Comparison of Eight Classical Lennard-Jones-Based H2 Molecular Models in the Gas Phase at Temperatures and Pressures Relevant to Hydrogen On-Board Storage Tanks.

This work compares eight classical H2 molecular models in the gas phase taken from the existing literature. All models are based on Lennard-Jones (LJ) 12-6 terms for the van der Waals interactions and hence easier to transfer to multiphase molecular simulations than more sophisticated potentials. The H2 potentials tested include one-site, two-site, three-site, and five-site models, with the sites being either the H atoms, the center-of-mass of the H2 molecule, or massless sites. For the multisite models, high-frequency H-H stretching modes can lead to poor equipartition of the kinetic energy, and the timestep for molecular dynamics (MD) simulations should be reduced to maintain a stable numerical integration of the equations of motion. As such, only those models with rigid bonds are considered. In the present case, 600 MD simulations of H2 gas were carried out over a large range of temperatures (-50 to +90 °C) and at densities corresponding to a pressure range of 50 to 2000 bar, which include the operating conditions of on-board storage tanks in hydrogen-fueled vehicles. Most of the models under study were found to reproduce reasonably well the experimental pVT phase diagram as well as the solubility. Discrepancies only became significant at the highest densities tested, and these could be used to rank the different models. All model diffusion coefficients were essentially indistinguishable from experimental results, and as such, kinetically dominated dynamic properties could not be used as a criterion for the choice of model. Among the eight models tested, two of them, i.e., the two-site model of Yang and Zhong and the one-site model derived from Buch performed very well over the range of conditions tested. They represent a good compromise between realism, simplicity, and computational efficiency.

Teachers' and students' perceptions of a sense of community in blended education.

Universities have renewed interest in blended learning in preparation for post-COVID education. However, unsatisfactory social interactions hinder the quality of blended learning, despite its potential for flexible and personalized learning. In this situation, a sense of community would provide essential academic and social benefits. To develop a sense of community among students, we need to further understand students' and teachers' perceptions concerning this subject by exploring their experiences in blended learning. Therefore, we investigated this for three blended courses using a qualitative case study approach. We conducted: (1) classroom observation; (2) document analysis of course content, assignments, and assessments; and (3) individual interviews with teachers (n = 3) and group interviews with students (n = 18). The results showed the main factors that appeared to contribute to sense of community: group learning activities within courses, non-academic and extracurricular activities across courses, and the campus as a physical place integrating academic and social life after COVID. Further, we identified two obstacles: students valued group learning but struggled to manage group dynamics, and despite teachers' efforts to encourage learning autonomy, students viewed teachers as the ultimate authority in the learning process, which strained the student-teacher relationship. Additionally, this study revealed the limitations that digital tools have for promoting sense of community, as students questioned whether these tools have added value for supporting intricate and in-depth conversations. Finally, based on these findings, we provided practical recommendations for the future development of sense of community in blended learning.

High-temperature molecular screening of hybrid polyOAPS-imide networks based on octa(aminophenyl)silsesquioxane for increased thermomechanical resistance.

A new family of hybrid hyper-cross-linked thin films based on inorganic polyhedral oligomeric silsesquioxane (POSS) cages covalently bound with short organic imides has recently been developed using interfacial polycondensation followed by high-temperature imidization. These polyPOSS-imide networks were aimed at gas separations under harsh conditions, but the aliphatic arms of the initial POSS precursor, octa(aminopropyl)silsesquioxane, were found to be a weak link. This work investigates the replacement of the aliphatic arm by a phenyl derivative, octa(aminophenyl)silsesquioxane (OAPS). Although this new precursor is expected to be more thermoresistant, it introduces extra degrees of complexity since the functional -NH2 group on the phenyl ring can either be attached at a meta, a para or an ortho position. In order to avoid a costly programme of synthesis and testing, molecular dynamics (MD) simulations have been used to efficiently screen a large number of candidate structures based on mixtures of the three OAPS isomers, the initial POSS and three organic precursors, the PMDA, 6FDA and ODPA dianhydrides. Following cross-linking at room temperature, twenty-two model networks were further relaxed at the imidization temperature and directly tested under harsh conditions at 300 °C. The screening stage included the characterization of their intercage single-links and double-links, which reinforce the structures, and intracage links, which have the opposite effect. Carrying out the cross-linking reactions to completion significantly improved the resistance to isotropic dilation. The initial POSS as well as the flexible 6FDA and ODPA linkers were found to be prone to large deformations, whereas the orthoOAPS, metaOAPS, paraOAPS and the PMDA linker prevented volume dilations. Upon uniaxial tension, the Young's moduli varied in the order paraOAPS < POSS ≈ metaOAPS < orthoOAPS for the inorganic precursors and in the order 6FDA < ODPA < PMDA for the organic precursors. In all cases, the networks based on either orthoOAPS and/or PMDA displayed superior resistance. Nine polyOAPS-imides were further heated up to 400 °C, i.e. closer to the expected degradation, and re-submitted to isotropic dilations and uniaxial tensions. They confirmed the trends found at 300 °C with no signs of structural collapse. Using OAPS as the inorganic precursor thus significantly reinforces the thermoresistance of these hybrid hyper-cross-linked networks.

