the ICA the value of the mean reflection coefficient measured in the common carotid artery, significantly increases from |Γ|_a = 0.45 for healthy individuals to |Γ|_a = 0.61 for patients with stenosis level of 90-99%, or ICA occlusion. Similarly, the time delay Δt decreases from 52 ms to 25 ms for the respective groups. The method described holds promise that it might be clinically useful as a non-invasive tool for localization of distal severe artery narrowing, which can assist in identifying early stages of atherosclerosis especially in regions, which are inaccessible for the ultrasound probe (e.g. carotid sinus or middle cerebral artery).     

Sonochemical approach for synthesis of zinc oxide-poly methyl methacrylate hybrid nanoparticles and its application in corrosion inhibition

Hybrid nanoparticles (HNPs) with zinc oxide and polymethyl metha acrylate (inorganic/ polymer) were synthesized through the exploitation of ultrasound approach. The synthesized HNPs were further characterized employing transmission electron microscopy and x-ray diffraction. ZnO-PMMA based HNPs exhibit excellent protection properties to mild steel from corrosion when gets exposed to acidic condition. Electrochemical impendence spectroscopy (EIS) analysis was accomplished to evaluate the corrosion inhibition performance of MS panel coated with 2 wt% or 4 wt% of HNPs and its comparison with bare panel and that of loaded with only standard epoxy coating., Tafel plot and Nyquist plot analysis depicted that the corrosion current density (I_corr) decreases from 16.7 A/m² for bare material to 0.103 A/m² for 4% coating of HNPs. Applied potential (E_corr) values shifted from negative to positive side. These results were further supported by qualitative analysis. The images taken over a period of time indicated the increase in lifetime of MS panel from 2 to 3 days for bare panel to 10 days for HNPs coated panel, showing that ZnO-PMMA HNPs have potential application in metal protection from corrosion by forming a passive layer.     

超声波在硫化矿发电浸出过程中的应用

本文将超声波作用于闪锌矿、方铅矿、镍精矿的发电浸出过程,采用双电池技术及依文思图研究超声影响发电浸出的作用过程。研究结果表明,超声作用使发电浸出输出电流和电压一定程度地升高,同时金属离子的浸出率也相应得到提高。     

Optimization and comparison of ultrasound/microwave assisted extraction (UMAE) and ultrasonic assisted extraction (UAE) of lycopene from tomatoes

The extracting technology including ultrasonic and microwave assisted extraction (UMAE) and ultrasonic assisted extraction (UAE) of lycopene from tomato paste were optimized and compared. The results showed that the optimal conditions for UMAE were 98 W microwave power together with 40 KHz ultrasonic processing, the ratio of solvents to tomato paste was 10.6:1 (V/W) and the extracting time should be 367 s; as for UAE, the extracting temperature was 86.4 °C, the ratio of the solvents to tomato paste was 8.0:1 (V/W) and the extracting time should be 29.1 min, while the percentage of lycopene yield was 97.4% and 89.4% for UMAE and UAE, respectively. These results implied that UMAE was far more efficient extracting method than UAE.     

Laser assisted ultrasound guided aspiration improves procedure time and reduces number of withdrawals

This study evaluated the performance of in-vitro freehand aspiration of a simulated cyst with ultrasound aspiration guided by a newly designed laser assisted (LA) device. The LA device was equipped with an adjustable light source generating a sector light plane. This laser light plane was parallel to and overlapped the ultrasound acoustical plane, to help with needle positioning. Five operators randomly performed 30 freehand or LA ultrasound guided aspirations of a simulated cyst. The frequency was set at 8 MHz and depth at 4 cm. Procedure time and number of syringe withdrawals were statistically compared before and after using the LA device. Both experienced and inexperienced operators required significantly less time to perform the aspiration and had fewer syringe withdrawals when using the LA device. The LA device provides a reference plane in space, allowing the operator to more accurately position and adjust needle direction. Additional in-vivo testing is required to test the clinical practicability.     

Simulation of phase separation with large component ratio for oil-in-water emulsion in ultrasound field

This paper presents an exploration for separation of oil-in-water and coalescence of oil droplets in ultrasound field via lattice Boltzmann method. Simulations were conducted by the ultrasound traveling and standing waves to enhance oil separation and trap oil droplets. The focus was to the effect of ultrasound irradiation on oil-in-water emulsion properties in the standing wave field, such as oil drop radius, morphology and growth kinetics of phase separation. Ultrasound fields were applied to irradiate the oil-in-water emulsion for getting flocculation of the oil droplets in 420 kHz case, and larger dispersed oil droplets and continuous phases in 2 MHz and 10 MHz cases, respectively. The separated phases started to rise along the direction of sound propagation after several periods. The rising rate of the flocks was significantly greater in ultrasound case than that of oil droplets in the original emulsion, indicating that ultrasound irradiation caused a rapid increase of oil droplet quantity in the progress of the separation. The separation degree was also significantly improved with increasing frequency or irradiation time. The dataset was rearranged for growth kinetics of ultrasonic phase separation in a plot by spherically averaged structure factor and the ratio of oil and emulsion phases. The analyses recovered the two different temporal regimes: the spinodal decomposition and domain growth stages, which further quantified the morphology results. These numerical results provide guidance for setting the optimum condition for the separation of oil-in-water emulsion in the ultrasound field.