Swelling of Poly(methyl acrylate) Brushes in Acetone Vapor.

Sensor platforms can benefit from the incorporation of polymer brushes since brushes can concentrate the analyte near the sensor surface. Brushes that absorb acetone vapor are of particular interest since acetone is an important marker for biological processes. We present a simple procedure to synthesize acetone-responsive poly(methyl acrylate) brushes. Using spectroscopic ellipsometry, we show that these brushes respond within seconds and swell by more than 30% when exposed to acetone vapor. Moreover, quartz crystal microbalance measurements demonstrate that the brushes can be exploited to increase the acetone detection sensitivity of sensors by more than a factor 6. Surprisingly, we find that the swelling ratio of the brushes in acetone vapor is independent of the grafting density and the degree of polymerization of the polymers in the brush. This is qualitatively different from swelling of the same brushes in liquid environments, where the swelling ratio decreases for increasing grafting densities. Yet, it indicates that the brushes are robust and reproducible candidates for implementation in vapor sensor systems.

Synergic Swelling of Interactive Network Support and Block Copolymer Films during Solvent Vapor Annealing.

We report the effect of "interactive" polymer network (PN) supports on the solvent-vapor processing of thin polymer films. Densely cross-linked surface-attached network exhibits under experimental time scale a glassy swelling behavior with the conformational states and solvent-uptake clearly sensitive to the degree of solvent vapor saturation in the atmosphere. Pretreatment of the thermally cured PN films by complete immersion or by swelling in saturated chloroform vapors facilitates relaxation of the residual stresses and induces irreversible changes to the network structure as revealed by the swelling/deswelling tests. The presence of a polymer film on top of the PN support results in a mutual influence of the layers on the respective swelling kinetics, steady-state solvent uptake, and chain dynamics. Using UV-vis ellipsometry, we revealed a significantly faster swelling and higher solvent uptake of glassy PN layer below a polymer film as compared to a single PN layer on silicon substrate. Remarkably, the swelling of the network support continues to increase even when the overall swelling of the bilayer is in a steady-state regime. Block copolymer films on PN supports exhibit a faster ordering dynamics and exceptional stability toward dewetting as compared to similar films on silicon wafers. The mechanical stress produced by continuously swelling PN is suggested to account for the enhanced segmental dynamics even at low solvent concentration in the block copolymer film. Apart from novel insights into dynamics of solvent uptake by heterogeneous polymer films, these results might be useful in developing novel approaches toward fast-processing/annealing of functional polymer films and fibers.

The influence of the dianhydride precursor in hyper-cross-linked hybrid polyPOSS-imide networks.

Hybrid organic/inorganic hyper-cross-linked membranes based on imides covalently bonded with polyhedral oligomeric silsesquioxanes (POSS) have recently been developed for gas-separation applications under high pressure and/or temperature conditions. Their molecular sieving capabilities have been shown to depend on the nature of the organic dianhydride precursor. In the present work, realistic molecular models of such polyPOSS-imide films based on the flexible 6FDA dianhydride are compared to those based on the shorter and more rigid PMDA dianhydride. The models creation procedure closely mimicks the mixing, polycondensation and imidization steps of the experimental scheme. The resulting networks are found to be highly heterogeneous in terms of both the number of links (from zero to the maximum possible of eight per POSS cage with an average of four) and their structure (interPOSS, intraPOSS, single-links, double-links) because of the eight-equivalent-arms nature of the POSS precursor. For both dianhydride precursors, crosslinking with POSS and the subsequent imidization step decrease the density, create additional void-space and increase the solubility of the resulting membranes. However, when compared to PMDA, the added flexibility of the central 6FDA bridge leads to a larger thermally-induced dilation of the networks and a larger volume loss per H2O over the imidization step. With their better ability to redensify and to adapt to the added constraints, the cagecage distances and cage(organic bridge)cage angles in the 6FDA polyPOSS-imides span a larger range than in their PMDA counterparts. In addition, the stiffness of the PMDA moiety results in more unrelaxed free volume remaining trapped in the PMDA polyPOSS-imides upon imidization, and as such, to significantly more open structures with less favourable interactions. As expected from their enhanced flexibility, the thermomechanical properties of the 6FDA networks are slightly lower than those based on PMDA. However, the better mechanical resistance of PMDA over 6FDA does not really become significant before very large volume dilations.

Formation and prevention of fractures in sol-gel-derived thin films.

Sol-gel-derived thin films play an important role as the functional coatings for various applications that require crack-free films to fully function. However, the fast drying process of a standard sol-gel coating often induces mechanical stresses, which may fracture the thin films. An experimental study on the crack formation in sol-gel-derived silica and organosilica ultrathin (submicron) films is presented. The relationships among the crack density, inter-crack spacing, and film thickness were investigated by combining direct micrograph analysis with spectroscopic ellipsometry. It is found that silica thin films are more prone to fracturing than organosilica films and have a critical film thickness of 300 nm, above which the film fractures. In contrast, the organosilica films can be formed without cracks in the experimentally explored regime of film thickness up to at least 1250 nm. These results confirm that ultrathin organosilica coatings are a robust silica substitute for a wide range of applications.

Enzymatically active ultrathin pepsin membranes.

Enzymatically active proteins enable efficient and specific cleavage reactions of peptide bonds. Covalent coupling of the enzymes permits immobilization, which in turn reduces autolysis-induced deactivation. Ultrathin pepsin membranes were prepared by facile interfacial polycondensation of pepsin and trimesoyl chloride. The pepsin membrane allows for simultaneous enzymatic conversion and selective removal of digestion products. The large water fluxes through the membrane expedite the transport of large molecules through the pepsin layers. The presented method enables the large-scale production of ultrathin, cross-linked, enzymatically active membranes.

Sieving of hot gases by hyper-cross-linked nanoscale-hybrid membranes.

Macromolecular networks consisting of homogeneously distributed covalently bonded inorganic and organic precursors are anticipated to show remarkable characteristics, distinct from those of the individual constituents. A novel hyper-cross-linked ultrathin membrane is presented, consisting of a giant molecular network of alternating polyhedral oligomeric silsesquioxanes and aromatic imide bridges. The hybrid characteristics of the membrane are manifested in excellent gas separation performance at elevated temperatures, providing a new and key enabling technology for many important industrial scale applications.

Controlled Localized Metal-Organic Framework Synthesis on Anion Exchange Membranes.

Metal-organic framework (MOF) films can be used in various applications. In this work, we propose a method that can be used to synthesize MOF films localized on a single side of an anion exchange membrane, preventing the transport of the metal precursor via Donnan exclusion. This is advantageous compared to the related contra-diffusion method that results in the growth of a MOF film on both sides of the support, differing in quality on both sides. Our proposed method has the advantage that the synthesis conditions can potentially be tuned to create the optimal conditions for crystal growth on a single side. The localized growth of the MOF is governed by Donnan exclusion of the anion exchange membrane, preventing metal ions from passing to the other compartment, and this leads to a local control of the precursor stoichiometry. In this work, we show that our method can localize the growth of both Cu-BTC and ZIF-8 in water and in methanol, respectively, highlighting that this method can used for preparing a variety of MOF films with varying characteristics using soluble precursors at room temperature.

Nonaqueous Interfacial Polymerization-Derived Polyphosphazene Films for Sieving or Blocking Hydrogen Gas.

A series of cyclomatrix polyphosphazene films have been prepared by nonaqueous interfacial polymerization (IP) of small aromatic hydroxyl compounds in a potassium hydroxide dimethylsulfoxide solution and hexachlorocyclotriphosphazene in cyclohexane on top of ceramic supports. Via the amount of dissolved potassium hydroxide, the extent of deprotonation of the aromatic hydroxyl compounds can be changed, in turn affecting the molecular structure and permselective properties of the thin polymer networks ranging from hydrogen/oxygen barriers to membranes with persisting hydrogen permselectivities at high temperatures. Barrier films are obtained with a high potassium hydroxide concentration, revealing permeabilities as low as 9.4 × 10-17 cm3 cm cm-2 s-1 Pa-1 for hydrogen and 1.1 × 10-16 cm3 cm cm-2 s-1 Pa-1 for oxygen. For films obtained with a lower concentration of potassium hydroxide, single gas permeation experiments reveal a molecular sieving behavior, with a hydrogen permeance of around 10-8 mol m-2 s-1 Pa-1 and permselectivities of H2/N2 (52.8), H2/CH4 (100), and H2/CO2 (10.1) at 200 °C.

Molecular Characterization of Membrane Gas Separation under Very High Temperatures and Pressure: Single- and Mixed-Gas CO2/CH4 and CO2/N2 Permselectivities in Hybrid Networks.

This work illustrates the potential of using atomistic molecular dynamics (MD) and grand-canonical Monte Carlo (GCMC) simulations prior to experiments in order to pre-screen candidate membrane structures for gas separation, under harsh conditions of temperature and pressure. It compares at 300 °C and 400 °C the CO2/CH4 and CO2/N2 sieving properties of a series of hybrid networks based on inorganic silsesquioxanes hyper-cross-linked with small organic PMDA or 6FDA imides. The inorganic precursors are the octa(aminopropyl)silsesquioxane (POSS), which degrades above 300 °C, and the octa(aminophenyl)silsesquioxane (OAPS), which has three possible meta, para or ortho isomers and is expected to resist well above 400 °C. As such, the polyPOSS-imide networks were tested at 300 °C only, while the polyOAPS-imide networks were tested at both 300 °C and 400 °C. The feed gas pressure was set to 60 bar in all the simulations. The morphologies and densities of the pure model networks at 300 °C and 400 °C are strongly dependent on their precursors, with the amount of significant free volume ranging from ~2% to ~20%. Since measurements at high temperatures and pressures are difficult to carry out in a laboratory, six isomer-specific polyOAPS-imides and two polyPOSS-imides were simulated in order to assess their N2, CH4 and CO2 permselectivities under such harsh conditions. The models were first analyzed under single-gas conditions, but to be closer to the real processes, the networks that maintained CO2/CH4 and CO2/N2 ideal permselectivities above 2 were also tested with binary-gas 90%/10% CH4/CO2 and N2/CO2 feeds. At very high temperatures, the single-gas solubility coefficients vary in the same order as their critical temperatures, but the differences between the penetrants are attenuated and the plasticizing effect of CO2 is strongly reduced. The single-gas diffusion coefficients correlate well with the amount of available free volume in the matrices. Some OAPS-based networks exhibit a nanoporous behavior, while the others are less permeable and show higher ideal permselectivities. Four of the networks were further tested under mixed-gas conditions. The solubility coefficient improved for CO2, while the diffusion selectivity remained similar for the CO2/CH4 pair and disappeared for the CO2/N2 pair. The real separation factor is, thus, mostly governed by the solubility. Two polyOAPS-imide networks, i.e., the polyorthoOAPS-PMDA and the polymetaOAPS-6FDA, seem to be able to maintain their CO2/CH4 and CO2/N2 sieving abilities above 2 at 400 °C. These are outstanding performances for polymer-based membranes, and consequently, it is important to be able to produce isomer-specific polyOAPS-imides for use as gas separation membranes under harsh conditions.

Polyoctahedral Silsesquioxane Hexachlorocyclotriphosphazene Membranes for Hot Gas Separation.

There is a need for gas separation membranes that can perform at high temperatures, for example, for CO2 capture in industrial processes. Polyphosphazenes classify as interesting materials for use under these conditions because of their high thermal stability, hybrid nature, and postfunctionalization options. In this work, thin-film composite cyclomatrix polyphosphazene membranes are prepared via the interfacial polymerization reaction between polyhedral oligomeric silsesquioxane and hexachlorocyclotriphosphazene on top of a ceramic support. The prepared polyphosphazene networks are highly crosslinked and show excellent thermal stability until 340 °C. Single gas permeation experiments at temperatures ranging from 50 to 250 °C reveal a molecular sieving behavior, with permselectivities as high as 130 for H2/CH4 at the low temperatures. The permselectivities of the membranes persist at the higher temperatures; at 250 °C H2/N2 (40), H2/CH4 (31) H2/CO2 (7), and CO2/CH4 (4), respectively, while maintaining permeances in the order of 10-7 to 10-8 mol m-2 s-1 Pa-1. Compared to other types of polymer-based membranes, especially the H2/N2 and H2/CH4 selectivities are high, with similar permeances. Consequently, the hybrid polyphosphazene membranes have great potential for use in high-temperature gas separation applications.

Poly(aryl cyanurate)-Based Thin-Film Composite Nanofiltration Membranes.

The successful synthesis of poly(aryl cyanurate) nanofiltration membranes via the interfacial polymerization reaction between cyanuric chloride and 1,1,1-tris(4-hydroxyphenyl)ethane (TPE), atop a polyethersulfone ultrafiltration support, is demonstrated. The use of cyanuric chloride allows for the formation of a polymer that does not contain hydrolysis-susceptible amide bonds that inherently limit the stability of polyamide nanofiltration membranes. In order to achieve a thin defect-free cross-linked film via interfacial polymerization, a sufficient number of each monomer should react. However, the reactivities of the second and third chloride groups of the cyanuric chloride are moderate. Here, this difficulty is overcome by the high functionality and the high reactivity of TPE. The membranes demonstrate a typical nanofiltration behavior, with a molecular weight cutoff of 400 ± 83 g·mol-1 and a permeance of 1.77 ± 0.18 L·m-2 h-1 bar-1. The following retention behavior Na2SO4 (97.1%) > MgSO4 (92.8%) > NaCl (51.3%) > MgCl2 (32.1%) indicates that the membranes have a negative surface charge. The absence of amide bonds in the membranes was expected to result in superior pH stability as compared to polyamide membranes. However, it was found that under extremely acidic conditions (pH = 1), the performance showed a pronounced decline over the course of 2 months. Under extremely alkaline conditions (pH = 13), after 1 month, the performance was lost. After 2 months of exposure to moderate alkaline conditions (pH = 12), the MgSO4 retention decreased by 14% and the permeance increased by 2.5-fold. This degradation was attributed to the hydrolysis of the aryl cyanurate bond that behaves like an ester bond.

Development of Thin-Film Composite Membranes for Nanofiltration at Extreme pH.

Water recycling is one of the most sustainable solutions to growing water scarcity challenges. However, wastewaters usually contain organic pollutants and often are at extreme pH, which complicates the treatment of these streams with conventional membranes. In this work, we report the synthesis of a robust membrane material that can withstand prolonged exposure to extreme pH (of 1 or 13 for 2 months). Polyamine thin film composite (TFC) membranes are prepared in situ by interfacial polymerization between 1,3,5-tris(bromomethyl)benzene (tBrMeB) and p-phenylenediamine (PPD). Contrary to conventional polyamide TFC membranes, enhanced pH stability is achieved by eliminating the carbonyl groups from the polymer network. The membranes showed pure water permeance and molecular weight cutoff (MWCO) of 0.28 ± 0.09 L m-2 h-2 bar-1 and 820 ± 132 g mol-1, respectively. The membrane performance is further enhanced by manipulating the monomer structures and replacing p-phenylenediamine with m-phenylenediamine, resulting in a higher permeance of 1.3 ± 0.3 L m-2 h-1 bar-1 and a lower MWCO of 566 ± 43 g mol-1. Given the ease of fabrication and excellent stability, this chemistry represents a step forward in the fabrication of robust membranes for industrial wastewater recycling.

Sound-driven fluid dynamics in pressurized carbon dioxide.

Using high-speed visualization we demonstrate that ultrasound irradiation of pressurized carbon dioxide (CO(2)) induces phenomena that do not occur in ordinary liquids at ambient conditions. For a near-critical mixture of CO(2) and argon, sonication leads to extremely fast local phase separation, in which the system enters and leaves the two-phase region with the frequency of the imposed sound field. This phase transition can propagate with the speed of sound, but can also be located at fixed positions in the case of a standing sound wave. Sonication of a vapor-liquid interface creates a fine dispersion of liquid and vapor, irrespective whether the ultrasound horn is placed in the liquid or the vapor phase. In the absence of an interface, sonication of the liquid leads to ejection of a macroscopic vapor phase from the ultrasound horn with a velocity of several meters per second in the direction of wave propagation. The findings reported here potentially provide a tunable and noninvasive means for enhancing mass and heat transfer in high-pressure fluids.

Preparation of Ti, Ti/TiC or Ti/TiN based hollow fibres with extremely low electrical resistivity.

Porous Ti based hollow fibres with extremely low electrical resistivity (4.1-9.6 µΩ m), orders of magnitude smaller than reported for Ti-fibres in the literature, were produced by dry-wet spinning of a mixture of Ti-particles, polyethersulfone (PES), and N-methylpyrrolidone (NMP). Utilizing a two-step thermal decomposition of PES, consisting of treatment in air at 475 °C, followed by treatment in argon at 800 °C, hollow fibres of entirely metallic Ti are obtained, as confirmed by XRD, SEM-EDS, and TGA-MS analyses. Only a thin oxide layer is formed due to ambient surface oxidation, as identified by XPS analysis. Carbonization of the polymer under an inert atmosphere can be used to produce a Ti/TiC-composite. To obtain a Ti/TiN composite, the porous Ti-tubes can be treated in nitrogen atmosphere at 800 °C. The porosity, pore size distribution, and bending-strength of the fibres were determined for a low (800 °C) and high (1100 °C) degree of sintering, and it was found that these are largely independent of the chemical surface composition. The presence of TiC or TiN, likely in an outer, but crystalline shell (based on XRD and XPS data), results in lower resistivity than of the pure Ti fibres, which can be attributed to the insulating layer of TiC or TiN preventing capacitive effects at the Ti/air interface. The developed preparation methodology results in porous metallic and composite Ti based fibres, which are very suitable for electrochemical applications.

Relaxation Dynamics of Thin Matrimid 5218 Films in Organic Solvents.

Polyimides are interesting polymer materials for organic solvent nanofiltration (OSN) applications because of their high excess free volume and high chemical and temperature resistance. However, an open challenge that remains for glassy polymer materials (i.e., polyimides) is their tendency to swell in organic solvents which can lead to a loss of performance. An understanding on how swelling influences the polymer properties and performance is then of crucial importance for assessing polyimide suitability in OSN applications. Here, the combination of in situ spectroscopic ellipsometry (iSE), broadband dielectric spectroscopy (BDS), and diffuse reflectance Fourier transform infrared spectroscopy (DRIFT-FTIR) is applied to study the molecular interaction of two organic penetrants, toluene and n-hexane, with Matrimid 5218 in detail. iSE shows that slightly cross-linked Matrimid 5218 swells approximately seven times more in toluene (swelling degree ≈ 28%) compared to in n-hexane (swelling degree ≈ 4%). Combined BDS and DRIFT-FTIR results indicate that toluene interacts with the benzene ring present in the diamine via π-π interactions, while n-hexane likely fills up the excess free volume and interacts via local van der Waals interactions. This work highlights the insights into the exact nature of the molecular interactions between the penetrant and polymer that can be gained from a combination of BDS and other techniques and how these insights can be used to estimate or understand solvent-induced swelling of polymers used in OSN applications.

Triple-Layer Nanofiber Membranes for Treating High Salinity Brines Using Direct Contact Membrane Distillation.

A composite, three-layered membrane for membrane distillation was prepared from electrospun polyvinylidene fluoride (PVDF) nanofibers supported by commercial polyethersulfone (PES) nanofiber based nonwoven from E.I. duPont de Nemours company (DuPont). The membranes were tested in direct contact membrane distillation (DCMD) using a 5.0 M sodium chloride brine as a feed solution. The triple layer membrane combines the hydrophobicity of PVDF and the robustness of the PES. The triple layer membrane demonstrated excellent performance in DCMD (i.e., relatively high water flux compared to the commercial PVDF membrane and a complete salt rejection of the brine) with mechanical properties imparted by the PES layer. This work is the first to demonstrate the use of a commercially produced nanofiber nonwoven for membrane distillation.

Importance of acoustic shielding in sonochemistry.

It is well known that sonochemistry is less efficient at high acoustic intensities. Many authors have attributed this effect to decoupling losses and shielding of the acoustic wave. In this study we investigate both phenomena for a 20 kHz ultrasound field with an intensity ranging from 40 to 150 W/cm2. Visualization of the bubble cloud has demonstrated that the void fraction below the ultrasound horn increases more than proportional with increasing power input. Nevertheless, the energy coupling between the horn and the liquid remains constant; this implies that decoupling losses are not reinforced for larger bubble clouds. On the contrary, microphone measurements have shown that due to the larger bubble cloud a substantial part of the supplied energy is lost at high power inputs. In striving towards more efficient sonochemistry, reduction of shielding appears as one of the major challenges.